JP3173897B2 - Cyclic olefin resin fiber and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber made of a cyclic olefin resin, and particularly to a fiber having excellent properties such as strength, elastic modulus, creep resistance, heat resistance, water resistance, chemical resistance, solvent resistance, and hand. It relates to olefin resin fibers.

[0002]

BACKGROUND OF THE INVENTION Various resins such as polyamide, polyacrylonitrile, polyester resin, polyethylene, polypropylene, polyvinyl chloride and the like have been used as resins for forming synthetic fibers. These synthetic fibers have unique characteristics, feel, and texture depending on the type of resin used as a raw material and the like, and are appropriately selected and used depending on the application. For example, specific products include clothing, rope, fishing line, nonwoven fabric, reinforcing materials for various resin compounds, and the like.

[0003] As described above, the uses of synthetic resin fibers are diversified, and there is a demand for the appearance of fibers having a wide range of properties that can respond to the diversification. By the way, in recent years, a cyclic olefin random copolymer which is a copolymer of ethylene and a cyclic olefin having an ethylenic double bond in the ring has attracted attention. About this cyclic olefin resin, for example, JP-A-60-168708, JP-A-63-243111, JP-A-63-243111
-305111 and 63-223013. This cyclic olefin-based resin is essentially an olefin-based resin, but is a very interesting resin whose properties vary widely depending on the polymerization amount of the cyclic olefin and the type or amount of the component to be copolymerized with the cyclic olefin. is there. A cyclic olefin ring-opened (co) polymer obtained by ring-opening (co) polymerizing the above-mentioned cyclic olefin also has excellent properties.

[0004] The cyclic olefin-based resin, which is a cyclic olefin random copolymer and a cyclic olefin ring-opening (co) polymer, has conventionally been used as a mechanical component utilizing mechanical strength and the like, as a base utilizing optical characteristics, and the like. It is generally used, and is not actually used as a fiber.

The present inventor produced a cyclic olefin-based resin fiber by spinning a cyclic olefin-based resin, and measured the characteristics thereof. As a result, the strength, elastic modulus, creep resistance, heat resistance,
The present inventors have found out that the properties such as water resistance, chemical resistance, solvent resistance, and texture are all excellent and arrived at the present invention.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel fiber having a wide range of properties that can respond to recent fiber diversification.

[0007] More specifically, the present invention relates to strength, elastic modulus,
It is an object of the present invention to provide a novel fiber having excellent properties such as heat resistance, chemical resistance, solvent resistance, and texture.

[0008]

SUMMARY OF THE INVENTION The cyclic olefin resin fibers of the present invention are:
A random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II] and / or a ring-opened polymer or a ring-opened copolymer of a cyclic olefin represented by the following formula [I] or [II] I met polymer or of these hydrogenated products
The glass transition temperature (Tg) is 100 to 200 ° C.
Of a cyclic olefin resin by melt spinning.
And left for 24 hours under a load of 1000 kg / cm ²
Creep resistance, expressed as the change in fiber length (%)
Less than 1% and leave the fiber in boiling water for 24 hours
Resistance expressed as the rate of change in tensile strength (%)
Is 1% or less. In addition, the present invention
The method for producing a cyclic olefin resin fiber according to
A fin-based resin is spun by a melt spinning method, and a load of 10
Fiber length when left under 00kg / cm ² for 24 hours
Creep resistance expressed by the amount of change (%)
And after leaving the fibers in boiling water for 24 hours,
When the water resistance expressed by the change rate (%) of the tensile strength is 1% or less
Characterized by obtaining a certain cyclic olefin resin fiber
I have.

[0009]

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[I] In the above formula [I], n is 0 or 1, m is 0 or a positive integer, r is 0 or 1, R ^{1 to} R ^18, R ^a and R ^b independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic group. And the monocyclic or polycyclic group may have a double bond;
¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.

[0011]

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... [II] In the above formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹
Are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, alicyclic hydrocarbon group, an atom or group selected from the group consisting of aromatic hydrocarbon group and an alkoxy group, R ⁹ is bonded And the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹⁰ is bonded to R
^The carbon atom to which ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ^{12 And 19} may combine with each other to form a monocyclic or polycyclic aromatic ring.

The cyclic olefin resin fiber of the present invention is made of a cyclic olefin resin having a repeating unit derived from a specific cyclic olefin as described above, and therefore has strength, elastic modulus, heat resistance, chemical resistance, and Solvent properties, properties such as hand are generally excellent, therefore the fiber of the present invention,
It can respond to recent fiber diversification.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the cyclic olefin resin fiber of the present invention will be specifically described. The cyclic olefin-based resin forming the fiber of the present invention comprises ethylene and the following formula [I]
Or a random copolymer with a cyclic olefin represented by [II] and / or a ring-opened polymer or a ring-opened copolymer of a cyclic olefin represented by the following formula [I] or [II] or a hydrogenated product thereof Consists of

[Types of Cyclic Olefin Component] The cyclic olefin resin can be produced from a cyclic olefin represented by the following formulas [I] and [II].

[0016]

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[I] In the above formula [I], n is 0 or 1, m is 0 or a positive integer, and r is 0 or 1.

Further, R ^{1 to} R ¹⁸ and R ^a and R
^b represents an atom or a group independently selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In addition, examples of the hydrocarbon group independently include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. A specific example of the cycloalkyl group includes a cyclohexyl group.

Further, in the above formula [I], R ¹⁵ and R
¹⁶ and includes a R ¹⁷ and R ¹⁸ may further have a R ^{1 5} and R ^17, R ¹⁶
And R ¹⁸ may be combined with R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ (together with each other) to form a monocyclic or polycyclic group. The monocyclic or polycyclic group thus formed may have a double bond.

Here, examples of the monocyclic or polycyclic group include:
The groups described below can be mentioned.

[0021]

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In the above exemplified groups, the carbon atoms numbered 1 and 2 are the same as those in the formula [I]
A group represented by ¹⁵ to R ¹⁸ represents a carbon atom of the alicyclic structure is bonded.

Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸
And may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

The cyclic olefin may be a cyclic olefin represented by the following formula [II] in addition to the cyclic olefin represented by the above formula [I].

[0025]

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... [II] In the above formula [II], p is 0 or a positive integer, preferably 0 to 3. In the above formula [II], m and n are 0, 1 or 2. further,
q is 0 or a positive integer, preferably 0 or 1.

R ^{1 to} R ¹⁹ are each independently
An atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group include an alkyl group having 1 to 10 carbon atoms,
A cycloalkyl group having 5 to 15 carbon atoms, 6 carbon atoms
To 12 aromatic groups. As specific examples of the alkyl group, methyl group, ethyl group, isopropyl group, isobutyl group, n-amyl group, neopentyl group, n-hexyl group, n-octyl group, n-decyl group and
Examples thereof include a 2-ethylhexyl group and the like, and specific examples of the cycloalkyl group include a cyclohexyl group, a methylcyclohexyl group and an ethylcyclohexyl group, and specific examples of the aromatic group. Represents a phenyl group, a naphthyl group, a biphenyl group and the like.

In the above formula [II], the carbon atom to which R ⁹ is bonded and the carbon atom to which R ¹³ is bonded, or the carbon atom to which R ¹⁰ is bonded and R ¹¹ are bonded to each other. The carbon atom may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. Preferred examples in this case include the following groups in which R ¹⁵ and R ¹² further form an aromatic ring when n = m = 0.

[0030]

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In the above formula, q has the same meaning as in formula [II]. Specific examples of the cyclic olefin represented by the above formula [I] or [II] used in the present invention include derivatives of the compounds described below.

A bicyclo [2.2.1] hept-2-ene derivative,
Tricyclo [4.3.0.1 ^2,5] -3- decene derivatives, tricyclo [4.3.0.1 ^2,5] -3- undecene derivatives, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives, pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene derivative,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- hexadecene derivative, pentacyclo ^{[7.4.0.1 2,5 .1 9,12 .0 8,13]} -3
- pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3-
Pentadecene derivatives, hexacyclo [6.6.1.1 ^3,6 .1
^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11,16] - 4-eicosene derivatives, heptacyclo [8.7.0.1 ^3,6 .1 ^10,17 .1
^12,17 .0 ^2,7 .0 ^11,16] -5-eicosene derivatives, heptacyclo ^{[8.8.0.1 4,7 .1 11,18 .1 13,16 .0} 3,8 .0 12,17] - 5-heneicosene derivatives, heptacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1
^11,18 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8.
0 ^12,17 ] -5-docosene derivative, nonacyclo [10.9.1.
1 ^4,7 .1 ^13,20 .1 ^15,18 .0 ^3,8 .0 ^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives, Nonashikuro [10.10.1.1 ^5,8. 1 ^14,21 .
1 ^16,19 .0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^15,20] -5-hexacosenoic derivatives.

1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative, cyclopentadiene-acenaphthylene adduct .

The formula [I] or [I
Examples of the specific compound of the cyclic olefin represented by I] include the compounds described below.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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Further, as the cyclic olefin represented by the formula [I] or [II], in addition to the above compounds, 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-propyl
-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, 2,3-dimethyl-1,4,5,
8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4, 4a,
5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2
-Bromo-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, 2,3-dichloro
-1,4,5,8-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-n-butyl-
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
Octahydronaphthalenes such as a, 5,8,8a-octahydronaphthalene can be exemplified.

The cyclic olefin represented by the above formula [I] or [II] can be easily produced by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by a Diels-Alder reaction. .

These cyclic olefins can be used alone or in combination. [Cyclic olefin resin] The cyclic olefin resin forming the fiber of the present invention is a copolymer (cyclic olefin random) obtained by addition polymerization of a cyclic olefin represented by the above formula [I] or [II] and ethylene. Copolymer), and / or a ring-opened polymer or a ring-opened copolymer (cyclic olefin-opened (co) polymer) of a cyclic olefin represented by the above formula [I] or [II], or hydrogenation thereof. Things.

The monomer copolymerized with the cyclic olefin compound represented by the above formula [I] or [II] in the cyclic olefin random copolymer is ethylene. However,
In the cyclic olefin resin used in the present invention,
In addition to ethylene, other olefin compounds may be copolymerized within a range that does not impair the properties of the fiber of the present invention. Here, ethylene and the above formula [I] or formula [I
Examples of other olefin compounds that can be copolymerized with the cyclic olefin compound represented by I] include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, Α-olefins having 3 to 20 carbon atoms such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene and 3a, 5,6 , 7a-Tetrahydro-4,7
Cycloolefins such as -methano-1H-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,
4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinyl-2-
Non-conjugated dienes such as norbornene; norbornene-2,
5-methylnorbornene-2,5-ethylnorbornene-2,5-
Isopropyl norbornene-2,5-n-butyl norbornene
And norbornenes such as -2,5-i-butylnorbornene-2,5,6-dimethylnorbornene-2, 5-chloronorbornene-2, 2-fluoronorbornene-2 and 5,6-dichloronorbornene-2 be able to. Among these,
Α-olefins having 3 to 15, especially 3 to 10 carbon atoms are preferred.

These other olefins can be used alone or in combination. When a compound having two or more double bonds in a molecule is used as a cyclic olefin other than the cyclic olefin represented by the formula [I] or [II], it may be used after hydrogenation for the purpose of improving weather resistance. it can.

Ethylene as described above and formula [I] or [I
The cyclic olefin represented by I] is usually reacted in a solvent using a catalyst comprising a vanadium compound soluble in the reaction solvent and an organoaluminum compound.

In the cyclic olefin random copolymer, the cyclic olefin represented by the formula [I] or [II] forms a structure represented by the following formula [Ia] or [II-b], respectively. Conceivable.

[0064]

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[Ia] In the above formula [Ia], n, m, r, R ^{1 to} R ¹⁸ ,
R ^a and R ^b have the same meaning as in the above formula [I].

[0066]

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[II-a] In the above formula [II-a], p, q, m, n, R ^{1 to} R ¹⁹
Has the same meaning as in formula [II] above.

The cyclic olefin ring-opening polymer or cyclic olefin ring-opening copolymer is a cyclic olefin ring-opening polymer or ring-opening copolymer represented by the above formula [I] or [II].

The ring-opened cyclic olefin polymer or ring-opened cyclic olefin copolymer is prepared by the above-mentioned formula [I] or [II]
In the cyclic olefin represented by, ruthenium, rhodium,
Catalysts comprising halides of metals such as palladium, osmium, indium and platinum, nitrates of these metals or acetylacetone compounds of these metals, and reducing agents; halides of metals such as titanium, palladium, zirconium and molybdenum Alternatively, it can be produced by (co) polymerizing in the presence of a catalyst comprising an acetylacetone compound of these metals and organoaluminum.

In the cyclic olefin ring-opening (co) polymer, the cyclic olefin [I] or [II] is considered to form a repeating unit represented by the following formula [Ib] or [II-b], respectively. .

[0071]

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[Ib] In the above formula [Ib], n, m, r, R ^{1 to} R ¹⁸ ,
R ^a and R ^b have the same meaning as in the above formula [I].

[0073]

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[II-b] In the above formula [II-b], p, q, m, n, R ^{1 to} R ¹⁹
Has the same meaning as in formula [II] above.

The hydrogenated product of the cyclic olefin ring-opening (co) polymer is obtained by reducing the cyclic olefin ring-opening (co) polymer obtained as described above with hydrogen in the presence of a hydrogenation catalyst. Can be manufactured.

In the above cyclic olefin ring-opening (co) polymer, cyclic olefin [I] or [II] is represented by the following formula [I]
-c] or [II-c].

[0077]

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[Ic] In the above formula [Ib], n, m, r, R ^{1 to} R ¹⁸ ,
R ^a and R ^b have the same meaning as in the above formula [I].

[0079]

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[II-c] In the above formula [II-b], p, q, m, n, R ^{1 to} R ¹⁹
Has the same meaning as in formula [II] above.

The cyclic olefin-based resin produced as described above is purified through a deashing step, a filtration step, a precipitation step, and the like, if necessary. For example, the deashing step is a step of removing a catalyst residue remaining in the resin by bringing the reaction solution into contact with an aqueous alkali solution. Further, the precipitation step is a step in which the reaction solution is charged into a poor solvent for the resin to precipitate the resin dissolved in the reaction solvent.

The cyclic olefin resin used in the present invention is described in JP-A-60-168708 and JP-A-61-120816.
No. 61-115912, No. 61-115916, No. 61-271308, No. 61-
In the gazettes of 272216, 62-252406 and 62-252407, the compound can be produced by appropriately selecting conditions according to the method proposed by the present applicant.

The iodine value of the cyclic olefin resin forming the fiber of the present invention is usually 5 or less, and most of them are 1 or less.
The intrinsic viscosity [η] of the cyclic olefin random copolymer, the cyclic olefin ring-opening (co) polymer, and the hydrogenated product of the ring-opening (co) polymer measured in decalin at 135 ° C. is usually 0.01 to 20 dl / g, particularly 0.05 to 10 dl / g, and more preferably 0.08 to 8 dl / g
It is preferable that

[0084] These cyclic olefin-based resins are generally amorphous or low-crystalline, and are preferably amorphous. Therefore, this cyclic olefin resin itself has good transparency. When the crystallinity of this cyclic olefin-based resin is measured by X-ray, it is usually 5% or less, most of which is 0%, and the melting point is observed even when the melting point is measured by a differential scanning calorimeter (DSC). There are many things that are not done.

As other properties of such a cyclic olefin resin, a glass transition temperature (Tg) and a softening temperature (TM
A) is high. Glass transition temperature (Tg) is usually 230 ° C. or less, preferably 50 to 230
° C, often in the range of 100-200 ° C. In the present invention, in order to perform good spinning, the softening temperature is 70 to 180 ° C., and in many cases 90 ° C.
It is preferable to use a cyclic olefin-based resin having a temperature in the range of -180 ° C.

The thermal decomposition temperature of the cyclic olefin resin is usually 350 to 420 ° C., and in many cases 370 to 420 ° C.
It is in the range of 00 ° C. As the mechanical properties of this cyclic olefin resin, the tensile modulus of the resin itself is usually in the range of 1 × 10 ^{4 to} 5 × 10 ⁴ Kg / cm ² , and the tensile strength is also usually 300 to 1500 kg / cm ^2. Within the range.

The density of the resin itself is usually 0.8
6 to 1.10 g / cm ³ , most of which are 0.88 to 1.08
g / cm ³ . The cyclic olefin-based resin fiber of the present invention can be produced by heating the above-mentioned cyclic olefin-based resin to a temperature lower than the thermal decomposition temperature and melting it, and spinning it by a usual method. Alternatively, a resin composition containing another resin can be spun.

That is, various polymers are blended with the above-mentioned cyclic olefin resin to form a so-called polymer alloy in which other resins are finely dispersed in the cyclic olefin resin, and this can be spun. Here, polymers capable of forming a polymer alloy together with the cyclic olefin-based resin are exemplified below.

(1) Polymers Derived from Hydrocarbons Having One or Two Unsaturated Bonds Specifically, polyethylene, polypropylene, polymethylbutene-1, poly4-methylpentene-1, polybutene- 1 and polyolefins such as polystyrene. These polyolefins may have a crosslinked structure.

(2) Halogen-containing vinyl polymer Specific examples thereof include polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, and chlorinated rubber.

(3) Polymers Derived from α, β-Unsaturated Acids and Their Derivatives More specifically, polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles, or copolymers with the monomers constituting the above-mentioned polymers Polymers (eg, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-acrylate copolymer) and the like can be mentioned.

(4) Polymers Derived from Unsaturated Alcohols and Amines or Their Acyl Derivatives or Acetals Specific examples include polyvinyl alcohol, polyvinyl acetate, polyvinyl polythreate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, Examples thereof include polyallyl phthalate, polyallyl melamine, and copolymers with monomers constituting the polymer (eg, ethylene and vinyl acetate copolymers).

(5) Polymer Derived from Epoxide Specific examples thereof include polymers derived from polyethylene oxide or bisglycidyl ether.

(6) Polyacetal Specifically, polyoxymethylene, polyoxyethylene,
Examples of the comonomer include polyoxymethylene containing ethylene oxide.

(7) Polyphenylene oxide. (8) Polycarbonate. (9) Polysulfone.

(10) Polyurethane and urea resins. (11) polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, specifically nylon 6, nylon 66, nylon 11,
Nylon 12 and the like can be mentioned.

(12) Polyesters derived from dicarboxylic acids and dialcohols and / or oxycarboxylic acids or corresponding lactones Specific examples include polyester terephthalate, polybutylene terephthalate, poly-1,4-dimethylol / cyclohexane terephthalate, and the like. Can be.

(13) Polymer having a crosslinked structure derived from aldehyde and phenol, urea or melamine Specific examples include phenol-formaldehyde resin, urea-formaldehyde resin, and melamine-formaldehyde resin.

(14) Alkyd resin Specific examples include glycerin / phthalic acid resin. (15) An unsaturated polyester resin derived from a copolyester of a saturated or unsaturated dicarboxylic acid and a polyhydric alcohol and obtained by using a vinyl compound as a crosslinking agent, and a halogen-containing modified resin.

(16) Natural Polymers Specific examples include cellulose, rubber, proteins, and derivatives thereof (eg, cellulose acetate, cellulose propionate, cellulose ether).

(17) Soft polymer Specific examples include rubbery components selected from the groups (i) to (v) described below.

[Soft Polymer Containing Cyclic Olefin Component (i)] The soft polymer containing a cyclic olefin component is the same type of cyclic olefin (formula [I]) as used in the production of ethylene and the cyclic olefin resin. ] Or [II]).
As the soft polymer (i), in addition to the cyclic olefin and ethylene as essential components, an α-olefin can be used as long as its properties are not impaired. As α-olefin, for example, propylene, 1-butene, 4-methyl
Examples thereof include 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among them, α-olefins having 3 to 20 carbon atoms are preferred. Norbornene, ethylidene norbornene,
Cyclic olefins such as dicyclopentadiene and cyclic dienes are also preferred.

In the soft polymer (i) containing a cyclic olefin component, the ethylene component is used in the range of 40 to 98 mol%, preferably 50 to 90 mol%. The α-olefin component is used in the range of 2 to 50 mol%, and the cyclic olefin component is 2 to 20 mol%, preferably 2 to 15 mol%.
It is used in an amount of mol%.

The soft polymer (i) has a glass transition temperature (Tg) of 0 ° C. or lower, preferably −10 ° C. or lower, and is measured in decalin at 135 ° C., unlike the above-mentioned cyclic olefin polymer. Intrinsic viscosity [η] is usually 0.01 to
It is 10 dl / g, preferably 0.8 to 7 dl / g. The soft polymer (i) has a crystallinity of usually from 0 to 10%, preferably from 0 to 7%, particularly preferably from 0 to 5%, as measured by the X-ray diffraction method.

The soft polymer (i) is disclosed in JP-A-60-168.
708, JP-A-61-120816, JP-A-61-115912, JP-A-61-11591
No. 6, JP-A-61-271308, JP-A-61-271308
It can be produced by appropriately selecting conditions according to the method proposed by the present applicant in Japanese Patent Application Laid-Open Nos. 1-272216, 62-252406 and 62-252406.

The polymer alloy of the cyclic olefin polymer and these rubbery components may be subjected to a cross-linking reaction in the presence of an organic peroxide. Such a cross-linkable polymer alloy has rigidity and impact resistance. Provide fibers with excellent properties.

[Α-Olefin Copolymer (ii)] α-Olefin copolymer (i) used as a soft polymer
i) is an amorphous or low-crystalline copolymer composed of at least two α-olefins. Specific examples include an ethylene / α-olefin copolymer and a propylene / α-olefin copolymer.

As the α-olefin constituting the ethylene / α-olefin copolymer, those having 3 to 20 carbon atoms are usually used, and specifically, propylene, 1-butene, 4-
Α-olefins such as methyl-1-butene, 1-hexene, 1-octene, 1-decene and mixtures thereof. Of these, α-olefins having 3 to 10 carbon atoms are particularly preferred.

The molar ratio of ethylene / α-olefin copolymer (ethylene / α-olefin) varies depending on the type of α-olefin, but is generally 40/60 to 95/5.
It is. The molar ratio is preferably from 40/60 to 90/10 when the α-olefin is propylene, and from 50/50 to 95/5 when the α-olefin has 4 or more carbon atoms. Preferably, there is.

As the α-olefin constituting the propylene / α-olefin copolymer, one having 4 to 20 carbon atoms is usually used, and specifically, 1-butene and 4-methyl-1-
Α- such as butene, 1-hexene, 1-octene, 1-decene
Olefins and mixtures thereof can be mentioned. Among them, α-olefins having 4 to 10 carbon atoms are particularly preferred.

In the propylene / α-olefin copolymer described above, the molar ratio of propylene to α-olefin (propylene / α-olefin) varies depending on the type of α-olefin, but is generally 50/50. ~ 95
/ 5.

[Α-olefin / diene copolymer (ii)
i)] α-olefin / diene copolymer rubber (iii) used as a soft polymer includes ethylene / α-olefin / diene copolymer rubber and propylene / α-olefin / diene copolymer rubber .

The α-olefin constituting these copolymer rubbers usually has 3 to 20 carbon atoms (propylene / α-olefin).
In the case of olefins, α-olefins of 4 to 20), for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and mixtures thereof are exemplified. be able to. Among them, α-olefins having 3 to 10 carbon atoms are preferred.

The diene components constituting these copolymer rubbers are 1,4-hexadiene, 1,6-octadiene, 2-diene,
Linear non-conjugated dienes such as methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene and 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene,
Methyltetrahydroindene, 5-vinylnorbornene,
Cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3- Examples thereof include diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene.

In the above-mentioned ethylene / α-olefin / diene copolymer rubber, the molar ratio of ethylene to α-olefin (ethylene / α-olefin) differs depending on the type of α-olefin. 60-90 / 1
0.

The content of the repeating unit derived from the diene component in these copolymer rubbers is usually 1 to 20 mol%, preferably 2 to 15 mol%. [Aromatic vinyl hydrocarbon / conjugated diene soft copolymer (iv)] The aromatic vinyl hydrocarbon / conjugated diene soft copolymer used as the soft polymer is an aromatic vinyl hydrocarbon, conjugated Diene-based random copolymers, block copolymers or hydrides thereof. Specifically, styrene-butadiene block copolymer rubber, styrene
Butadiene / styrene block copolymer rubber, styrene / isoprene block copolymer rubber, styrene / isoprene / styrene block copolymer rubber, hydrogenated styrene / butadiene / styrene block copolymer, hydrogenated styrene / isoprene / styrene block copolymer Polymer rubber, styrene / butadiene random copolymer rubber, and the like are used.

In these copolymer rubbers, the molar ratio of aromatic vinyl hydrocarbon to conjugated diene (aromatic vinyl hydrocarbon / conjugated diene) is generally from 10/90 to 70/30.
It is. Further, the hydrogenated copolymer rubber is a copolymer rubber obtained by hydrogenating a part or all of the double bonds remaining in the above-mentioned copolymer rubber.

[Soft polymer or copolymer (v) consisting of isobutylene or isobutylene / conjugated diene] The isobutylene-based soft polymer or copolymer (v) used as the soft polymer is specifically, Isobutylene rubber, polyisoprene rubber, polybutadiene rubber, isobutylene / isoprene copolymer rubber, and the like.

The properties of the soft polymers (ii) to (v) are usually such that the intrinsic viscosity [η] measured in decalin at 135 ° C. is usually. The range is from 0.01 to 10 dl / g, preferably from 0.08 to 7 dl / g, and the glass transition temperature (Tg) is usually 0 ° C or lower, preferably -10 ° C or lower,
Particularly preferably, it is -20 ° C or lower. The crystallinity measured by the X-ray diffraction method is usually in the range of 0 to 10%, preferably 0 to 7%, and particularly preferably 0 to 5%.

The polymer as described above can be used by kneading it with a cyclic olefin resin, and the kneaded product in which another resin is dispersed in the cyclic olefin resin is further mixed with an organic peroxide. By performing the treatment, a crosslinked structure can be formed in the resin kneaded product and used.

Examples of the organic peroxide used herein include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, and 1,1-bis (t-butylperoxy) cyclohexane 2,2-bis ( Peroxy ketals such as t-butyl peroxy) octane, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxy peroxide, 1,1,3,3-tetra Hydroperoxides such as methylbutyl hydroperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy)
Dialkyl peroxides such as hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-3, diacyl peroxides such as lauroyl peroxide and benzoyl peroxide, t-butyl peroxyacetate,
t-butyl peroxybenzoate, 2,5-dimethyl-2,5-
Peroxyesters such as di (benzoylperoxy) hexane can be mentioned.

The amount of the above-mentioned organic peroxide component is usually 0.00.0 parts by weight per 100 parts by weight of the resin component constituting the fiber.
It is 1 to 1 part by weight, preferably 0.05 to 0.5 part by weight. And, when treated with an organic peroxide for the purpose of further increasing the crosslinking efficiency, when a compound having two or more radically polymerizable functional groups in the molecule is further contained, a fiber excellent in impact resistance can be obtained. It is preferred.

Examples of the compound having two or more radically polymerizable functional groups in a molecule include divinylbenzene, vinyl acrylate, and vinyl methacrylate. These compounds are used as the resin component 100 constituting the fiber.
Usually 1 part by weight or less, preferably 0.1 part by weight, relative to parts by weight.
It is used in an amount of 1 to 0.5 parts by weight.

When such a soft polymer (the soft copolymer (i) to (v)) is used, the soft polymer is usually 5-1 to 100 parts by weight of the cyclic olefin resin.
By using 50 parts by weight, preferably 5 to 100 parts by weight, particularly preferably in the range of 10 to 80 parts by weight,
The resulting fibers have a good balance of properties such as impact strength, rigidity, heat deformation temperature and hardness. The polymer alloy preferably has a melt flow index (MFR; ASTM D1238 condition) of 0.1 to 100. .

[Other Additives] In addition to the above-mentioned other resins, the cyclic olefin-based resin forming the fiber of the present invention is heat-resistant and weather-resistant as long as the object of the invention is not impaired. , An antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax, an organic or inorganic filler, and the like.

For example, a stabilizer incorporated as an optional component includes 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, zinc stearate, calcium stearate, fatty acid metal salts such as calcium 1,2-hydroxystearate, glycerin monostearate, Examples include polyhydric alcohol fatty acid esters such as glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination. For example, tetrakis [methylene-3- (3.
5-di-t-butyl-4-hydroxyphenyl) propionate], a combination of methane, zinc stearate, and glycerin monostearate.

Examples of the organic or inorganic filler include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, domite, and calcium sulfate. , Potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass peas,
Calcium silicate, montmorillonite, pentonite,
Examples thereof include graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber.

The cyclic olefin polymer and other components are
Mixing can be performed using a known method. For example, each component can be mixed simultaneously. [Production of Fiber] The fiber of the present invention can be obtained by adding a composition containing the above-mentioned cyclic olefin resin and, if necessary, other components, by a conventionally known fiberizing method.

Examples of the spinning method for fiberization include dry spinning, wet spinning, melt spinning, and emulsion spinning. Among these spinning methods, the melt spinning method is particularly preferred.

In this melt spinning method, a cyclic olefin resin (or composition) is heated to a temperature not lower than the melting point (or softening point) and lower than the decomposition temperature, preferably at a temperature of 120 to 300 ° C., to obtain a molten state. This is a method of extruding from a nozzle and winding the extruded resin while cooling it. In this method, various types of nozzles can be used, but a nozzle having an L / D value of about 10 / 0.5 to 60/3 mm is suitable. The extrusion speed of the resin from the nozzle is generally 0.01 to 100 m / min, preferably 0.05 to 10 m / min.
It is about. The winding speed of the monofilament extruded at the above speed is usually 10 to 10,000 m.
/ min, preferably 100 to 5,000 m / min. Therefore, the monofilament extruded from the nozzle is usually stretched during winding. The stretching ratio at this time is usually 10 to 10,000, preferably 100 to 5,000.

The raw yarn obtained by spinning as described above can be subjected to a post-treatment process for removing impurities, stretching under tension, heat treatment, refining, dyeing, and the like.

The fiber thus obtained is used for clothing, rope,
It can be used for applications such as fishing line, non-woven fabric and reinforcing agent for compounds of various resins.

[0133]

As described above, the cyclic olefin resin fiber of the present invention comprises:
Maintaining sufficient formability, strength, elastic modulus, creep resistance,
Excellent heat resistance, water resistance, chemical resistance, solvent resistance and texture.

[0134]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

A polymer as a raw material was prepared by the method described below, and after spinning, various characteristics were examined. Methods for measuring and evaluating various physical properties are described below.

(1) Tensile modulus: ASTM at a temperature of 23 ° C.
It was measured by a method according to -D3822. (2) Tensile strength: measured at a temperature of 23 ° C. by a method according to ASTM-D3822. (3) TMA softening temperature: The ambient temperature is raised from room temperature at a rate of 10 ° C./min under a load of 100 kg / cm ² , and the temperature at which the fiber length is extended by 10% is defined as the softening temperature.

(4) Crepe resistance: The fiber was left standing at various temperatures for 24 hours under a load of 1000 kg / cm ² , and the change in fiber length was measured. (5) Water resistance: Measured based on the rate of change in tensile strength after leaving the fiber in boiling water for 24 hours.

(6) Hand: The texture was evaluated by the feel of the prepared nonwoven fabric. [Preparation Method of Cyclic Olefin Polymer] (Preparation of Catalyst) VO (OC ₂ H ₅ ) Cl ₂ was diluted with cyclohexane to prepare a vanadium catalyst having a vanadium concentration of 18.6 mmol / l-cyclohexane. On the other hand, ethyl aluminum sesquichloride (Al
(C ₂ H ₅ ) _1.5 Cl _1.5 ) was diluted with cyclohexane to prepare an organoaluminum catalyst having an aluminum concentration of 164 mmol / L-cyclohexane.

(Polymerization) A polymerization vessel with a baffle plate and a stirrer having an inner diameter of 700 mm, a total volume of 570 liters and a reaction volume of 300 liters, and a heat transfer area of 1
The polymerization solution is withdrawn from the bottom of a vertical multi-tube cooler of 9.4 m ² and a polymerization vessel equipped with a stirrer, and the polymerization solution is circulated through the multi-tube cooler and returned to the polymerization vessel in a circulation line. using a polymerization apparatus equipped with a circulation pump provided, (hereinafter also referred to simply as "tetracyclododecene") ethylene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene And butene-1 were continuously copolymerized.
In addition, butene-1 is a butene in the obtained copolymer.
The amount of the repeating unit derived from -1 was supplied so as to be 1.2 mol%.

At the time of this reaction, the vanadium catalyst (V catalyst) prepared by the above method was supplied into the polymerization reactor in such an amount that the V catalyst concentration in the polymerization reactor was 0.35 mmol / l. In addition, the V catalyst was previously diluted with cyclohexane as a polymerization solvent so that the concentration of the V catalyst immediately before being supplied to the polymerization reactor was 1.8 times the concentration of the catalyst in the polymerization machine. And fed to the polymerization vessel.

On the other hand, ethylaluminum sesquichloride, which is an organoaluminum compound, was supplied to the polymerization vessel in such an amount that Al / V = 8.0. Moreover, the solution was diluted with cyclohexane as a polymerization solvent in advance so that the concentration immediately before being supplied to the polymerization vessel was 11 times the concentration in the polymerization vessel, and then supplied to the polymerization vessel.

These V catalysts and organoaluminum catalysts are located near the tip of the upper stage blade of a stirrer provided with six vertical disturber blades having a diameter of 0.25 m in two stages, and are most strongly stirred. The mixture was supplied to the section, and the catalyst was promptly dispersed and mixed.

233 kg of cyclohexane as a polymerization solvent
/ h into the polymerization vessel. 2.69 kg / h of ethylene
And a hydrogen gas as a molecular weight regulator of 2.2 N
It was supplied at a rate of 1 liter / h to the gas phase in the polymerization reactor. 4.3kw /
The polymerization liquid was vigorously stirred with a stirrer having a power of KL.

The reaction temperature was adjusted so that the polymerization temperature became 10 ° C. by circulating a 25% by weight methanol / water mixture as a refrigerant through a jacket and a shell-and-tube cooling shell attached to the outside of the polymerization vessel. Further, a nitrogen gas was introduced into the polymerization vessel to adjust the polymerization pressure to 1.0 kg / cm ² -G.

For cleaning the inner wall of the polymerization vessel, the following method was used. That is, a pan (spray disk) having a partly perforated hole was attached to a gas phase portion of a shaft connecting the stirrers. Cyclohexane solvent in an amount of 30 kg / h, tetracyclododecene in an amount of 14.2 kg / h, and butene-1 in a volume of 0.4 kg were added to the spray disk.
It was supplied in an amount of 1 kg / h. The above components were sprayed onto the inner wall of the polymerization reactor from the holes of the spray disk by the centrifugal force generated in the spray disk rotating with the rotation of the stirrer. The sprayed tetracyclododecene, cyclohexane and butene-1 dropped into the liquid phase while cleaning the inner wall surface.

Under the above conditions, a copolymerization reaction of ethylene, tetracyclododecene and butene-1 was continuously carried out, and a hexane solution having a concentration of ethylene / tetracyclododecene / butene-1 copolymer of 30 g / l was obtained. Obtained.

(Deashing) Ethylene extracted from the polymerization vessel
To a cyclohexane solution of the tetracyclododecene-butene-1 copolymer, boiler water at 80 ° C. and a NaOH solution having a concentration of 4% by weight, which is a pH regulator, were added to stop the copolymerization reaction. Was removed (demineralized) from the solution.

The cyclohexane solution after demineralization is once stored in a container with a stirrer having an inner diameter of 900 mm and an effective volume of 1.0 m ³ , and is stored by flowing normal-temperature water through a jacket attached to the outside of the container. Three cyclohexane solutions
Cooled to 0-40 ° C.

(Filtration) The thus-cooled cyclohexane solution was washed with an outer diameter of 63.5 mm, an inner diameter of 28 mm and a length of 1 mm.
The filter was continuously supplied at a rate of 261 kg / h to a filter having 34 nominal 1 μm cotton filter filters (manufactured by Nippon Shokubai Co., Ltd., vertical wide filter) having a m of 261 kg / h.

Next, a filter provided with three depth type filters (BX filters manufactured by Bolston) of a nominally 2 μm borosilicate glass macrofiber nonwoven fabric having an outer diameter of 64 mm, an inner diameter of 51 mm, and a length of 476 mm, The above filtrate was continuously supplied at an amount of 261 kg / h and filtered. The differential pressure at this time was 1.5 kg / cm ² or less.

Next, filtration was performed by disposing three depth type filters (AQ filters manufactured by Bolsonton) of non-woven fabric made of borosilicate glass microfiber having a nominal diameter of 0.9 mm, an inner diameter of 51 mm, and a length of 476 mm. The filtrate was continuously supplied to the vessel at a rate of 261 kg / h and filtered. The differential pressure at this time was 1.5 kg / cm ² or less.

In addition, filtration using three non-woven fabric depth-type filters made of borosilicate glass microfiber having a nominal outer diameter of 59 mm, an inner diameter of 51 mm, and a length of 476 mm (AAQ filters manufactured by Bolsonton) was arranged. The filtrate was continuously supplied to the vessel at a rate of 261 kg / h and filtered. The differential pressure at this time was 1.5 kg / cm ² or less.

Finally, a filter provided with one pleated filter of a non-woven fabric made of SUS 304 having a nominal diameter of 61 mm and a length of 510 μm and made of SUS 304 metal (PSP03 filter, manufactured by Planswick) was placed in the filter. 261 kg / h of filtrate
And filtered continuously.

(Precipitation) Acetone was added to the cyclohexane solution filtered as described above to precipitate a copolymer.
The precipitated copolymer was separated.

After extracting and removing unreacted monomers from the obtained cyclic olefin random copolymer, the copolymer was separated, dried, pelletized, and further dried. ¹³ C-NM of the copolymer obtained as described above
The ethylene content measured by R analysis was 65 mol%, the tetracyclododecene content was 34 mol%, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.45 dl / g, DS
Glass transition temperature (Tg) measured by the C method is 127 ° C.
Met.

[0156]

Example 1 The copolymer obtained as above was melted at 230 ° C. in a cylindrical barrel having a diameter of 10 mm.
D = 20/1 mm is extruded through a nozzle at a speed of 0.1 m / min, and the extruded resin is wound up at a winding speed of 300 m / min while being air-cooled and stretched to form a cyclic olefin-based random copolymer. A monofilament was obtained.

Using the obtained monofilament, physical properties were measured and evaluated according to the above-mentioned methods. Table 1 shows the results.

[0158]

Example 2 A monofilament was obtained in the same manner as in Example 1, except that the temperature of the resin during spinning was changed to 220 ° C.

Using the obtained monofilament, physical properties were measured and evaluated according to the above-mentioned methods. Table 1 shows the results.

[0160]

Example 3 A monofilament was obtained in the same manner as in Example 1, except that the winding speed during spinning was changed to 150 m / min.

Using the obtained monofilament, physical properties were measured and evaluated according to the above-mentioned methods. Table 1 shows the results.

[0162]

[Table 1]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-258815 (JP, A) JP-A-61-2271308 (JP, A) JP-A-62-223013 (JP, A) JP-A-62-26713 252406 (JP, A) JP-A-61-272216 (JP, A) JP-A-5-132815 (JP, A) European Patent Application Publication 503422 (EP, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) D01F 6/30 C08F 210/02 C08F 232/08

Claims (3)

(57) [Claims] 1. A random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II] and / or a ring opening weight of a cyclic olefin represented by the following formula [I] or [II]: A ring-opened copolymer or a hydrogenated product thereof having a glass transition temperature (Tg) of 100 to 200 ° C.
Olefin resin spun by a melt spinning method and left for 24 hours under a load of 1000 kg / cm ² .
1% creep resistance expressed as change in fiber length (%)
And the tensile strength after leaving the fiber in boiling water for 24 hours.
Water resistance expressed as change rate (%) is 1% or less
Characteristic cyclic olefin-based resin fiber; In the formula [I], n is 0 or 1, m is 0 or a positive integer, r is 0 or 1, and R ^{1 to} R
¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring. May be formed, and the monocyclic or polycyclic group may have a double bond. Further, when R ¹⁵ and R ¹⁶ or R ¹⁷ and R ^{18 represent an} alkylidene group, May form a group]; ... in [II] [Formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, R ¹
To R ¹⁹ are each independently a hydrogen atom, a halogen atom,
Represents an atom or group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and a carbon atom to which R ⁹ is bonded and R ¹³ are bonded to each other. And the carbon atom to which R ¹⁰ is bonded and the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. When m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R
^{And 19} may combine with each other to form a monocyclic or polycyclic aromatic ring. 2. A random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II], and / or a ring-opening weight of a cyclic olefin represented by the following formula [I] or [II]: A cyclic olefin resin having a glass transition temperature (Tg) of 100 to 200 ° C., which is a coalesced or ring-opened copolymer or a hydrogenated product thereof, is spun by a melt spinning method under a load of 1000 kg / cm ^2. 1% creep resistance expressed as the change in fiber length (%) when left for 24 hours at
And a cyclic olefin-based resin fiber having a water resistance of 1% or less expressed by a change rate (%) in tensile strength after leaving the fiber in boiling water for 24 hours. Method for producing olefin-based resin fiber; ... [I] [In the formula [I], n is 0 or 1, m is 0 or a positive integer, r is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ may combine with each other to form a monocyclic or polycyclic group; and it may be monocyclic or polycyclic group optionally having a double bond and, R ¹⁵
And R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group]; ... in [II] [Formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, R ¹
To R ¹⁹ are each independently a hydrogen atom, a halogen atom,
Represents an atom or group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and a carbon atom to which R ⁹ is bonded and R ¹³ are bonded to each other. And the carbon atom to which R ¹⁰ is bonded and the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. When m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R
^{And 19} may combine with each other to form a monocyclic or polycyclic aromatic ring. 3. A catalyst comprising a vanadium compound soluble in a reaction solvent and an organoaluminum compound, wherein a random copolymer of ethylene and a cyclic olefin represented by the above formula [I] or [II] is used. A copolymer obtained by reacting in a solvent, wherein the ring-opened polymer or ring-opened copolymer of the cyclic olefin represented by the above formula [I] or [II] is: i) ruthenium, rhodium, palladium, osmium,
Of a metal selected from the group consisting of indium and platinum,
A catalyst comprising a halide, nitrate or acetylacetone compound and a reducing agent, or ii) a catalyst comprising a halide or acetylacetone compound of a metal selected from the group consisting of titanium, palladium, zirconium and molybdenum and an organic aluminum door The method for producing a cyclic olefin-based resin fiber according to claim 2, which is a copolymer obtained by polymerization or copolymerization in the presence of any catalyst.