JP2939520B2 - Textile - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an excellent hydrolysis resistance,
The present invention relates to a polyolefin-based fiber which has light resistance, chemical resistance, and elasticity and can be effectively used in various fields such as a garment field and an industrial field.

[0002]

2. Description of the Related Art Conventionally, synthetic fibers have been used in various fields such as clothing and industry. Among them, polyurethane fibers are widely used in the field of garments due to their excellent elasticity, and various denier yarns are produced in the field of clothing, for example, for socks, swimwear, leotards, body suits, girdle, cords and the like. Have been. However, while polyurethane fibers have excellent properties, they are disadvantageous in that they are easily susceptible to hydrolysis because they are high molecular substances composed of isocyanate bonds, and have problems in hot water resistance, light resistance, and chemical resistance. Have.
For example, clothes sewn with polyurethane fibers do not always have sufficient dry cleaning resistance. Due to such drawbacks, polyurethane fibers have not been sufficiently used for industrial purposes.

[0003] On the other hand, polyolefin fibers are not subjected to hydrolysis and are used for industrial purposes and miscellaneous goods. However, polyolefin-based fibers have a drawback that they do not have elastic recovery (elasticity). Therefore, the fields of use of polyolefin-based fibers are limited, and they are not widely used in the field of clothing. The present invention has been made in view of the above circumstances, and is excellent in hydrolysis resistance, light resistance, chemical resistance, and elasticity, and therefore can be suitably used in various fields such as clothing and industry. It is an object of the present invention to provide a polyolefin-based fiber that can be used.

[0004]

Means for Solving the Problems In order to achieve the above object, the fiber of the present invention is a fiber using a cyclic olefin copolymer obtained by copolymerizing a cyclic olefin and an α-olefin, a) The glass transition point (Tg) is set to a value of 50 ° C. or less. (b) The content of the repeating unit derived from the α-olefin is [X], and the content of the repeating unit derived from the cyclic olefin is [Y] and [X]:
The ratio of [Y] is in the range of 70 to 99.8 mol%: 30 to 0.2 mol%, and (c) formed from a cyclic olefin-based copolymer soluble in decalin at 135 ° C. I have.

Hereinafter, the present invention will be described in more detail.
The fiber of the present invention comprises a cyclic olefin-based copolymer obtained by copolymerizing a cyclic olefin and an α-olefin. Here, although it does not necessarily limit as said alpha-olefin, 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, Examples include an octyl group and an octadecyl group. Specific examples of the α-olefin that provides a 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.

The cyclic olefin is not particularly limited, but has 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, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom. .

Here, specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and the like. An alkyl group having 1 to 20 carbon atoms such as a hexyl group, an aryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a benzyl group, an alkylaryl group or an arylalkyl group, a methylidene group, an ethylidene group, a propylidene group; Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as an alkylidene group having 1 to 20 carbon atoms, a vinyl group and an allyl group. ^{However, R b, R c, R} f, R g excluding an alkylidene group. When any one of R ^d , R ^e , and R ^{h to} R ^m is an alkylidene group, the carbon atom to which it is bonded has no other substituent.

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

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

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 needs to have a glass transition temperature (Tg) of 50 ° C. or less. When such a copolymer is used, the glass transition temperature (Tg)
At the above temperature, there is an effect that a fiber which is soft and has excellent elastic recovery can be obtained. A more preferred glass transition temperature (Tg) is 30 ° C. or less, particularly 20 ° C.
It is as follows. The glass transition temperature (Tg) can be arbitrarily changed by changing the type and composition of the monomer of the copolymer according to the intended use and required physical properties.

In the cyclic olefin copolymer used in the present invention, the ratio of the content [x] of the repeating unit derived from α-olefin and the content [y] of the repeating unit derived from cyclic olefin ([x]: [Y]) differs depending on the type and combination of the α-olefin and the cyclic olefin, and cannot be generally specified, but is usually 70 to 99.8 mol%: 30 to 0.2 mol%, preferably 80 to 99 mol%: 20 to 1 mol%. When the content of the cyclic olefin repeating unit [y] is more than 30 mol% or less than 0.2 mol%, the elastic recovery of the fiber may be 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, there is. The absence of a gel-like crosslinked structure can be confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C.

The cyclic olefin copolymer has an intrinsic viscosity [η] of 0.005 to 2 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 fiber may decrease, and if it exceeds 20 dl / g, the moldability into the fiber may deteriorate. More preferred intrinsic viscosity [η] is 0.05 to 10 dl / g.

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

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 fiber may decrease. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.

Further, the cyclic olefin copolymer is D
Preferably, the broad melting peak by SC is below 90 ° C. Copolymers whose DSC has a sharp melting peak at 90 ° C. or higher may have insufficient randomness in the arrangement of cyclic olefin and α-olefin and insufficient elasticity when formed into fibers. is there. The broad melting peak by DSC was 10-85.
More preferably, it is 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 sharply observed. No peak.

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

The cyclic olefin copolymer used in the present invention may be a copolymer consisting of only those having 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 former case, it may be a mixture of copolymers having different Tg whose glass transition temperature (Tg) is 50 ° C. or lower. 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) is selected from the group 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.

Such transition metal compounds include various compounds. In particular, compounds containing a transition metal of Group IVB or VIII, particularly a transition metal selected from Group IVB of the periodic table, ie, titanium (Ti) ), A compound containing zirconium (Zr) or hafnium (Hf) can be suitably used, and in particular, a cyclopentadienyl compound represented by the following general formula (I), (II) or (III) or 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,
It represents a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. R ¹ , R ² , R ³ and R ⁴ each represent a σ-binding ligand, a chelating ligand, or a ligand such as a Lewis base. 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, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, an acyloxy group having 1 to 20 carbon atoms, Allyl group,
Examples of the substituent include a substituted allyl group and a substituent containing a silicon atom.
Examples of the chelating ligand include an acetylacetonate group and a substituted acetylacetonate group. A represents a crosslink by a covalent bond. a, b, and c are each an integer of 0 to 3, d and e are each an integer of 0 to 2, f is an integer of 0 to 6, g, h, i, and j are each 0.
Shows an integer of ~ 4. Two or more of R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. The above Cp
Has a substituent, the substituent has 1 to 2 carbon atoms.
An alkyl group of 0 is preferred. 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. 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 an iso group as an alkyl group having 1 to 20 carbon atoms.
-Propyl group, n-butyl group, octyl group, 2-ethylhexyl group; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group as an alkoxy group having 1 to 20 carbon atoms; an 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, (trimethylsilyl) methyl group as a substituent containing a silicon atom: dimethyl ether, diethyl ether, tetrahydrofuran as a 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 and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; and linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof; cyclic unsaturated hydrocarbons include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of the crosslink by the covalent bond of A include a methylene crosslink, a dimethylmethylene crosslink, an ethylene crosslink, a 1,1′-cyclohexylene crosslink, a dimethylsilylene crosslink, a dimethylgermylene crosslink, and a dimethylstannylene crosslink.

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

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

Compound of Formula (III) Ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) dichloro zirconium, ethylene bis (tetrahydroindenyl) dimethyl zirconium, ethylene bis (tetrahydroindenyl) dichloro zirconium, dimethylsilylene bis (cyclo Pentadienyl) dimethyl zirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [ Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethyl zirconium, ethylidene (9-
Fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclobutyl (9-fluorenyl) (cyclopentane Dienyl) dimethyl zirconium,
Dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3
5-trimethylcyclopentadienyl) dimethyl zirconium, dimethylsilylenebis (indenyl) dichlorozirconium

The compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) do not impair the effects. Examples of such compounds include compounds of formula (IV) above, for example, tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrachloro zirconium,
Tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2
5-di-t-butylphenoxy) dimethyl zirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate), or hafnium,
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 replaced with titanium.

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

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

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

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

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

In the formulas (V) and (VI), L ¹ is a Lewis base, and M ³ and M ⁴ are VB group, VIB group and V
IIB, VIII, IB, IIB, IIIA, IVA and
Element selected from Group VA, IIIB group of M ⁵ and M ^6, respectively Periodic Table, IVB group, VB group, VIB group, VIIB group, VIII
Family, 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 carbon atoms
Aryloxy group having 20 to 20 carbon atoms, 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, 1 to 20 carbon atoms an acyloxy group, an organic metalloid 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; k is an integer of 1 to 7 as 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
Etc., Li Specific examples of ^{M 5, Na, Ag, Cu} , B
r, I, I _3, etc., Mn Specific examples of M ^6, Fe, C
o, Ni, Zn and the like. Z ¹ Specific examples of the to Z ^n, for example, dimethylamino group as a dialkylamino group, a diethylamino group; methoxy group as alkoxy group having 1 to 20 carbon atoms, an ethoxy group, n- butoxy group;
A phenoxy group, 2,6-dimethylphenoxy group, naphthyloxy group as an aryloxy group having 6 to 20 carbon atoms; a methyl group, an ethyl group, an n-propyl group, an iso-propyl group as an alkyl group having 1 to 20 carbon atoms; n-butyl group, n-octyl group, 2-ethylhexyl group; phenyl group, p-tolyl group, benzyl group, 4-tert-butylphenyl group as an aryl group, alkylaryl group or arylalkyl group having 6 to 20 carbon atoms , 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, 5-trifluorophenyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group; F, Cl, Br, I as a halogen atom; pentamethylantimony group, trimethylsilyl group, trimethyl gel as an organic metalloid group Examples include a mill group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. R ⁷ , R ¹⁰
Specific examples include the same as those described above. Specific examples of the substituted cyclopentadienyl group for R ⁸ and R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Can be Here, the alkyl group usually has 1 to 6 carbon atoms,
The number of substituted alkyl groups can be selected from an integer of 1 to 5. Among the compounds of the formulas (V) and (VI), M ³ and M ⁴
Is preferably boron.

Among the compounds of the formulas (V) and (VI), the following compounds 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, benzyltriphenyltetraborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (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 (pentafluoroammonium) Methyldiphenylammonium phenyl) borate, methyltriphenylammonium tetra (pentafluorophenyl) borate Dimethyldiphenyltetra (pentafluorophenyl) borate Phenyl ammonium, 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) borate (p-cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (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 the formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate, ferrocenium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (1,1′-dimethylferrocenium), decamethylferrocenium tetra (pentafluorophenyl) borate, acetylferrocenium tetra (pentafluorophenyl) borate, formylferrocenium tetra (pentafluorophenyl) borate, tetra (Pentafluorophenyl) cyanoferrocenium borate, silver tetra (pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate,
Lithium tetra (pentafluorophenyl) borate, sodium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (tetraphenylporphyrin manganese), tetra (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetra (penta Fluorophenyl) borate (zinc tetraphenylporphyrin), silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate,

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

[0042]

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

[0043]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization, and the preferred number of repeating units is 3 to 50.) A cyclic alkylaluminoxane having a repeating unit represented by the formula: Among the compounds of the formulas (VII) to (IX),
Preferred are compounds of the formula (VII), and particularly preferred are compounds of the formula (VII) having r = 3, among which trialkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum.

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

The catalyst used in the production of the cyclic olefin-based copolymer has the above-mentioned components (a) and (b) or components (a), (b) and (c) as main components. is there. In this case, the use conditions of the component (a) and the component (b) are not limited, but the ratio (molar ratio) of the component (a) to the component (b) is 1: 0.01 to 1: 100, and particularly 1: 1. 0.
5 to 1:10, preferably 1: 1 to 1: 5. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily.

The amount of component (c) used is generally 0 to 2,000 mol, preferably 5 to 2,000 mol, per mol of component (a).
It is 1,000 mol, particularly preferably 10 to 500 mol. When the component (c) is used, the polymerization activity can be improved. However, when the amount is too large, a large amount of the organic aluminum compound remains in the polymer, which is not preferable. The use form of the catalyst is not limited. For example, the components (a) and (b) may be brought into contact with each other in advance, or the contact product may be separated and washed before use. May be used.
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 polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization and gas phase polymerization may be used.
Further, a batch method or a continuous method may be used. Regarding the polymerization conditions,
Polymerization temperature is -100 to 250C, especially -50 to 200C
It is preferable that Further, the ratio of the catalyst to the reaction raw material is expressed as raw material monomer / component (a) (molar ratio)
Alternatively, the raw material monomer / the component (b) (molar ratio) is 1
It is preferably from 10 to 10 ⁹ , particularly preferably from 100 to 10 ⁷ . Further, the polymerization time is usually 1 minute to 10 hours, and the reaction pressure is normal pressure to 100 kg / cm ² G, preferably normal pressure to 50 kg / cm ^2.
cm ² G. As a method of adjusting the molecular weight of the polymer,
The amount of each catalyst component, the selection of the polymerization temperature, and the polymerization reaction in the presence of hydrogen can be used.

When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, pentane, hexane,
Aliphatic hydrocarbons such as heptane and octane, and halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent.

In the present invention, if necessary, other resins, elastomers and the like can be added to the cyclic olefin copolymer. For example, dyeability, antistatic properties, and hydrophilicity can be imparted by adding a polar group-containing polymer. Specific examples of resins and elastomers that can be blended include polyolefin, polyester, polyamide, polyolefin-based elastomer, polyester-based elastomer, polyamide-based elastomer, vinyl chloride-based elastomer, and polyurethane-based elastomer.

Further, various additives such as a filler and a stabilizer can be blended. Specific examples of the additive that can be blended include the following.
Examples of the filler include an inorganic filler and an organic filler, and a known filler can be used without any particular limitation. Examples of usable fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, aluminum nitride, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, Examples include potassium titanate, barium titanate, barium sulfate, calcium sulfite, talc, clay, mica, calcium silicate, montmorillonite, bentonite, carbon black, graphite, aluminum powder, molybdenum sulfide, and the like. Various additives include heat stabilizers, weather stabilizers, antistatic agents, slip agents, anti-blocking agents,
Anti-fog agent, lubricant, foaming agent, dye, pigment, natural oil, synthetic oil,
A wax or the like can be blended, and the blending ratio can be determined as appropriate. For example, as a stabilizer blended as an optional component, specifically, tetrakis (methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, β- (3,5-di -T-
Butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamidobis (ethyl-3)
(3,5-di-t-butyl-4-hydroxyphenyl)
Phenolic antioxidants such as propionate), fatty acid metal salts such as zinc stearate, calcium stearate and calcium 1,2-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate And polyhydric alcohol fatty acid esters such as pentaerythritol distearate and pentaerythritol tristearate. These may be blended singly or in combination. For example, tetrakis (methylene-3 (3,5-di-
A combination of t-butyl-4-hydroxyphenyl) propionate) methane with zinc stearate and glycerin monostearate can be exemplified.

The fiber of the present invention comprises the above-mentioned cyclic olefin copolymer. In this case, the shape of the fiber of the present invention is not particularly limited, and may be any shape such as a circular cross-section, an irregular cross-section, and a flat cross-section. The fiber diameter is not limited, and may be any diameter according to the purpose and application. The fibers include not only long fibers but also short fibers, flocculent fibers, and fibers formed as a nonwoven fabric.

The method for producing the fiber of the present invention is not limited, and the fiber can be produced by a conventional method using the above-mentioned cyclic olefin copolymer. For example, the following spinning step, drawing step and heat treatment step as required Can be suitably adopted. Spinning A known melt spinning method can be employed, but the spinning temperature is 10 to 70 times higher than the melting point of the cyclic olefin copolymer.
It is preferable that the temperature is higher by 20 ° C, especially 20 to 50 ° C. If the spinning temperature is lower than a temperature higher by 10 ° C. than the melting point of the cyclic olefin-based copolymer, the discharge amount from the spinneret decreases, and it may be difficult to adjust the yarn diameter. On the other hand, if the spinning temperature exceeds a temperature 70 ° C. higher than the melting point of the cyclic olefin-based copolymer, the quality of the spun yarn may be reduced. When the spun yarn is a thick denier yarn of 1,000 denier or more, a cooling liquid bath is provided immediately below the spinneret, and after cooling the spun yarn in the cooling liquid bath, the torque is reduced. It is preferable to wind the spun yarn with a winder or the like. When a cooling liquid bath is provided, the temperature in the cooling liquid bath is desirably set to a temperature 20 to 100 ° C. lower than the spinning temperature. On the other hand, when the spun yarn is a fine denier yarn of less than 1,000 denier, it is not always necessary to provide a cooling liquid bath, and it can be cooled and solidified well in air. In addition, as the spinning method, in addition to the melt spinning,
Wet spinning using a copolymer solution may be used.
There are no particular restrictions on the spinning device, winding device, and the like that can be used in the production of the fiber of the present invention, and any of those conventionally used can be suitably used.

After spinning of the cyclic olefin-based copolymer as described above, stretching can be performed if necessary. In this case, any of known stretching apparatuses can be used for stretching the undrawn yarn obtained by spinning.
Specifically, for example, a non-contact stretching device using heated steam, a hot wire electric heater, or the like, a heating multi-stage stretching device provided with one or more contact heaters, and the like can be suitably used. In the stretching, the stretching temperature is preferably in a temperature range 5 to 30 ° C. higher than the glass transition temperature of the cyclic olefin-based copolymer. If the stretching temperature is less than about 5 ° C. higher than the glass transition temperature of the cyclic olefin-based copolymer, the stretchability may decrease, and a sufficient stretching effect may not be obtained. On the other hand, if the stretching temperature exceeds a temperature higher by 30 ° C. than the glass transition temperature of the cyclic olefin-based copolymer, fluff or wrap occurs during stretching, and stable stretching may not be performed. Further, the stretching ratio is preferably 1.5 or more, particularly preferably 2 to 10. If the draw ratio is less than 1.5, a fiber having a predetermined strength may not be obtained.

Heat Treatment In the production of the fiber of the present invention, after the spinning and stretching of the cyclic olefin copolymer as described above, a heat treatment can be carried out if desired. By performing the heat treatment, the strength of the obtained fiber can be further improved. In this case, the heat treatment is desirably performed in a temperature range lower than the melting point of the cyclic olefin-based copolymer, and when the cyclic olefin-based copolymer exhibits a crystallization temperature, it is higher than the crystallization temperature, and It is desirable to perform in a temperature range lower than the point. The heat treatment may be performed under tension of the drawn yarn obtained by drawing, or may be performed under relaxation.

[0055]

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. In this case, prior to the production of the fibers, the following Reference Examples 1 to 3
Were produced, and the fibers of Examples 1 to 5 were produced using these cyclic olefin copolymers.

Reference Example 1 (1) Preparation of Ferrocenium Tetra (pentafluorophenyl) borate 20 mmol of ferrocene (Cp ₂ Fe) and 40 sulfuric acid
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 At room temperature in a nitrogen atmosphere, 15 l of toluene, 23 mmol of triisobutylaluminum (TIBA), and 0.11 mmol of biscyclopentadienyl zirconium dichloride were placed in a 30-liter autoclave at room temperature. 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 piperon 11-EA type manufactured by Toyo Boulding Co., Ltd., a measuring piece having a width of 4 mm, a length of 40 mm, and a thickness of 0.1 mm was measured at a heating rate of 3 ° C./min and a frequency of 3.5 Hz. The glass transition temperature (Tg) was determined from the peak of the loss modulus of elasticity (E ″) of the sample, and the Tg was 3 ° C. ALC / OPC150C manufactured by Waters, Inc. was used as a measuring device, and 1,2,4-trichlorobenzene solvent was used. 135 ° C
The weight average molecular weight Mw, number average molecular weight Mn, and molecular weight distribution (Mw / Mn) were calculated in terms of polyethylene.
Mw is 54,200, Mn is 28,500, Mw / Mn
= 1.91. Using a Perkin-Elmer 7 series DSC at a rate of 10 ° C./min, -50 ° C.
When the melting point (Tm) was measured in the range of 150 ° C., the Tm
Was 73 ° C (broad peak) ° C.

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

Reference Example 3 In (2) of Reference Example 1, the amount of biscyclopentadienyl zirconium dichloride was 0.064 mmol, the amount of ferrocenium tetra (pentafluorophenyl) borate was 0.11 mmol, A cyclic olefin 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 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 5 The cyclic olefin copolymer a1 obtained in Reference Examples 1 to 3
Using a to a3, the fibers of Examples 1 to 5 shown in Table 1 below were produced. In this case, the cyclic olefin-based copolymers a1 to a
3 was heated to a resin temperature shown in Table 1, melted, and then spun at a winding speed shown in Table 1 using a capillary having an inner diameter of 0.3 mm to obtain a denier fiber shown in Table 1. The tensile strength, elongation, and tensile strength retention of the obtained fibers of Examples 1 to 5 were measured. The same measurement was performed using a commercially available polyurethane fiber (reference). Table 1 shows the results.

The measurement of each item was performed as follows. Tensile strength, elongation: distance between chucks 20 mm, tensile speed 2
The measurement was performed according to JIS-K7113 under the condition of 0 mm / min. Tensile strength retention: After immersing the fiber in water at 30 ° C. (sodium hypochlorite concentration 30 ppm, pH 7.5) for 24 hours, the tensile strength is measured in the same manner as above, and the retention against the initial value is determined. Was. As is clear from Table 1, the fibers of the present invention (Examples 1 to 5)
It can be seen that 5) has excellent elasticity and retains its mechanical properties even after being immersed in chlorinated water for a long time.

[0063]

[Table 1]

[0064]

As described above, the fibers of the present invention are:
It is excellent in hydrolysis resistance, light resistance, and chemical resistance, has good elasticity, and hardly changes in appearance such as mechanical properties and color tone during use. Therefore, the fiber of the present invention can be suitably used in various fields, such as for clothing such as apparel and textile, or for industrial use, sundries and the like.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D01F 6 / 04,6 / 30

Claims (1)

(57) [Claims] 1. A fiber using a cyclic olefin copolymer obtained by copolymerizing a cyclic olefin and an α-olefin, (a) having a glass transition point (Tg) of 50 ° C. or less; (B) When the content of the repeating unit derived from the α-olefin is [X] and the content of the repeating unit derived from the cyclic olefin is [Y], [X]:
The ratio of [Y] is in the range of 70 to 99.8 mol%: 30 to 0.2 mol%, and (c) a cyclic olefin copolymer which is soluble in decalin at 135 ° C. Fiber.