JPH05112678A - Flame-retardant resin composition and electric wire coated with the composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in flame retardancy, mechanical properties and flame retardant acceptability, thus suitable for the outdoor materials in the civil engineering/construction industry (e.g. electric wires). CONSTITUTION:The objective composition can be obtained by incorporating (A) 100 pts.wt. of a copolymer <=30 deg.C (pref. <=10 deg.C) in glass transition temperature and 0.005-20dl/g in intrinsic viscosity, produced by copolymerization between (1) a cyclic olefin (e.g. norbornene, 5-methylnorbornene) and (2) an (alpha-olefin (e.g. ethylene, propylene) with (B) 5-250 pts.wt. of a flame retardant (e.g. magnesium hydroxide, tetrabromoethane, trimethyl phosphate), and, if necessary, (C) 1-100 pts.wt. of a thermoplastic elastomer and/or (D) a polyolefin resin. The other objective electric wires can be produced by coating the original wires with this composition.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has excellent flame retardancy and mechanical properties and can be suitably used as various materials in the fields of civil engineering / construction, telecommunications, automobiles / machines, etc. It relates to a flammable resin composition.

[0002]

2. Description of the Related Art In the field of using electric insulating materials made of synthetic resin, various members or outer coating materials, as means for improving the flame retardant properties of the materials used, Various methods are known. Specifically, when the material used is a polyolefin such as polyethylene or polypropylene, it is known to add halogen, phosphorus or an inorganic flame retardant. However, when trying to achieve higher flame retardancy, generally, there is no drastic measure simply by increasing the amount of flame retardant used, and as a result, the flame retardance finally obtained. The resin composition causes a phenomenon that one or more characteristics such as mechanical strength, processability, flexibility and water resistance are remarkably deteriorated.

The applicant of the present invention is a flame-retardant resin composition comprising an ethylene-based copolymer having a specific structure and a flame-retardant filler, which realizes high flame-retardant properties while maintaining high mechanical strength properties. Have already filed an application (Japanese Patent Application Laid-Open No. Sho 6)
4-65148). However, this composition does not necessarily have sufficient elasticity and low temperature characteristics.

Further, in JP-A-2-255848, a cyclic olefin random copolymer (ethylene-cyclic olefin copolymer having a softening temperature of 70 ° C. or higher), a halogen flame retardant, an antimony flame retardant and polytetrafluoroethylene are disclosed. Is disclosed, and a flame-retardant cyclic olefin polymer composition is disclosed, which is said to have excellent mechanical properties and flame retardancy. However, this composition has a high glass transition temperature (Tg) and poor low temperature characteristics.
There are problems that the flexural modulus is high and the applications are limited, and that a large amount of inorganic additives cannot be added.

The present invention has been made in view of the above circumstances and has excellent flame retardancy and mechanical properties, and
A flame-retardant resin composition and a flame-retardant resin coating which have excellent flame-retardant acceptability and can be suitably used as various materials (eg, electric wires) in the fields of civil engineering / construction, telecommunications, automobiles / machines, etc. The purpose is to provide electric wires.

[0006]

In order to achieve the above object, the present invention provides a copolymer (A) obtained by copolymerizing a cyclic olefin and an α-olefin, which has a glass transition temperature (Tg The flame-retardant resin composition comprises 100 parts by weight of a cyclic olefin-based copolymer having a temperature of 30 ° C. or lower, and 5-250 parts by weight of the flame retardant (B). In this case, it is preferable to add 1 to 100 parts by weight of the thermoplastic elastomer (C) to the above composition to prepare a flame-retardant resin composition containing the polyolefin resin (D). Further, the present invention is
Provided is an electric wire coated with the flame-retardant resin composition.

The present invention will be described in more detail below. Component (A) The α-olefin used in the copolymerization of the cyclic olefin-based copolymer that is the component (A) of the composition of the present invention is not necessarily limited, but the following general formula [X] is used.

[Chemical 1] (In the formula [X], R ^a represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). In the repeating unit represented by the above general formula [X], ^Ra represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, isopropyl group, isobutyl group, n-butyl group, n-hexyl group, octyl group, octadecyl group and the like. be able to. Further, specific examples of the α-olefin that gives the repeating unit represented by the general formula [X] include, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1 -Hexene, 1-octene, decene, eicosene and the like can be mentioned.

Further, as the cyclic olefin used for copolymerization of the cyclic olefin copolymer used in the present invention,
Although not necessarily limited, the following general formula [Y]

[Chemical 2] (In the formula [Y], R ^{b to} R ^m are each a hydrogen atom or a carbon number 1
~ 20 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 ¹ or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. ) The cyclic olefins represented by In the cyclic olefin represented by the above general formula [Y], R ^{b to} R ^m are each a hydrogen atom or a carbon number of 1 to 2.
0 represents a hydrocarbon group or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom. Where the carbon number is 1 to
Specific examples of the hydrocarbon group of 20 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, isobutyl group, t-butyl group, hexyl group, and other alkyl groups having 1 to 20 carbon atoms, phenyl group, tolyl group, aryl groups having 6 to 20 carbon atoms, such as benzyl group, alkylaryl groups, or arylalkyl groups C1, methylidene, ethylidene, propylidene, etc.
Examples of the alkenyl group having 2 to 20 carbon atoms such as an alkylidene group, a vinyl group and an allyl group.
However, R ^b , R ^c , R ^f , and R ^{g do not} include an alkylidene group. When any of R ^d , R ^e and R ^{h to} R ^m is an alkylidene group, the carbon atom to which it is bonded has no other substituent.

Specific examples of the substituent containing a halogen atom include halogen groups such as fluorine, chlorine, bromine and iodine, and halogen substitution having 1 to 20 carbon atoms such as chloromethyl group, bromomethyl group and chloroethyl group. An alkyl group etc. can be mentioned. 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 number 1 to 20 such as a methoxycarbonyl group and an ethoxycarbonyl group. Alkoxycarbonyl group and the like can be mentioned. Specific examples of the substituent containing a nitrogen atom 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 represented by the general formula [Y] are, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6
-Trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 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-1,2,3,4,4a, 5 8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 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-1,4,5,5
8-Dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-cyclohexyl-1,
4,5,8-Dimethano-1,2,3,4,4a, 5
8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4
a, 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.

The cyclic olefin copolymer used in the present invention is basically a copolymer of the above-mentioned α-olefin component and cyclic olefin component.
In addition to these two essential components, other copolymerizable unsaturated monomer components may be used, if necessary, within a range that does not impair the object of the present invention. Specific examples of the unsaturated monomer that may be optionally copolymerized include the above α
-Of the olefin components not previously used,
Among the above-mentioned cyclic olefin components, those not previously used, cyclic dienes such as dicyclopentadiene and norbornadiene, butadiene, isoprene,
Examples thereof include chain dienes such as 1,5-hexadiene and monocyclic olefins such as cyclopentene and cycloheptene.

The cyclic olefin copolymer must have a glass transition temperature (Tg) of 30 ° C. or lower. By using such a copolymer, it is possible to obtain a molded article or a covering material that can be suitably used even at low temperatures. A more preferable glass transition temperature (Tg) is 20 ° C. or lower, particularly 10 ° C. or lower. This glass transition temperature (Tg) can be arbitrarily changed by changing the kind and composition of the monomer of the copolymer according to the intended use and the required physical properties.

In the cyclic olefin copolymer used in the present invention, the content rate of the α-olefin repeating unit [x]
The ratio of the content [y] of cyclic olefin repeating units ([x]: [y]) differs depending on the type and combination of α-olefin and cyclic olefin and cannot be generally specified, but is usually 80-99.9 mol%: 20-0.1 mol%, preferably 82-99.5 mol%: 18-0.5 mol%, particularly preferably 85-98
Mol%: 15 to 2 mol%. When the content [x] of the α-olefin repeating unit is less than 80 mol%, the glass transition point and the tensile elastic modulus of the copolymer become high,
The molded product has insufficient impact resistance and elasticity. On the other hand, α-
When the content [x] of the olefin repeating unit exceeds 99.9 mol%, the effect of introducing the cyclic olefin component becomes insufficient.

The cyclic olefin copolymer is a substantially linear copolymer in which α-olefin repeating units and cyclic olefin repeating units are randomly arranged, and does not have a gel-like crosslinked structure. Preferably. It can be confirmed that the copolymer does not have a gel-like crosslinked structure by completely dissolving the copolymer 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 molded product may decrease, and if it exceeds 20 dl / g, the moldability of the copolymer may deteriorate. More preferable 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
And the molecular weight distribution (Mw / Mn) is 1.3.
It is preferable that it is -4, especially 1.4-3. When the molecular weight distribution (Mw / Mn) is greater than 4, the content of low molecular weight substances increases, which may cause surface stickiness when molded into a molded product.

The cyclic olefin-based copolymer preferably has a crystallinity of 0 to 40% as measured by an X-ray diffraction method. If the crystallinity exceeds 40%, the elastic recovery and transparency of the molded product may deteriorate. More preferable crystallinity is 0 to 30%, especially 0 to 25%.

Further, the cyclic olefin copolymer is D
It is preferred that the broad melting peak by SC is below 90 ° C. A copolymer having a sharp melting peak at 90 ° C or higher by DSC has insufficient randomness in the arrangement of cyclic olefins and α-olefins, resulting in insufficient elasticity when molded into a molded product. There is. The broad melting peak by DSC is 10 to 85.
More preferably in the range of ° C. In the DSC measurement, the melting point (melting) peak of the cyclic olefin-based copolymer used in the present invention is not seen sharply, and especially in the case of low crystallinity, it is almost impossible to measure at the ordinary polyethylene measurement condition level. There are no peaks.

The cyclic olefin copolymer used in the present invention preferably has a tensile elastic modulus of less than 2000 Kg / cm ² . Tensile elastic modulus is 2000 kg / cm ²
When it is above, the impact resistance may be insufficient when used for a molded product. More preferable tensile elastic modulus is 50 to
It is 1,500 Kg / cm ² .

The cyclic olefin-based copolymer used in the present invention may be a copolymer having only the physical properties in the above range, and may partially include the copolymer having the physical properties outside the above range. It may be one that has been. In the latter case, all physical property values may be 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 a main component or the following compound (a),
It can be efficiently produced by copolymerizing an α-olefin and a cyclic olefin using a catalyst containing (b) and (c) as a main component. (A) Transition metal compound (b) Compound which reacts with transition metal compound to form an ionic complex (c) Organoaluminum compound

In this case, as the transition metal compound (a), there are IVB group, VB group, VIB group, VIIB group, VI of the periodic table.
Transition metal compounds containing transition metals belonging to Group II can be used. As the above 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 such a transition metal compound include various compounds. Particularly, a compound containing a transition metal of IVB group or VIII group, particularly a transition metal selected from IVB group of the periodic table, that is, titanium (Ti). ), Zirconium (Zr) or hafnium (Hf) is preferably used, and in particular, a cyclopentadienyl compound represented by the following general formula (I), (II) or (III) or a compound thereof A derivative, 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 d R 2 e ... (II) (Cp-A f -Cp) M 1 R 1 d R 2 e ... (III) M ¹ R ¹ _g R ² _h R ³ _i R ⁴ _j (IV)

[In the formulas (I) to (IV), M ¹ is Ti, Zr.
Or Hf atom, Cp is a cyclopentadienyl group,
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 is shown. R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms.
Aryl group, alkylaryl group or arylalkyl group, acyloxy group having 1 to 20 carbon atoms, allyl group, substituted allyl group, σ-bonding ligand such as substituent containing silicon atom, acetylacetonato group, A chelating ligand such as a substituted acetylacetonate group or a ligand such as a Lewis base is shown, and A is a covalent bond.
a, b, and c each represent an integer of 0 to 3, d and e each represent an integer of 0 to 2, f represents an integer of 0 to 6, and g, h, i, and j each represent an integer of 0 to 4. Two or more of R 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. ]

Examples of the substituted cyclopentadienyl group 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,
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like can be mentioned. Specific examples of R ^{1 to} R ⁴ 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, an n-propyl group, and iso as an alkyl group having 1 to 20 carbon atoms.
-Propyl group, n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as alkoxy group having 1 to 20 carbon atoms; aryl group having 6 to 20 carbon atoms, A phenyl group as an alkylaryl group or an arylalkyl group,
Tolyl group, xylyl group, benzyl group; heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group as a substituent containing a silicon atom, (trimethylsilyl) methyl group: dimethyl ether, diethyl ether, tetrahydrofuran as Lewis base , Ethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N,
Amines such as N-dimethylaniline, pyridine, 2,2′-bipyridine, phenanthroline, phosphines such as triethylphosphine and triphenylphosphine; ethylene, butadiene, 1-pentene, isoprene, pentadiene as chain unsaturated hydrocarbons, 1-Hexene and derivatives thereof; examples of cyclic unsaturated hydrocarbons include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of the crosslinks by the covalent bond of A include methylene crosslinks, dimethylmethylene crosslinks, ethylene crosslinks, 1,1′-cyclohexylene crosslinks, dimethylsilylene crosslinks, dimethylgermylene crosslinks, and dimethylstannylene crosslinks.

Examples of such compounds include the following and compounds in which zirconium of these compounds is replaced with titanium or hafnium. Compound 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) dimethyl zirconium,
Bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydride zirconium, bis (cyclopentadienyl) monochloromonohydride zirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

Compounds of the formula (III) ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclo) Pentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [ Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, ethylidene (9-
Fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutyl (9-fluorenyl) (cyclopenta) Dienyl) dimethyl zirconium,
Dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,3)
5-trimethylcyclopentadienyl) dimethyl zirconium, dimethylsilylene bis (indenyl) dichlorozirconium

Other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III), the effects are not impaired. Examples of such compounds include compounds of the formula (IV), for example, tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium,
Tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,
5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate), or these zirconiums with hafnium,
Examples thereof include a zirconium compound having one or more kinds of an alkyl group, an alkoxy group, and a halogen atom such as a compound substituted with titanium, a hafnium compound, and a titanium compound.

The transition metal compound containing a Group VIII transition metal is not particularly limited, and specific examples of the chromium compound include, for example, tetramethyl chromium, tetra (t-butoxy) chromium, bis (cyclopentadienyl). ) Chromium, hydridotricarbonyl (cyclopentadienyl)
Chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) chromium, tris (allyl)
Examples thereof include chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate), and the like.

Specific examples of the manganese compound include 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, dinitrogen bis (bis (tricyclohexylphosphine) nickel), and 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, allyl nickel 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 dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium,
Dichlorobis (triethylphosphine) palladium, bis (t-butyl isocyanide) 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)
Examples include (1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium ditetrafluoroborate, and the like.

As the compound (b), any compound can be used as long as it is a compound which reacts with the transition metal compound (a) to form an ionic complex. A compound composed of a bound anion, particularly a coordination complex compound composed of a cation and an anion in which a plurality of groups are bonded to an element can be preferably used. The compound consisting of such a cation and an anion in which a plurality of groups are bound to an element is represented by the following formula (V) or (VI)
The compound represented by can be preferably used. ([L ¹ −R ⁷ ] ^{k +} ) _p ([M ³ Z ¹ Z ² … Z ⁿ ] ^(nm)- ) _q … (V) ([L ² ] ^{k +} ) _p ([M ⁴ Z ¹ Z ² …. Z ⁿ ] ^(nm)- ) _q (VI) (where L ² is M ⁵ , R ⁸ R ⁹ M ⁶ , R ¹⁰ ₃ C or R ¹¹ M ⁶ )

In the formulas (V) and (VI), L ¹ is a Lewis base, M ³ and M ⁴ are VB group, VIB group and V of the periodic table, respectively.
IIB, VIII, IB, IIB, IIIA, IVA and
Elements selected from the VA group, M ⁵ and M ^6, are IIIB group, IVB group, VB group, VIB group, VIIB group, VIII of the periodic table, respectively.
Element selected from group, IA group, IB group, IIA group, IIB group and VIIA group, Z ^{1 to} Z ⁿ are a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 6 respectively.
To C20 aryloxy group, C1 to C20 alkyl group, C6 to C20 aryl group, alkylaryl group, arylalkyl group, C1 to C20 halogen-substituted hydrocarbon group, C1 to C20 2 represents an acyloxy group, an organic metalloid group or a halogen atom, and two or more of Z ^{1 to} Z ⁿ may be bonded to each other to form a ring. R ⁷
Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 6 to
20 represents an aryl group, an alkylaryl group or an arylalkyl group, R ⁸ and R ⁹ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹⁰ is a C 1-20 group. An alkyl group, an aryl group, an alkylaryl group or an arylalkyl group is shown. R ¹¹ is tetraphenylporphyrin,
A macrocyclic ligand such as phthalocyanine is shown. m is M ³ , M
An integer of 1 to 7 with a valence of ⁴ , n is an integer of 2 to 8, k is an integer of 1 to 7 with an ionic valence of [L ¹ -R ⁷ ], [L ² ],
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amine such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-promo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine Phosphines such as fin, triphenylphosphine and diphenylphosphine,
Examples thereof include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, thioethers such as diethyl thioether and tetrahydrothiophene, and esters such as ethyl benzoate. Specific examples of M ³ and M ⁴ include B, Al, Si, P, As and Sb.
As specific examples of M ⁵ , Li, Na, Ag, Cu, B
Specific examples of M ⁶ , such as r, I, and I ₃ , include Mn, Fe, and C.
o, 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;
Phenoxy group, 2,6-dimethylphenoxy group, naphthyloxy group as aryloxy group having 6 to 20 carbon atoms; methyl group, ethyl group, n-propyl group, iso-propyl group, as alkyl group having 1 to 20 carbon atoms, n-butyl group, n-octyl group, 2-ethylhexyl group; aryl group having 6 to 20 carbon atoms, phenyl group as alkylaryl group or arylalkyl 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, pentachlorophenyl group, 3,4, as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms 5-trifluorophenyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group; F, Cl, Br, I as halogen atom; pentamethylantimony group, trimethylsilyl group, trimethylgel as organic metalloid group Examples thereof include a mil group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. R ⁷ , R ¹⁰
Specific examples of the above include the same as those listed above. Specific examples of the substituted cyclopentadienyl group for R ⁸ and R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group and a pentamethylcyclopentadienyl group. Be done. Here, the alkyl group usually has 1 to 6 carbon atoms,
The number of substituted alkyl groups can be selected as an integer of 1 to 5. Among the compounds of formulas (V) and (VI), M ³ , M ⁴
Is preferably boron.

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

Triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triphenylammonium tetra (pentafluorophenyl) borate, tetrabutylammonium tetra (pentafluorophenyl) borate, Tetra (pentafluorophenyl) borate (tetraethylammonium), tetra (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetra (pentafluorophenyl) borate (benzyltri (n-butyl) ammonium), tetra (pentafluoro) Phenyl) methyl diphenylammonium borate, tetra (pentafluorophenyl) methyl triphenylammonium borate Dimethyl diphenyl (pentafluorophenyl) borate Phenylammonium, anilinium tetra (pentafluorophenyl) borate, methylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, trimethylanilinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) ) Dimethyl borate (m-nitroanilinium), dimethyl tetra (pentafluorophenyl) borate (p-bromoanilinium), pyridinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (p-
Cyanopyridinium), tetra (pentafluorophenyl) borate (N-methylpyridinium), tetra (pentafluorophenyl) borate (N-benzylpyridinium), tetra (pentafluorophenyl) borate (O-cyano-N-methylpyridinium), Tetra (pentafluorophenyl) boric acid (p-cyano-N-methylpyridinium), tetra (pentafluorophenyl) boric acid (p-
Cyano-N-benzylpyridinium), trimethylsulfonium tetra (pentafluorophenyl) borate, benzyldimethylsulfonium tetra (pentafluorophenyl) borate, tetraphenylphosphonium tetra (pentafluorophenyl) borate, tetra (3,5-ditrifluoromethylphenyl) ) Dimethylanilinium borate, triethylammonium hexafluoroarsenate,

Compound of formula (VI) : ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin-manganese), ferrocenium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (1,1′-dimethylferrocenium), decamethylferrocenium tetra (pentafluorophenyl) borate, acetylferrocenium tetra (pentafluorophenyl) borate, formylferrocenium tetra (pentafluorophenyl) borate, tetra Cyanoferrocenium (pentafluorophenyl) borate, silver tetra (pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate,
Lithium tetra (pentafluorophenyl) borate, Sodium tetra (pentafluorophenyl) borate, Tetra (pentafluorophenyl) boric acid (Tetraphenylporphyrin manganese), Tetra (pentafluorophenyl) boric acid (Tetraphenylporphyrin iron chloride), Tetra (penta Fluorophenyl) boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate,

Compounds other than those represented by formulas (V) and (VI) such as tri (pentafluorophenyl) boron and 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 those represented by the following general formula (VII), (VIII) or (IX). R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group or an arylalkyl group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms, Q is a hydrogen atom, It represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is in the range of 1 ≦ r ≦ 3.) Specific examples of the compound of formula (VII) include trimethylaluminum, triethylaluminum, and triisobutyl. Examples thereof include aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride and ethyl aluminum sesquichloride.

[0042]

[Chemical 3] (R ¹² represents the same as in formula (VII). S represents the degree of polymerization, and is usually 3 to 50.) A chain aluminoxane.

[0043]

[Chemical 4] (R ¹² has the same meaning as in formula (VII), s represents the degree of polymerization, and the preferred number of repeating units is 3 to 50.) A cyclic alkylaluminoxane having a repeating unit. Among the compounds of formulas (VII) to (IX),
Preferred are compounds of the formula (VII), particularly preferred are compounds of the formula (VII) with r = 3, and among them, trialkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum.

As a method for producing the aluminoxane, there may be mentioned a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor 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 then brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization and then water is added, water of crystallization contained in a metal salt, etc. , A method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water.

The catalyst used for producing the cyclic olefin-based copolymer is mainly composed of the above-mentioned component (a) and component (b) or the above-mentioned component (a), component (b) and component (c). 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, and particularly 1: 0.
It is preferably 5 to 1:10, and more preferably 1: 1 to 1: 5. The operating temperature is preferably in the range of −100 to 250 ° C., and the pressure and time can be set arbitrarily.

The amount of the component (c) used is usually 0 to 2,000 mol, preferably 5 to 1 mol of the component (a).
The amount is 1,000 mol, particularly preferably 10 to 500 mol. When the component (c) is used, the polymerization activity can be improved, but if it is too much, a large amount of the organoaluminum compound remains in the polymer, which is not preferable. The mode of use of the catalyst is not limited, and for example, the components (a) and (b) may be contacted in advance, or the contact product may be separated and washed before use. May be used.
Further, the component (c) may be used by being brought into contact with a contact product of the component (a), the component (b) or the component (a) and the component (b) in advance. The contact may be made in advance or in the polymerization system. Further, the catalyst component can be added to the monomer or the polymerization solvent in advance, or can be added to the polymerization system.

Polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization may be used. Further, a batch method or a continuous method may be used. Regarding the polymerization conditions, the polymerization temperature is preferably -100 to 250 ° C, particularly preferably -50 to 200 ° C. The ratio of the catalyst to the reaction raw material is 1 to 1 of the raw material monomer / the above component (a) (molar ratio) or the raw material monomer / the above (b) component (molar ratio).
It is preferably 0 ⁹ , and particularly preferably 100 to 10 ⁷ . Further, the polymerization time is usually 1 minute to 10 hours, and the reaction pressure is atmospheric pressure to
100 Kg / cm ² G, preferably normal pressure to 50 Kg / c
m ² G. The method for controlling the molecular weight of the polymer can be based on the amount of each catalyst component used, the selection of the polymerization temperature, and further the polymerization reaction in the presence of hydrogen.

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, fats such as pentane, hexane, heptane and octane. Group hydrocarbons, halogenated hydrocarbons such as chloroform and dichloromethane, and the like can be used. These solvents may be used alone or in combination of two or more. Also, α-
A monomer such as an olefin may be used as a solvent.

Component (B) As the flame-retardant (filler) material which is the component (B) of the composition of the present invention, a known flame-retardant agent can be used in a usual case. , Halogen-based and phosphorus-based. First, as an inorganic metal compound-based flame retardant magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, dolomite, zirconium hydroxide, calcium hydroxide, barium hydroxide, tin oxide hydrate, zinc metaborate, barium metaborate, Tribasic lead sulfate, antimony oxide, tin oxide, zirconium oxide,
Examples thereof include molybdenum oxide, magnesium oxide, barium carbonate, calcium carbonate, zinc carbonate, and basic lead sulfite.

As the halogen-based flame retardant, tetrabromoethane, tetrabromobutane, tetrabromobisphenol A (TBA), hexabromobenzene, decabromodiphenyl ether, tetrabromoethane (TB
E), bromine-based compounds such as tetrabromobutane (TBB) and hexabromocyclodecane (HBCD) and chlorine such as chlorinated paraffin, chlorinated polyphenyl, chlorinated polyethylene, diphenyl chloride, perchloropentacyclodecane and chlorinated naphthalene. Examples thereof include a system, and when used in combination with antimony trioxide or the like, the effect is further enhanced. Further, as the phosphorus-based flame retardant, there are generally phosphate-based, phosphite-based, and phosphonate-based, and specifically, trimethyl phosphate, triethyl phosphate, tributyl phosphate trioctyl phosphate, tributoxy. Ethyl phosphate, octyl diphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate,
Triphenyl phosphate, tri (β-chloroethyl) phosphate, tris- (chloroethyl) phosphate, tris- (2-chloropropyl) phosphate, tris- (2,3-dichloropropyl) phosphate, tris- (2 , 3-Dipropyl) phosphate, tris- (bromochloropropyl) phosphate, bis- (2,3-dibromopropyl) -2,3-dichloropropylphosphate, bis- (chloropropyl) -monooctyl phosphate Examples thereof include phosphates such as polyphosphates and aromatic phosphates or halogenated phosphates.

In the present invention, when the flame retardant (B) is blended with the cyclic olefin copolymer (A), the amount of the cyclic olefin copolymer (A) is 5 to 100 parts by weight relative to the cyclic olefin copolymer.
The amount of the flame retardant is preferably 250 parts by weight, particularly 10 to 200 parts by weight when the main component is an inorganic metal compound-based flame retardant. If the amount of flame retardant (B) is out of this range,
When the compounding amount of is too small, the effect of adding the flame retardant is not sufficiently exerted, and when the compounding amount is too large, the mechanical strength originally possessed as a synthetic resin tends to be lowered. , Was not preferable.

The flame retardant used here is arbitrarily selected from the above-mentioned various substances according to the purpose. The flame retardant used here is appropriately selected from the various types described above and used.
At this time, it is more preferable to use one that has been surface-treated with a material selected from stearic acid, valmitic acid, oleic acid or metal salts thereof, wax, organic silane compound, organic boron compound, organic titanate compound and the like. The result can be played. Further, carbon black or the like may be added to improve flame retardancy.

Component (C) The composition of the present invention comprises (I) a thermoplastic elastomer comprising an α-olefin-based copolymer and a styrene-based copolymer and / or (II) a 1,2-polybutadiene-based thermoplastic elastomer. It is preferable to blend an elastomer. by this,
The elongation and low temperature strength of the molded product can be maintained.

(I) Thermoplastic Elastomer The α-olefin polymer in the thermoplastic elastomer (I) is an amorphous or low crystalline α-olefin copolymer formed from at least two kinds of α-olefins. Polymers such as ethylene / propylene copolymers, propylene / butene-1 copolymers, propylene / isobutylene copolymers, copolymers of ethylene and propylene and dienes, or blends of these polymers, unsaturated carvone Examples thereof include graft polymers and block copolymers in which an acid or a derivative thereof is grafted. The α-olefin polymer is preferably one in which the molar ratio of the comonomer is adjusted so that it becomes a soft resin or a rubber-like resin. Further, styrene or a derivative thereof is used as one of the monomer constituent components and at least one of the glass transition temperatures is 0 ° C.
The following are amorphous to low crystalline copolymers, specifically styrene / isobutylene copolymers, styrene / butadiene copolymers, styrene / butadiene block copolymer rubbers, styrene / butadiene / styrene block copolymers Polymer rubber, styrene / isoprene block copolymer rubber, styrene / isoprolene / styrene block copolymer rubber, hydrogenated styrene / butadiene / styrene block copolymer rubber, hydrogenated styrene / isoprene / styrene block copolymer rubber, styrene -Butadiene random copolymer rubber etc. are mentioned.

(II) 1,2-Polybutadiene-Based Thermoplastic Elastomer The 1,2-polybutadiene-based thermoplastic elastomer has a 1,2-bond content of 90% or more, a molecular weight of 100,000 to several hundreds of thousands, and a crystallinity. Is a low crystallinity thermoplastic elastomer having a syndioctatic structure of 15 to 35%, and particularly one having a rubber-like property with an elongation of 300% or more is used. Specific examples of this elastomer include "JS
R RB805 "," JSR RB810 "," JSR
RB820 "," JSR RB830 "," JSR
RB840 ”, (trade name, made by Japan Synthetic Rubber) and the like. This elastomer has good compatibility with the above-mentioned cyclic polyolefin-based copolymer and forms a uniform composition. The thermoplastic elastomer (I) and / or (II)
The compounding amount is 1 to 100 parts by weight with respect to 100 parts by weight of the cyclic olefin copolymer. If it is less than 1 part by weight, the flame retardance is not improved, and if it exceeds 100 parts by weight, the properties of the base cyclic olefin copolymer are impaired.

Component (D) The resin composition of the present invention further comprises the above (A) to (C).
The polyolefin resin (D) may be blended separately from the components. Examples of the polyolefin resin include ethylene / unsaturated carboxylic acid ester copolymers such as ethylene / vinyl acetate resins, ethylene / propylene copolymers,
Ethylene / butene-1 copolymer, ethylene / octene-
A copolymer selected from the group consisting of 1, etc., a polymer modified with an unsaturated carboxylic acid or a derivative thereof, or
And so on. The blending amount of the polyolefin resin as the component (D) is 1 to 100 parts by weight, preferably 2 to 80 parts by weight, more preferably 3 to 50 parts by weight, based on 100 parts by weight of the cyclic olefin copolymer. ..

Optional components Further , other additives include 2,6-di-t-butylparacresol, phenyl-β-naphthylamine,
Antioxidants represented by lauryl stearyl thiodipropionate, tridecyl phosphite, N-salicyloyl-N'-aldehyde hydrazine, N, N'-diphenyl oxide, 2-hydroxybenzophenone,
Phenyl salicylate, 2-hydroxyphenyl benzotriazole, ethyl-2-cyano-3,3'-diphenyl acrylate, nickel dibutyl dicytocarbamate, and other bis (2,2,6,6,-) known as hindered amines. Tetramethylpiperidinyl-4)
There are ultraviolet absorbers represented by sebacate, various stabilizers, pigments, crosslinking agents, crosslinking aids, foaming agents, nucleating agents and the like.

In order to obtain the flame-retardant resin composition of the present invention, the above-mentioned materials are kneaded by a device known as a usual mixing means such as a Banbury mixer, a single-screw or twin-screw kneader, and a kneader. It can be obtained.

The flame-retardant resin composition thus obtained may then be extruded into a tube or a sheet, or may be extruded into a film using an inflation or T-die method. By using injection molding, rotation molding, compression molding, extrusion coating, press molding, or the like, molding can be performed into a required shape.

The flame-retardant resin composition according to the present invention which can be molded in such a manner is required to have flexibility and flame retardancy, such as electric wires, cables, sealing materials, master batches, packings, hoses, There are various applications such as sheets and films.

Examples of more specific uses are shown below. Electric wire cable: automobile cable, booster cable,
Pump cables, communication cables Civil engineering / construction materials: Water blocking materials, joint materials Home appliances parts: Hoses (washing machines, futon dryers, air conditioners), protectors, connectors, rubber covers, insulators Automotive parts: Exterior parts bumpers, air dam skirts ， Side mall, Mudguard ，
Necking plate, air spoiler interior parts Ceiling material skin, instrument panel pad, door trim skin Others Air duct hose, actuator, lamp housing, weather strip, cable conduit coating

Next, the electric wire of the present invention will be described. The electric wire of the present invention is coated with the flame-retardant resin of the present invention.
The method for coating the electric wire is not particularly limited, but an extruder is usually used. The electric wire includes both single wire and double wire. A single-screw extruder is generally used as the extruder body. The procedure of coating the electric wire with this extruder will be described. First, the conductor or strand to be resin-coated is introduced into the crosshead of the extruder. On the other hand, the coating resin (composition) is supplied from the hopper into the cylinder, is melted by the heat applied from the circumference of the cylinder while being pushed forward by the screw, and is sent to the crosshead. The tip of the crosshead is provided with a die (female) and a nipple (male) as thickness-regulating dies for applying a coating with a predetermined thickness. Extrusion is provided between the nipple and the die. Then, the conductor or the wire is coated with the resin.

The resin-coated electric wire has a wide variety of uses, and examples thereof include communication cables, electric power cables, and indoor / outdoor covered wires.

[0064]

EXAMPLES Next, the present invention will be illustrated concretely by examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, physical properties were measured as follows. Mw, Mn, Mw / Mn Waters ALC / GPC-1 [column; Tosoh TSK GMH-6 × 2], solvent; 1,2,4-trichlorobenze, temperature; 135 ° C., measured in terms of polyethylene. Intrinsic viscosity [η] Measured in decalin at 135 ° C. Norbornene content From the ratio of the sum of the peaks due to ¹³ C-NMR around 30 ppm due to ethylene and the peaks due to methylene at the 5 and 6 positions of norbornene and the peak due to methylene groups at 7 position of norbornene near 32.5 ppm. I asked. Vibron II manufactured by Toyo Boulding Co., Ltd. as a glass transition temperature (Tg) measuring device
EA type, width 4mm, length 40mm, thickness 0.1m
The measurement piece of m was measured at a temperature rising rate of 3 ° C./min and a frequency of 3.5 Hz, and the loss elastic modulus (E ″) at this time was obtained. Melting point (Tm) Perkin Elmer 7 series DSC 1
It measured in the range of -50 degreeC-150 degreeC with the temperature rising rate of 0 degreeC / min. Reference Example 1 (1) Preparation of Ferrocenium Tetra (pentafluorophenyl) borate 20 mmol of ferrocene (Cp ₂ Fe) and concentrated sulfuric acid 40
The solution was reacted with milliliter at room temperature for 1 hour to obtain a dark blue solution. This solution was added to 1 liter of water and stirred, and the obtained deep blue aqueous solution was added to 500 ml of an aqueous solution of 20 mmol of lithium tetra (pentafluorophenyl) borate. The pale blue solid that has precipitated is filtered off and washed with water 5
After washing 5 times with 00 ml and drying under reduced pressure, the desired product ferrocenium tetra (pentafluorophenyl) borate ([Cp ₂ Fe] [B (C
₆ F ₅ ) ₄ ]) 17 mmol was obtained.

(2) Copolymerization of ethylene and 2-norbornene In a nitrogen atmosphere, at room temperature, in a 30 liter autoclave, 15 liters of toluene, 23 mmol of triisobutylaluminum (TIBA), 0.075 mmol of biscyclopentadienylzirconium dichloride were added. , Tetra (pentafluorophenyl) prepared in (1) above
Ferrocenium borate (0.15 mmol) was added in this order, and then 1.5 liters of a toluene solution containing 70% by weight of 2-norbornene (10 parts as 2-norbornene was added).
Mol) was added and the temperature was raised to 90 ° C., and then the reaction was carried out for 110 minutes while continuously introducing ethylene so that the ethylene partial pressure became 7 kg / cm ² . After the reaction was completed, the polymer solution was put 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-based copolymer (a1) was 2.84 Kg. The polymerization activity was 415 Kg / gZr.

The obtained cyclic olefin copolymer (a
The physical properties of 1) were as follows. 30 of ¹³ C-NMR
The sum of the peaks based on ethylene and the peaks based on methylene at the 5th and 6th positions of norbornene appearing around ppm and 3
The norbornene content calculated from the ratio with the peak based on the methylene group at the 7-position of norbornene appearing at around 2.5 ppm was 7.0 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.23 dl / g, and the crystallinity determined by X-ray diffractometry was 1.0%. As a measuring device, a Toyo Boulding Co., Ltd. Bybaron 11-EA type is used, and a measuring piece having a width of 4 mm, a length of 40 mm and a thickness of 0.1 mm is 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 loss elastic modulus (E ″) of Tg was 3 ° C. ALC / OPC150C manufactured by Waters was used as a measuring device, and 1,2,4-trichlorobenzene solvent was used. , 135 ° C
Then, when the weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution (Mw / Mn) were calculated in terms of polyethylene,
Mw is 54,200, Mn is 28,500, Mw / Mn
= 1.91. Perkin Elmer 7 series DSC at a temperature rising rate of 10 ° C./min.
The melting point (Tm) was measured in the range of 150 ° C.
Was 73 ° C. (broad peak) ° C.

Reference Example 2 A cycloolefin copolymer (a2) was obtained in the same manner as in Reference Example 1 except that the amount of 2-norbornene used in Reference Example 1 (2) was 7.5 mol. .. The yield of the cyclic olefin-based copolymer (a2) was 2.93 Kg, and the polymerization activity was 428 Kg / gZr. Further, the norbornene content determined in the same manner as in Reference Example 1 was 4.9 mol%, the intrinsic viscosity [η] was 1.22 dl / g, the glass transition temperature (Tg) was −7 ° C., Mw was 72,400, Mn. Is 36,400, M
The w / Mn was 1.99 and the melting point (Tm) was 84 ° C. (broad peak).

Reference Example 3 In (2) of Reference Example 1, the amount of biscyclopentadienyl zirconium dichloride used was 0.064 mmol, the amount of ferrocenium tetra (pentafluorophenyl) borate used was 0.11 mmol, and A cycloolefin copolymer (a3) was obtained in the same manner as in Reference Example 1, except that the amount of norbornene used was 7.5 mol, the polymerization temperature was 70 ° C., and the ethylene partial pressure was 9 Kg / cm ² . The yield of the cyclic olefin-based copolymer (a3) was 2.36 Kg, and the polymerization activity was 460 Kg / gZr. The norbornene content determined in the same manner as in Reference Example 1 was 4.5 mol%, the intrinsic viscosity [η] was 3.07 dl / g, and the glass transition temperature (T
g) is -8 ° C, Mw is 213,000, Mn is 114,
000, Mw / Mn 1.87, melting point (Tm) 81 ° C.
(Broad peak).

Examples 1 to 7 and Comparative Examples 1 to 2 As shown in Table 1, 100 parts by weight of the cycloolefin copolymers (a1) to (a3) obtained in Reference Examples 1 to 3 were difficult to obtain. A flame retardant (magnesium hydroxide: Mg (OH) ₂ : N-1 manufactured by Kamishima Chemical Co., Ltd.) was mixed and kneaded under the following kneading conditions to obtain pellets of a flame-retardant resin composition. Kneading conditions (1) Kneading machine: Twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd.) (2) Screw shape: 2 reverse types, L / D = 31.30
φ, double thread (3) Screw rotation direction: same direction, rotation speed: 150r
pm (4) Resin temperature: 185 ° C. Resin pressure: 23 kg / cm ² Discharge rate: 4.3 kg / hr Then, using an pellet made of the above flame retardant resin composition, an injection molding machine (manufactured by Toshiba Machine Co., Ltd.) : IS80EP)
In this way, injection molding was performed under the conditions of a set temperature of 280 ° C., a mold temperature of 50 ° C., and an injection pressure of 1040 Kg / cm ² to obtain a molded product (70 mm × 70 mm × 2 mm). Using the above pellets, an extruder (L / D = 22) was used to extrude and coat a conductor having a core wire outer diameter of 1.8 mmφ with a 10 μm paper separator in a thickness of 1.8 mm to obtain a coated electric wire. It was The results of measuring the flame retardancy (oxygen index, vertical combustion test) and mechanical properties such as tensile elongation at break, tensile strength at break, tensile modulus and shore hardness of the obtained molded product are shown in Table 1.
Shown in.

The measurement of each item was carried out as follows. Tensile elastic modulus: JIS-K7113 using autograph
According to. Tensile breaking strength: JIS-K711 using autograph
Was performed according to 3. Tensile breaking elongation: JIS-K711 using autograph
Was performed according to 3. Oxygen index: Performed according to JIS-K7201. Shore hardness (D): Measured according to JIS-K7215. Vertical combustion test: Conducted in accordance with uL44, and those having a burning time of 60 seconds or less were judged to be acceptable, and those having a combustion time of more than 60 seconds were judged to be unacceptable. As is clear from Table 1, even if the flame-retardant resin composition of the present invention (Examples 1 to 5) contains a flame retardant in the cyclic olefin copolymer in order to improve flame retardancy, It can be seen that the mechanical properties such as tensile elongation at break of the molded product can be maintained.

[0071]

[Table 1]

[0072]

As described above, the flame-retardant resin composition of the present invention has excellent flame retardancy and mechanical properties, and is used as a material for outdoor materials in the fields of civil engineering / construction and telecommunications. Can be suitably used as. In addition, an electric wire coated with the flame-retardant resin composition has excellent properties.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location C08L 101/00 LSY 7167-4J H01B 3/44 B 9059-5G // H01B 7/34 B 7244-5G

Claims (4)

[Claims] 1. A copolymer obtained by copolymerizing (A) a cyclic olefin and an α-olefin, wherein 100 parts by weight of a cyclic olefin copolymer having a glass transition temperature (Tg) of 30 ° C. or lower. And (B) 5 to 250 parts by weight of a flame retardant, a flame retardant resin composition. 2. (C) Thermoplastic elastomer 1 to 100
The flame-retardant resin composition according to claim 1, wherein parts by weight are blended. 3. The flame-retardant resin composition according to claim 1, which further comprises (D) a polyolefin resin. 4. An electric wire coated with the flame-retardant resin composition according to claim 1.