JP2000265330A - Conjugate fiber and woven, knitted or nonwoven fabric formed from the same fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a conjugate fiber excellent in shape retaining properties after adsorbing an oil and suitable for an oil adsorbent, a filter material, etc., by composing the fiber of a specific cyclic olefinic polymer and a resin such as an acyclic polyolefin-based resin. SOLUTION: This fiber comprises (A) one or more kinds of cyclic olefinic polymers selected from the group consisting of (i) an ethylene-cyclic olefin random copolymer of ethylene and a cyclic olefin represented by formula I [n and q are each 0 or 1; m is 0 or a positive integer; R1 to R18, Ra and Rb are each H, a halogen, a (halogen-substituted)hydrocarbon or the like] or formula II [p and q are each 0 or a positive integer; m and n are each 0-2; R1 to R19 are each H, a halogen, a (halogen-substituted)hydrocarbon or the like], (ii) a ring opening (co)polymer of the cyclic olefin represented by formula I or II, (iii) a hydrogenated material of the component (ii) and (iv) a graft modified material of the component (i), (i) or (iii) and (B) a resin selected from the group consisting of an acyclic polyolefin-based resin, a polyester-based resin and a polyamide-based resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conjugate fiber having a resin portion made of a cyclic olefin polymer, and a woven, knitted or non-woven fabric formed from the conjugate fiber. The present invention relates to an oil adsorbent having excellent shape retention after oil absorption using a cloth or a nonwoven fabric and a filter material having excellent absorption performance.

[0002]

BACKGROUND OF THE INVENTION Fibers composed of a cyclic olefin polymer are already known from Japanese Patent Application Laid-Open No. 6-158420. This fiber has excellent strength, elastic modulus and heat resistance,
It is said that it can be used as a compound reinforcing material for clothes, ropes, fishing lines, nonwoven fabrics, and various resins because of its good moldability.

[0003] Further, there is an oil adsorbent as an application to which the excellent oil absorbing property of the cyclic olefin polymer is applied. For example, in the event of a tanker accident, a polypropylene oil mat (oil absorbent cloth) or the like is conventionally laid on the sea surface to absorb oil spills in order to prevent oil spilled from the tanker from spreading and to prevent adverse effects on fisheries. Such methods have been taken. When a fiber made of a cyclic olefin polymer was used as the oil adsorbent, for example, when a nonwoven fabric was used, the oil was absorbed into the resin more quickly than the conventional one, and the oil absorption efficiency was excellent, but the oil absorption efficiency was excellent. There was a problem that the substance was dissolved when immersed in oil for a long time.

Therefore, a method using a woven or non-woven fabric mixed with fibers of another resin, for example, polypropylene or polyamide, as described in JP-A-8-144165 has been proposed. However, even in this method, shape retention after adsorbing oil is poor, and there is a problem in handling.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems associated with the prior art, and to provide a cyclic olefin polymer having excellent shape retention even after adsorbing oil or the like. It is an object of the present invention to provide a conjugate fiber consisting of: a woven fabric, a knitted fabric, or a nonwoven fabric using the conjugate fiber;

[0006]

Means for Solving the Problems The conjugate fiber according to the present invention is at least one selected from the group consisting of the following [A-1], [A-2], [A-3] and [A-4]. And a resin (B) selected from the group consisting of a non-cyclic polyolefin resin, a polyester resin, and a polyamide resin.

[A-1] An ethylene / cyclic olefin random copolymer obtained by copolymerizing ethylene and a cyclic olefin represented by the following formula (I) or (II):

Embedded image (In the formula (I), n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently hydrogen. An atom, a halogen atom or a hydrocarbon group optionally substituted by halogen, wherein R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and It may have a double bond, and R ¹⁵ and R ¹⁶ or R ^15
17 and R ¹⁸ may form an alkylidene group. ),

[0008]

Embedded image (In the formula (II), p and q are 0 or a positive integer,
m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group which may be substituted by halogen,
The carbon atom to which R ⁹ or R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are bonded directly or via an alkylene group having 1 to 3 carbon atoms. When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. ),

[A-2] A ring-opened polymer or copolymer of a cyclic olefin represented by the above formula (I) or (II),
3] A hydride of the above ring-opened polymer or copolymer [A-2], and [A-4] a graft modified product of the above [A-1], [A-2] or [A-3].

In the present invention, the cyclic olefin polymer
(A) is preferably a conjugate fiber that continuously forms at least a part of the fiber surface in the length direction, and as the fiber forming the shape, the cyclic olefin polymer (A)
Resin part (a) made of resin and resin part made of resin (B)
(b) and a side-by-side type conjugate fiber, or a sheath made of the cyclic olefin polymer (A), and a core-sheath conjugate fiber composed of a core made of the resin (B). No.

In the present invention, the cyclic olefin polymer
(A) is an ethylene • obtained by copolymerizing ethylene with the cyclic olefin represented by the above formula (I) or (II).
It is preferably a cyclic olefin random copolymer [A-1], and more preferably a tetracyclododecene-based ethylene / cyclic olefin random copolymer.

Further, according to the present invention, there is provided a woven fabric, a knitted fabric or a nonwoven fabric formed from the above-mentioned conjugate fiber. A preferred embodiment of a woven, knitted or nonwoven fabric is a woven, knitted or nonwoven fabric in which the conjugate fibers are formed from electretized conjugate fibers.

Further, according to the present invention, it is possible to provide an oil-adsorbing material and a filter material using the woven fabric, knitted fabric or non-woven fabric, which have an oil stain removing function such as a spectacle wipe, a glass wipe, a wiper and the like. It is suitably used for a wiping material for removing oil stains and a deodorizing filter for removing various odors.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The conjugate fiber according to the present invention and a woven, knitted or non-woven fabric formed from the fiber will be specifically described below.

Composite fiber The composite fiber according to the present invention is a cyclic olefin polymer (A).
And a resin (B) selected from the group consisting of acyclic polyolefin resins, polyester resins, and polyamide resins
It is composed of First, the cyclic olefin polymer
(A) will be described.

Cyclic olefin polymer (A) In the present invention, the following [A-1], [A-2], [A-3], [A-4] ] Can be used alone, or they can be used in combination. Among these, an ethylene / cyclic olefin random copolymer [A-1] is preferably used.

[A-1] An ethylene / cyclic olefin random copolymer obtained by copolymerizing ethylene with a cyclic olefin represented by the following formula (I) or (II):

Embedded image

(In the formula (I), n is 0 or 1, m
Is 0 or a positive integer; q is 0 or 1;
^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group optionally substituted with halogen, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring. And the monocyclic or polycyclic ring may have a double bond, and may form an alkylidene group with R ¹⁵ and R ¹⁶ or with R ¹⁷ and R ^18. You may. ),

[0019]

Embedded image

(In the formula (II), p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ¹
To R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group which may be substituted with halogen, and a carbon atom to which R ⁹ or R ¹⁰ is bonded and R ¹³ are bonded to each other. May be directly or via an alkylene group having 1 to 3 carbon atoms, or may be bonded to the carbon atom to which R ¹¹ is bonded. When n = m = 0, R ¹⁵ and R ¹² or R ^{12 15} and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ),

[A-2] A ring-opened polymer or copolymer of a cyclic olefin represented by the above formula (I) or (II);
3] A hydride of the above ring-opened polymer or copolymer [A-2], and [A-4] a graft modified product of the above [A-1], [A-2] or [A-3].

The softening temperature (TM) of the cyclic olefin polymer (A) measured with a thermal mechanical analyzer
A) is 60 ° C. or higher, preferably 70 ° C. or higher, and the glass transition point (Tg) is 30 ° C. or higher, preferably 60 ° C. or higher, and more preferably 70 to 200 ° C.

The degree of crystallinity of this cyclic olefin polymer (A) measured by X-ray analysis is preferably 0 to 20%, more preferably 0 to 2%. The intrinsic viscosity [η] of the cyclic olefin polymer (A) measured in decalin is 0.05 to 10 dl / g, preferably 0.3 to 10 dl / g.
-2.0 dl / g, more preferably 0.4-1.2 d
1 / g is desirable.

The iodine value of such a cyclic olefin polymer (A) is usually 5 or less, and most of them are 1 or less. Here, the cyclic olefin represented by the above formula (I) or (II) forming the cyclic olefin polymer (A) used in the present invention will be described first.

Cyclic olefin In the cyclic olefin represented by the above formula (I), n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, ^Ra and ^Rb
Are each independently the following atoms or hydrocarbon groups, and when q is 0, each bond is bonded to 5
Form a member ring.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group optionally substituted with halogen. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the hydrocarbon group independently include an alkyl group usually having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group.

More specifically, 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. Examples thereof include a cyclohexyl group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. These hydrocarbon groups may be substituted with a halogen atom.

Further, in the above formula (I), R ^{15 to} R ¹⁸
May be bonded to each other (together with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed may have a double bond.

In the cyclic olefin represented by the above formula (II), p and q are 0 or a positive integer, and m and n
Is 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

The halogen atom has the same meaning as the halogen atom in the above formula (I). Further, as the hydrocarbon group, each independently an alkyl group having 1 to 20 carbon atoms,
Examples thereof include a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group. More specifically, as the alkyl group,
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 cycloalkyl group includes a cyclohexyl group; an aromatic hydrocarbon group; Examples thereof include an aryl group and an aralkyl group, specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group and a phenylethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group.
These hydrocarbon groups and alkoxy groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or a carbon atom having 1 to 1 carbon atoms.
And 3 may be bonded via an alkylene group. That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ , or the groups represented by R ¹⁰ and R ¹¹ cooperate with each other, methylene group (-CH ₂ -), ethylene group (-CH ₂ CH ₂ -) or propylene group _{(-CH 2 CH 2 CH 2 -} ) to form one alkylene group of the.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. In this case, as the monocyclic or polycyclic aromatic ring, for example, the following n = m = 0
In the above, a group in which R ¹⁵ and R ¹² further form an aromatic ring can be mentioned.

[0034]

Embedded image Here, q has the same meaning as q in the formula (II).

The cyclic olefins represented by the above formula (I) or (II) are more specifically exemplified below.
As an example,

Embedded image (In the above general formula, the numbers 1 to 7 indicate the position numbers of carbon atoms) and derivatives obtained by substituting the compound with a hydrocarbon group Is mentioned.

As the substituted hydrocarbon group, 5-methyl, 5,
6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5-phenyl, 5-benzyl, 5-tolyl, 5- (ethyl Phenyl), 5-
(Isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- (anthracenyl), and 5,6-diphenyl.

Still other derivatives include cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a -
Bicyclo [2.2.1] -2-heptene derivatives such as hexahydroanthracene can be exemplified.

In addition, tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene, 5-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene and other tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives, tricyclo [4.4.0.1
^2,5 ] -3-undecene, 10-methyltricyclo [4.4.0.1 ^2,5 ]
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivatives such as -3-undecene,

[0039]

Embedded image In tetracyclo shown [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, and this hydrocarbon group include derivatives substituted.

As the hydrocarbon groups, 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2,10 -Dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl
-9-ethyl, 9-isobutyl-2,7-dimethyl, 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,1
2-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8
-Ethylidene-9-methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-
n-propylidene, 8-n-propylidene-9-methyl, 8-n-propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8 -Isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8-isopropylidene-9-isopropyl, 8-
Isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-
Fluoro, 8,9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl, 8- (ethylphenyl),
8- (isopropylphenyl), 8,9-diphenyl, 8- (biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8- (anthracenyl), 5,6-diphenyl and the like are exemplified. be able to.

[0041] Furthermore, - tetracyclo such (cyclopentadiene acenaphthylene adduct) and adduct of cyclopentadiene [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives, pentacyclo [6.5.1.1 ^{3, 6.0 2,7} .0 ^9,13] -4-pentadecene and its derivatives, pentacyclo [7.4.0.1 ^2,5 .1
^9,12 .0 ^8,13] -3-pentadecene and its derivatives, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene and derivatives thereof, pentacyclo [6.6.1.1 ^{3 , 6.0} 2,7.0 ^9,14 ]-
4-hexadecene and its derivatives, hexacyclo [6.6.
1.1 ^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene and its derivatives, heptacyclo ^{[8.7.0.1 2,9 .1 4,7 .1 11,17 .0} 3, ⁸ .0
^12,16 ] -5-Eicosene and its derivatives, heptacyclo
^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11,16] -4- eicosene and its derivatives, heptacyclo [8.8.0.1 ^2,9 .1 ^4,7. 1
^11,18 .0 ^3,8 .0 ^12,17] -5-heneicosene and its 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 and its derivatives, nonacyclo
^{[10.9.1.1 4,7 .1 13,20 .1 15,18 .0} 2, 10 .0 3,8 .0 12,21 .0
^14,19] -5-pentacosene and derivatives thereof.

Specific examples of the above formula (I) or formula (II) which can be used in the present invention are as described above. More specific structures of these compounds are described in the application of the present applicant. And paragraphs [0032] to [0054] of JP-A No. 7-145213, and in the present invention, those exemplified in the above specification may be used as the cyclic olefin of the present invention. it can.

As a method for producing the cyclic olefin represented by the general formula (I) or (II) as described above, for example,
A Diels-Alder reaction between cyclopentadiene and an olefin having a corresponding structure can be mentioned.

These cyclic olefins can be used alone or in combination of two or more. The cyclic olefin polymer used in the present invention can be prepared by using the cyclic olefin represented by the formula (I) or (II) as described above, for example, in JP-A-60-168708, JP-A-61-120816, 61
-115912, 61-115916, 61-271308, 61-2722
Nos. 16, 62-252406, 62-252407, etc., according to the method proposed by the present applicant, and by appropriately selecting conditions, it can be produced.

[A-1] Ethylene / cyclic olefin random copolymer [A-1] Ethylene / cyclic olefin random copolymer is composed of a structural unit derived from ethylene, usually 20 to
In a quantity of 95 mol%, preferably 30 to 90 mol%, the structural units derived from cyclic olefins are usually from 5 to 80 mol%.
Mol%, preferably 10 to 70 mol%. The composition ratio of ethylene and cyclic olefin is ¹³
It is measured by C-NMR.

In the [A-1] ethylene / cyclic olefin random copolymer, the structural units derived from ethylene and the structural units derived from the cyclic olefin are randomly arranged and bonded, It has a substantially linear structure. The fact that the copolymer is substantially linear and does not have a substantially gel-like cross-linked structure means that when the copolymer is dissolved in an organic solvent, the solution contains an insoluble component. You can confirm by not having. For example, when measuring the intrinsic viscosity [η], the copolymer
It can be confirmed by complete dissolution in decalin at 35 ° C.

In the [A-1] ethylene / cyclic olefin random copolymer used in the present invention, the above-mentioned formula (I)
Alternatively, at least a part of the cyclic olefin represented by (II) is considered to constitute a repeating unit represented by the following formula (III) or (IV).

[0048]

Embedded image In the formula (III), n, m, q, R ^{1 to} R ¹⁸ and R
^a and R ^b have the same meaning as in formula (I).

[0049]

Embedded image In formula (IV), n, m, p, q and R ¹ to R ^{1 9} are the same meaning as in formula (II).

The [A-1] ethylene / cyclic olefin random copolymer used in the present invention may have a composition derived from another copolymerizable monomer, if necessary, as long as the object of the present invention is not impaired. It may have a unit.

Examples of such other monomers include olefins other than the above-mentioned ethylene or cyclic olefin. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, Methyl-1-butene, 3-
Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-
Α- having 3 to 20 carbon atoms such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene
Olefin, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene and cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano Cycloolefins such as -1H-indene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene and 5-vinyl-2 Non-conjugated dienes such as -norbornene.

These other monomers can be used alone or in combination. [A-1] Ethylene
In the cyclic olefin random copolymer, structural units derived from other monomers as described above usually have 20 units.
It may be contained in an amount of up to 10 mol%, preferably up to 10 mol%.

The [A-1] ethylene / cyclic olefin random copolymer used in the present invention comprises ethylene and formula (I)
Alternatively, it can be produced by using the cyclic olefin represented by (II) by the production method disclosed in the above-mentioned publication. Among these, this copolymerization is carried out in a hydrocarbon solvent, and using a catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent as the catalyst, [A-1] ethylene / cyclic olefin random copolymer is used. It is preferred to produce a polymer.

In this copolymerization reaction, a solid group IV metallocene catalyst can also be used. Where solid IV
The group metallocene-based catalyst is a catalyst comprising a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organic aluminum oxy compound, and an organic aluminum compound optionally added. Here, the group IV transition metal is zirconium, titanium or hafnium, and these transition metals have a ligand containing at least one cyclopentadienyl skeleton. Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group or an indenyl group, a tetrahydroindenyl group, and a fluorenyl group which may be substituted with an alkyl group. These groups may be bonded via another group such as an alkylene group. Examples of the ligand other than the ligand having a cyclopentadienyl skeleton include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

As the organoaluminum oxy compound and the organoaluminum compound, those usually used for producing an olefin resin can be used. As such a solid group IV metallocene catalyst, those described in, for example, JP-A-61-221206, JP-A-64-106, and JP-A-2-173112 can be used.

[A-2] Ring-opened polymer or copolymer of cyclic olefin [A-2] Ring-opened polymer or copolymer of cyclic olefin is represented by the above formula (I) or (II) It is a ring-opened polymer of a cyclic olefin or a copolymer containing a ring-opened polymerized unit of a cyclic olefin represented by the above formula (I) and / or (II). In the case of a copolymer, two or more different cyclic olefins are used in combination.

In the ring-opened polymer or ring-opened copolymer of cyclic olefin, at least a part of the cyclic olefin represented by the above formula (I) or (II) is represented by the following formula (V) or (VI). It is considered to constitute a repeating unit to be performed.

[0058]

Embedded image In the formula (V), n, m, q and R ^{1 to} R ¹⁸ and R ^a and R ^b have the same meanings as in the formula (I). .

[0059]

Embedded image In formula (VI), n, m, p, q and R ¹ to R ^{1 9} are the same meaning as in formula (II).

Such a ring-opening polymer or ring-opening copolymer can be produced by the production method disclosed in the above-mentioned publication, for example, by subjecting a cyclic olefin represented by the above formula (I) to ring-opening polymerization. It can be produced by polymerization or copolymerization in the presence of a catalyst. As such a ring-opening polymerization catalyst, a catalyst comprising a metal halide selected from ruthenium, rhodium, palladium, osmium, indium or platinum, a nitrate or an acetylacetone compound, and a reducing agent, or titanium, palladium, zirconium Or a metal halide or acetylacetone compound selected from molybdenum or the like,
A catalyst comprising an organoaluminum compound can be used.

[A-3] A hydride of the ring-opened polymer or copolymer [A-3] A hydride of the ring-opened polymer or copolymer used in the present invention is obtained as described above. It is obtained by hydrogenating a ring polymer or a copolymer [A-2] in the presence of a conventionally known hydrogenation catalyst.

In the hydride of the ring-opened polymer or copolymer [A-3], at least a part of the cyclic olefin represented by the formula (I) or (II) is represented by the following formula (VI)
It is considered to constitute the repeating unit represented by (I) or (VIII).

[0063]

Embedded image In the formula (VII), n, m, q and R ^{1 to} R ¹⁸ and R ^a and R ^b have the same meaning as in the formula (I).

[0064]

Embedded image N in formula (VIII), m, p, q, R 1 ~R 1 9 formula (I
It has the same meaning as I).

[A-4] Graft Modified Product The graft modified product of the cyclic olefin polymer is the above-mentioned [A-1] ethylene / cyclic olefin random copolymer,
[A-2] a ring-opened polymer or copolymer of a cyclic olefin,
Or [A-3] a graft modified product of a hydride of a ring-opening polymer or copolymer.

Examples of the modifier used herein include unsaturated carboxylic acids, and specific examples thereof include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid and crotonic acid. , Isocrotonic acid, endocis-bicyclo [2.2.1] hept-5-ene-
Unsaturated carboxylic acids such as 2,3-dicarboxylic acid (Nadic acid ^TM ), and derivatives of these unsaturated carboxylic acids such as unsaturated carboxylic anhydrides, unsaturated carboxylic halides,
Examples thereof include unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and unsaturated carboxylic acid ester compounds.

The derivatives of unsaturated carboxylic acids include, more specifically, maleic anhydride, citraconic anhydride, maleenyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

Among these modifiers, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic anhydrides such as maleic acid, nadic acid and anhydrides of these acids are preferably used. These modifiers can be used in combination of two or more.

The modification rate of the graft-modified cycloolefin polymer used in the present invention is usually 10 mol%.
It is desirable that: Such a cyclic olefin polymer-grafted product can be produced by blending a cyclic olefin polymer with a modifier so as to obtain a desired modification ratio and graft-polymerizing the modified olefin polymer. The modified product can be prepared by mixing the modified product with an unmodified cyclic olefin-based resin.

In order to obtain a graft-modified product of a cyclic olefin polymer from a cyclic olefin resin and a modifier, a conventionally known polymer modification method can be widely applied. For example, a graft modified product is obtained by adding a modifying agent to a cyclic olefin polymer in a molten state and performing graft polymerization (reaction), or by adding a modifying agent to a solvent solution of the cyclic olefin polymer and performing a graft reaction. Can be obtained.

Such a graft reaction is usually carried out at 60 to 3
It is performed at a temperature of 50 ° C. The graft reaction can be performed in the presence of a radical initiator such as an organic peroxide and an azo compound.

A modified product having the above modification rate can be directly obtained by a graft reaction between a cyclic olefin polymer and a modifying agent, or a highly modified product is previously obtained by a graft reaction between a cyclic olefin resin and a modifying agent. After obtaining a modified product having a modified ratio, the modified product can be obtained by diluting the modified product with an unmodified cyclic olefin-based polymer so that a desired modification ratio is obtained.

In the present invention, the cyclic olefin polymer (A)
Any of [A-1], [A-2], [A-3] and [A-4] as described above can be used alone, or a combination of these can be used.

Of these, an ethylene / cyclic olefin random copolymer [A-1] is preferably used. Further, a tetracyclododecene-based ethylene / cyclic olefin random copolymer is preferable. In the present invention, other various polymers may be blended with the cyclic olefin polymer, if necessary, as long as the object of the present invention is not impaired.

Resin (B) Cyclic olefin polymer constituting conjugate fiber of the present invention
Resin (B) other than (A) is an acyclic polyolefin resin,
It is selected from the group consisting of polyester resins and polyamide resins. Each resin will be described.

The non-cyclic polyolefin resin is a linear or branched polyolefin having no cyclic structure, and includes a polymer or copolymer of an α-olefin having 2 to 20 carbon atoms. Specifically, polyethylene,
Examples include polypropylene, a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, and a copolymer of propylene with ethylene and / or an α-olefin having 4 or more carbon atoms. Examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. These may be used alone or in combination of two or more.

Examples of the polyester resin include polyethylene terephthalate, polytetramethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polybutylene terephthalate, and polycyclohexane terephthalate. These may be used alone or in combination of two or more.

As the polyamide resin, nylon 6,
Nylon 66, nylon 6/66 copolymer, nylon
6, 10, nylon 7, nylon 9, nylon 11, or a mixture thereof. These may be used alone or in combination of two or more.

The conjugate fiber of the present invention is preferably such that the cyclic olefin-based polymer (A) is formed so that at least a part of the fiber surface is continuously formed in the length direction. The resin may be of various shapes, such as a resin formed alternately along the circumferential direction in a fan shape in a fiber cross section, or a resin formed alternately in a strip shape. Among them, a side-by-side type composite fiber or a core-sheath type composite fiber is preferable in terms of easy production. Hereinafter, the side-by-side type composite fiber and the core-sheath type composite fiber will be described.

Side-by-side conjugate fiber The side-by-side conjugate fiber according to the present invention comprises a resin part (a) composed of the cyclic olefin polymer (A) and a resin part (b) composed of the resin (B). Have been. As a method for producing the side-by-side type conjugate fiber, various known methods are employed. A preferable method is a two-layer film including a layer of the cyclic olefin polymer (A) and a layer of the resin (B). And fibrillating the film.

An example of this method will be described. First, the cyclic olefin polymer (A) and the resin (B) are melted by different extruders, respectively, and sent to a laminating die to form a two-layer film. The method for forming the two-layer film may be a T-die method or an inflation method. The formed two-layer film is further stretched in the machine direction. The stretching ratio is usually
At 3 to 10 times, the thickness of the film after stretching is determined according to the desired fineness. Next, the two-layer film is defibrated by passing through a porcupine or the like to obtain a side-by-side type composite fiber. If a spinneret having a composite spinning nozzle configured to form and discharge a side-by-side structure is used, it can be manufactured in the same manner as a core-sheath type composite fiber described later.

The side-by-side type conjugate fiber has a weight composition ratio of the cyclic olefin polymer (A) / resin (B) [(A) /
(B)] is 10/90 to 60/40, preferably 20 /
80 to 40/60. Further, the fineness of the side-by-side type composite fiber according to the present invention as described above is usually 1 to 3.
0d, preferably 3 to 15d.

Further, in the present invention, if necessary, the resin constituting the conjugate fiber is added to the resin within a range that does not impair the object of the present invention.
Coloring agents, heat stabilizers, lubricants, nucleating agents, other polymers and the like can be blended.

Examples of the coloring agent include inorganic coloring agents such as titanium oxide and calcium carbonate, and organic coloring agents such as phthalocyanine. Examples of the heat stabilizer include phenol-based stabilizers such as BHT (2,6-di-t-butyl-4-methylphenol).

As the lubricant, for example, oleic acid amide, erucic acid amide, stearic acid amide and the like can be mentioned. In the present invention, in particular, a cyclic olefin polymer
It is preferable to add 0.1 to 0.5% by weight of a lubricant to (A) because the friction fastness of the obtained composite fiber is improved.

Further, it is preferable to add a modified resin with an unsaturated carboxylic acid to each resin constituting the conjugate fiber, because it suppresses delamination in the fibrillation step.

Core-sheath type composite fiber The core-sheath type composite fiber according to the present invention comprises a sheath portion made of the cyclic olefin polymer (A) and a core portion made of the resin (B). As a method for producing the core-sheath type composite fiber, various known methods are employed, and a preferable method is a composite spinning method. An example of this method will be described.
First, a composite spinning nozzle configured to melt a cyclic olefin-based polymer (A) and the resin (B) by different extruders, and to form a core-sheath structure to discharge each melt. Is discharged from a spinneret having a composite spinning to obtain a core-sheath type composite fiber.

The core-sheath type conjugate fiber has a cyclic olefin polymer (A) / resin (B) weight ratio [(A) / (B)] of 5%.
/ 95-50 / 50, preferably 10 / 90-30 / 7
0. The core-sheath type conjugate fiber according to the present invention has a fineness of usually 1 to 30 d, preferably 3 to 15 d.
It is.

Further, in the present invention, a coloring agent, a heat stabilizer, a lubricant, a nucleating agent, other polymers, and the like can be blended into the conjugate fiber as needed, as long as the object of the present invention is not impaired. Specifically, those exemplified for the side-by-side type conjugate fiber can be exemplified. The core-sheath type conjugate fiber according to the present invention as described above has a fineness of 30 d or less, and is preferably 15 d or less from the viewpoint that a nonwoven fabric having more excellent flexibility can be obtained.

The core-in-sheath type conjugate fiber according to the present invention may be of a concentric type in which a circular core portion is wrapped in a donut-shaped sheath portion having the same center in the fiber cross section. An eccentric type in which the center of the sheath is shifted and the core is surrounded by the sheath may be used. Further, an eccentric core-sheath composite fiber whose core part is partially exposed on the fiber surface may be used.

A woven fabric, a knitted fabric or a woven fabric formed from a conjugate fiber
Nonwoven Next, woven fabric formed of composite fibers according to the present invention, (hereinafter referred to as cloth) knitted fabric or nonwoven fabric is described. The fabrics formed from the conjugate fiber according to the present invention can take the form of a woven fabric, a knitted fabric, or a non-woven fabric depending on the use as long as the conjugate fiber of the present invention is used as a constituent fiber. For example, when the composite fiber is used for a filter material, it is preferable to use an electret fiber. To form an electret, for example, a two-layer film composed of the layer of the cyclic olefin polymer (A) and the layer of the resin (B) is formed, and after applying a DC voltage treatment to the film, the film is disintegrated. Obtained by fibering.

Specifically, for example, a woven fabric is preferred for use as an industrial wiper for machine maintenance or a rug such as a factory, and a knitted fabric is preferred for use as a carpet underlay or a shape retaining material for packaging materials. Further, for applications such as oil adsorbents and filter materials, nonwoven fabrics are preferred mainly from the viewpoint of economy. Here, the nonwoven fabric will be particularly described.

The nonwoven fabric comprising the conjugate fiber of the present invention is produced by a known method. When the conjugate fiber is a side-by-side type conjugate fiber, after the side-by-side type conjugate fiber is manufactured as described above, the fiber is cut into a predetermined length according to the purpose of use, opened, and a web is formed using the cotton. .
Subsequently, a confounding process such as needle punching, water jet, ultrasonic fusion, and embossing is performed to obtain a nonwoven fabric made of a side-by-side type composite fiber.

When the composite fiber is a core-sheath type composite fiber,
For example, a nonwoven fabric can be manufactured by a spun bond method using a composite spinning nozzle. That is, the composite is configured such that the cyclic olefin polymer (A) and the resin (B) are separately melted by an extruder or the like, and each melt is formed into a desired core-sheath structure and discharged. By discharging from a spinneret having a spinning nozzle, a core-sheath type composite fiber is spun. The spun conjugate fiber is cooled by a cooling fluid, and tension is further applied to the conjugate fiber by drawing air to a predetermined fineness, collected as it is on a collection belt and deposited to a predetermined thickness, Form the resulting web. Next, the same entanglement processing as described above is performed to obtain a nonwoven fabric made of the core-sheath type composite fiber.

The non-woven fabric comprising the conjugate fiber according to the present invention comprises
Usually, the basis weight is 10 to 1000 g / m. ^TwoAnd oil adsorbent
100-600 g / m^TwoOf filter material
For applications, 10 to 150 g / m^TwoIs used.

Further, the nonwoven fabric composed of the conjugate fiber according to the present invention may have a melt-blown nonwoven fabric formed of fibers having an ultrafine fiber diameter laminated on one or both surfaces of the nonwoven fabric. The fibers forming the melt blown nonwoven fabric are not particularly limited, and include, for example, single fibers made of a conventionally known thermoplastic resin, and core-sheath type or side-by-side type composite fibers.

The conjugate fiber of the present invention uses an oil-absorbing cyclic olefin polymer (A), and a resin (B) selected from the group consisting of an acyclic polyolefin resin, a polyester resin and a polyamide resin. Since it is a conjugate fiber, it has excellent shape retention after oil absorption. Woven, knitted or non-woven fabrics produced using these fibers can be dispersed in seawater or air by utilizing the excellent oil-absorbing properties and contaminant-adsorbing properties of the cyclic olefin polymer (A). Oil adsorbents and filter materials; deodorant filter materials such as tobacco odor, formalin odor, dry cleaning odor, and naphthalene odor;
Wiper materials such as eyeglass wipes, glass wipes, and oil stain removal;
Further, it can be suitably used for a rust-preventing cloth or the like in which oil is absorbed by utilizing its excellent shape retention after oil absorption.

[0098]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
Incidentally, the oil absorption of the nonwoven fabric obtained in Examples and Comparative Examples,
Evaluation of shape retention was performed by the following method.

(1) Evaluation of Oil Absorption A 10 cm × 10 cm test piece was placed on a test piece having a height of 10 cm.
1 ml of the test oil was dropped from the position (2) using a pipette for 2 seconds, and the shape of the oil spot on the test piece was measured. The oil spot is regarded as an ellipse and its major axis,
The minor axis was measured with a ruler to determine (major axis + minor axis) / 2. This operation was repeated for five samples, and their average value was calculated. The larger this is, the better the oil absorption is.

(2) Evaluation of Shape Retention A test piece of 10 cm × 10 cm was floated on a test oil horizontally on the oil surface and held for 5 minutes. Thereafter, one of the four corners of the test piece was hung with clips. After standing for 30 minutes, the test piece was transferred onto a wire mesh knitted with an iron wire having a diameter of 1.5 mm and a mesh size of 15 mm, and the shape change was visually observed.

(Example 1) Polypropylene (MFR (AST
0.5g (Measurement based on M D1238, temperature 230 ° C, load 2.16kg)
/ 10 min) 500 g of maleic anhydride-modified polypropylene (3% by weight of maleic anhydride graft modification)
g at the same time, extruder with 40 mm diameter (L / D = 40)
And heated and melt-kneaded at 220 ° C. to prepare a resin composition 1. Then ethylene and tetracyclo [4.4.0.1 ^{2, 5} .1
^7,10 ] -3-dodecene random copolymer (glass transition temperature 80 ° C, specific gravity 1.02, MFR (according to ASTM D1238, temperature 26
9500 g of maleic anhydride-modified polypropylene (500 g of maleic anhydride graft-modified) was heated and melt-kneaded at 250 ° C. in the same manner as in resin composition 1 to obtain a resin composition. Preparation 2 was prepared. These resin compositions 1 and 2 are fed to separate extruders to form a two-layer blown film having a thickness of 40 μm and a resin composition 1 / resin composition 2 = 3/1 in cross-sectional area ratio at 240 ° C. did.

The film was 5.9 mechanically oriented at 90 ° C.
It is stretched twice on a hot plate and rolled into a needle-shaped roll to break it into a mesh.
After delicately winding and winding, cut to 60 mm with a cutter and open cotton
The cotton is opened by a machine and the thickness of each resin part (resin composition 1 / tree
Fat composition 2) 30 μm / 27 μm side-by-side type
A composite fiber was obtained. Convert the obtained fiber into a web with a card
25g / m per entangled with needle punch ^Two, Thickness 0.
A 31 mm nonwoven fabric was produced. Oil absorption evaluation of this non-woven fabric
The results are shown in Table 1, and the results of shape retention evaluation are shown in Table 2.

(Example 2) Polypropylene as a core material
(MFR (according to ASTM D1238, temperature 230 ℃, load 2.16kg)
Measurement) 60 g / 10 min), using ethylene and tetra as sheath material.
Cyclo [4.4.0.1^2,5.1 ^7,10] -3-Dodecene random co-weight
Merging (glass transition temperature 80 ° C, specific gravity 1.02, MFR (A
(STM D1238 compliant, temperature 260 ° C, load 2.16kg) 30g
/ 10 min) to a separate extruder, melt-knead and spun
Spindle with 0.6mmφ hole and 1093 holes
Melt at a discharge rate of 1.0 g / min per hole using
Spinning is performed, the cross-sectional area ratio is core / sheath = 8/2, fineness 2.
A 5d concentric core-sheath composite fiber was obtained. Capture this as it is
After being deposited on the collecting surface, hot embossing (emboss area ratio 8
%) And 25 g / m per unit area^Two, Thickness 0.19
mm nonwoven fabric was produced. Oil absorption evaluation result of this nonwoven fabric
Are shown in Table 1, and the results of shape retention evaluation are shown in Table 2.

Comparative Example 1 Ethylene and tetracyclo [4.
4.0.1 ^{2,5.1 7,10} ] -3-Dodecene random copolymer (glass transition temperature 80 ° C, specific gravity 1.02, MFR (ASTM D1238
Compliant, measured at a temperature of 260 ° C and a load of 2.16 kg) 30 g / 10 min)
Is supplied to an extruder, melt-kneaded, and melt-spun by a spun bond method using a spinneret having 60 holes of 0.6 mmφ at a discharge rate of 1.0 g / min per single hole to form a melt-spun material on a collecting surface. And then partially joined by hot embossing (emboss area ratio: 8%), with a basis weight of 25 g / m ² and a thickness of 0.14 mm.
Was manufactured. Table 1 shows the results of oil absorption evaluation of this nonwoven fabric, and Table 2 shows the results of shape retention evaluation.

Example 3 Polypropylene (MFR (AST
0.5g (Measurement based on M D1238, temperature 230 ° C, load 2.16kg)
/ 10 min) to 9000 g of polycarbonate (GE company,
500 g of Lexan ^TM 101) and 500 g of maleic anhydride-modified polypropylene (maleic anhydride graft-modified amount: 3% by weight) were extruded into an extruder (L / D = 40 mmφ).
40), and heated and melted and kneaded at 220 ° C. to prepare a resin composition 1. Next, ethylene and tetracyclo [4.4.0.1
^2,5 .1 ^7,10] -3-random copolymer of dodecene (glass transition temperature 80 ° C., a specific gravity of 1.02, MFR (ASTM D1238 compliant,
Measurement at a temperature of 260 ° C and a load of 2.16 kg) 30 g / 10 min) 950
0g and the ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
A resin composition 2 was obtained by mixing 500 g of a maleic anhydride graft-modified product of a random copolymer of -3-dodecene (the amount of maleic anhydride graft-modified 0.69% by weight) with a tumble blender. These resin compositions 1 and 2 were supplied to separate extruders, and at 250 ° C., the resin composition 1 /
A two-layer blown film having a resin composition 2 = 2/1 and a thickness of 40 μm was formed.

The film was placed at 90 ° C. in the machine direction by 5.9.
The film is stretched twice on a hot plate, and the stretched film is separated by 8 m between electrodes.
continuous with 0.5 second residence time on the corona discharge electrode
And a DC voltage of -9 kV is applied.
And defibrate in a mesh form, and after winding, use a cutter.
Cut to 60mm, open with a cotton opener,
Thickness (resin composition 1 / resin composition 2) 30 μm / 27 μ
m of side-by-side type conjugate fiber was obtained. The resulting fiber
Is made into a web with a card and entangled with a needle punch.
30g / m ^TwoAnd a non-woven fabric having a thickness of 0.42 mm.
Table 1 shows the results of the oil absorption evaluation of this nonwoven fabric, and the shape retention evaluation.
Table 2 shows the results.

Example 4 The two-layer blown film obtained in Example 1 was stretched 5.9 times in the machine direction at 90 ° C. on a hot plate, laid on a needle-shaped roll, and defibrated into a mesh. After winding, it was cut to 5 mm with a cutter to obtain a side-by-side composite fiber assembly. After beaten with a beater together with 20 parts by weight of this aggregate and 80 parts by weight of non-pulverized pulp, 8 g of fiber (dry weight) in 1 liter of water is mixed with 50 g of a 15% by weight aqueous solution of polyacrylamide and 2.5 g of a surfactant. The mixture was charged, stirred, and squeezed with a tappy tester and dried to produce a nonwoven fabric having a basis weight of 30 g / m ² . Table 1 shows the results of oil absorption evaluation of this nonwoven fabric, and Table 2 shows the results of shape retention evaluation.

Example 5 Polypropylene (MFR (AST
0.5g (Measurement based on M D1238, temperature 230 ° C, load 2.16kg)
/ 10 min) 95 parts by weight of 5 parts by weight of maleic anhydride-modified polypropylene (3% by weight of maleic anhydride graft modification) simultaneously with an extruder having a diameter of 40 mmφ (L / D = 40)
And heated and melt-kneaded at 220 ° C. to prepare a resin composition 1. Then ethylene and tetracyclo [4.4.0.1 ^{2, 5} .1
^7,10 ] -3-dodecene random copolymer (glass transition temperature 80 ° C, specific gravity 1.02, MFR (according to ASTM D1238, temperature 26
Melting and kneading with 95 parts by weight and 5 parts by weight of maleic anhydride-modified polypropylene (maleic anhydride graft-modified amount: 3% by weight) at 250 ° C. in the same manner as in the resin composition 1 under the conditions of 0 ° C. and a load of 2.16 kg) 30 g / 10 min) Thus, a resin composition 2 was prepared. These resin compositions 1 and 2 are fed to separate extruders to form a two-layer blown film having a thickness of 40 μm and a resin composition 1 / resin composition 2 = 3/1 in cross-sectional area ratio at 240 ° C. did.

This film was 5.9 degrees at 90 ° C. in the machine direction.
It is stretched twice on a hot plate, woven into a mesh shape with a needle-shaped roll, wound up, cut into 60 mm with a cutter, opened with a cotton-opening machine, and the thickness of each resin part (resin composition 1 / Resin composition 2) A 30 μm / 27 μm side-by-side conjugate fiber was obtained. 10 g / m of the obtained fiber with a card
And the web into ² basis weight, further rayon fiber 70 parts by weight of 1.5d cut into 38mm this web, 56m
A fiber web of 20 g / m ² was formed by mixing and feeding a 30 d part of 3d polyester fiber cut to m with a card and molded, and entangled with a water jet from the rayon fiber and polyester fiber side to produce a nonwoven fabric. Table 1 shows the results of oil absorption evaluation of this nonwoven fabric, and Table 2 shows the results of shape retention evaluation.

[0110]

[Table 1]

[0111]

[Table 2]

[0112]

The composite fiber according to the present invention is excellent in oil absorbency and excellent in shape retention after oil absorption. Woven, knitted or nonwoven fabrics formed using these fibers are suitably used as oil adsorbents and filter materials due to the excellent oil absorbency and adsorbability of contaminants of the cyclic olefin polymer (A).

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 67/00 C08L 67/00 77/00 77/00 D01F 8/12 D01F 8/12 Z 8/14 8/14 Z D03D 15/00 D03D 15/00 A D04B 1/14 D04B 1/14 D04H 1/42 D04H 1/42 XK (72) Inventor Masahiro Takada 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Chemicals (72) Inventor Haruo Yuasa In the first place of Mitsui Chemicals Co., Ltd., Asahi-cho, Yokkaichi-shi, Mie (72) Inventor Motoyuki Ezaki 3-5-2 Kasumigaseki, Chiyoda-ku, Tokyo Mitsui Chemicals, Inc. F-term (Reference) 4J002 BB03X BB05X BB10W BB12X BB14X BB15X BK00W CE00W CF04X CF06X CF07X CF08X CL01X CL03X CL05X FA04W FA04X GK01 GN00 4L002 AA05 AA07 AB05 AC00 EA00 FA06 4A04 ABA07 BA08A31AA19 AA07 AA07 AA08 4L047 AA14 AA21 AA23 AA27 AB02 BA03 BA04 BA09 BB09 CA19 CB07 CB10 CC12 CC16 4L048 A A15 AA20 AA28 AA30 AA42 AB01 AC00 CA00 DA24 DA40

Claims (14)

[Claims] Claims: 1. An at least one cyclic olefin polymer (A) selected from the group consisting of the following [A-1], [A-2], [A-3] and [A-4]; Composite fiber composed of a resin (B) selected from the group consisting of a cyclic polyolefin-based resin, a polyester-based resin, and a polyamide-based resin; [A-1] ethylene and represented by the following formula (I) or (II) Ethylene / cyclic olefin random copolymer obtained by copolymerization with a cyclic olefin; (In the formula (I), n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently hydrogen. An atom, a halogen atom or a hydrocarbon group optionally substituted by halogen, wherein R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and It may have a double bond, and R ¹⁵ and R ¹⁶ or R ^15
17 and R ¹⁸ may form an alkylidene group. ), Embedded image (In the formula (II), p and q are 0 or a positive integer,
m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group which may be substituted by halogen,
The carbon atom to which R ⁹ or R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are bonded directly or via an alkylene group having 1 to 3 carbon atoms. When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. ), [A-2] a ring-opened polymer or copolymer of a cyclic olefin represented by the above formula (I) or (II), [A-3] a ring-opened polymer or copolymer [A-2] ] [A-4] a graft-modified product of the above [A-1], [A-2] or [A-3]. 2. The conjugate fiber according to claim 1, wherein the cyclic olefin polymer (A) forms at least a part of the fiber surface continuously in the length direction. 3. A side-by-side type composite fiber comprising a resin part (a) composed of the cyclic olefin polymer (A) and a resin part (b) composed of the resin (B). The conjugate fiber according to the above. 4. The side-by-side conjugate fiber is obtained by forming a two-layer film comprising a layer of the cyclic olefin polymer (A) and a layer of the resin (B), and defibrating the film. The conjugate fiber according to claim 3, which is obtained. 5. The conjugate fiber according to claim 2, wherein the conjugate fiber is a core-sheath type conjugate fiber composed of a sheath made of the cyclic olefin polymer (A) and a core made of the resin (B). 6. An ethylene / cyclic olefin random copolymer obtained by copolymerizing ethylene with the cyclic olefin represented by the formula (I) or (II), wherein the cyclic olefin polymer (A) is [ The conjugate fiber according to any one of claims 1 to 5, which is A-1]. 7. The conjugate fiber according to claim 6, wherein the cyclic olefin polymer (A) is a tetracyclododecene-based ethylene / cyclic olefin random copolymer. 8. A woven, knitted or non-woven fabric formed from the conjugate fiber according to claim 1. 9. The composite fiber according to claim 8, wherein the composite fiber is formed from electret composite fiber.
A woven, knitted or non-woven fabric. 10. The two-layered film comprising the electretized conjugate fiber and the layer of the cyclic olefin-based polymer (A) and the layer of the resin (B) is subjected to a DC voltage application treatment. The woven fabric, the knitted fabric or the nonwoven fabric according to claim 9, which is obtained by defibrating the fabric. 11. An oil absorbent using the woven, knitted or non-woven fabric according to claim 8. 12. A filter material using the woven, knitted or non-woven fabric according to claim 8. 13. A wiping material for removing oily dirt having an oily dirt removing function such as eyeglass wiping, glass wiping, or a wiper prepared using the oil sorbent according to claim 11. 14. A deodorizing filter for removing various odors produced by using the filter material according to claim 12.