JPH08144165A - Cycle olefin fiber-mixed fabric and the use thereof - Google Patents

Abstract

PURPOSE: To provide a fabric made of cyclic olefin-mixed fiber which is suitably useful as an oil absorption cloth because of its well-balanced properties, strength, elasticity, resistance to creep, heat, water, chemicals and solvent, and fabric hand. CONSTITUTION: Mixed nonwoven or woven fabric is produced by mixing the fibers formed from a polymer selected from the group consisting of (I-1) a random copolymer of ethylene and a cyclic olefin of formula I (n, q are each 0, 1; m is 0 or a positive integer; R<1> -R<18> , R<a> , R<b> are each H, a halogen, a hydrocarbon group, R<15> -R<18> may bond to each other to form a monocyclic or polycyclic ring) or of formula II (p, q are each 0 or 1 or more integer; m, n are 0-2; R<1> -R<19> are each H, a halogen, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy), (I-2) a ring-opening (co)polymer of this cyclic olefin, (I-3) a hydrogenated product of I-2, (I-4) graft-modified products of I-1, I-2 and I-3 with the fibers selected from the group consisting of polyamide, polyester, polyolefin, glass, boron and carbon fibers.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a cyclic olefin resin mixed cloth and its use. More specifically, it contains a cyclic olefin resin fiber as an essential component, and has strength, elastic modulus, creep resistance, heat resistance, water resistance and chemical resistance. The present invention relates to a cyclic olefin-based resin mixed cloth which has excellent properties such as properties, solvent resistance, and texture, and can be suitably used as an oil-absorbing cloth, and the use thereof.

[0002]

BACKGROUND OF THE INVENTION Conventionally, for example, when a tanker accident occurs, a polypropylene oil mat or the like is put on the sea surface in order to prevent the oil spilled from the tanker from spreading and to prevent the fishery from being adversely affected. Methods such as laying and absorbing the spilled oil are adopted. However, with this polypropylene oil mat (oil absorbing cloth),
There is a problem that the oil absorption efficiency is not sufficient.

By the way, as the resin forming the synthetic fiber, in addition to the above polypropylene, various resins such as polyamide, polyacrylonitrile, polyester resin, polyethylene and polyvinyl chloride can be cited. Synthetic fibers made of these resins have unique characteristics, feels, and textures depending on the type of resin used as the raw material, and are suitable for applications such as clothing, ropes, fishing lines, non-woven fabrics, and reinforcing materials for various resin compounds. Is appropriately selected and used. However, a nonwoven fabric made of these synthetic fibers is not always sufficient in terms of oil absorption efficiency to be used as an oil mat.

Therefore, when the present inventors searched for various resins in order to obtain an oil mat excellent in oil absorption efficiency,
A non-woven fabric composed of a cyclic olefin random copolymer fiber, which is a copolymer of a cyclic olefin having an ethylenic double bond in the ring and ethylene, absorbs oil, swells rapidly, and serves as an oil absorbing cloth (oil mat). It has been found that although it has excellent oil absorption efficiency, it has a problem that it is inferior in chemical resistance such as being dissolved when immersed in oil for a long time. Further, it has been found that when a non-woven fabric or a woven fabric made of the cyclic olefin random copolymer fiber is used for a purpose other than the oil absorbing cloth, it is not always sufficient depending on the use.

As a result of further studies, a non-woven fabric (mixed non-woven fabric) or a woven fabric (mixed woven fabric) composed of the cyclic olefin resin fiber and the fibers of polypropylene, polyamide, etc. [both are collectively referred to as “blended fabric”] Say]
Is excellent in oil absorption efficiency, chemical resistance, strength, elastic modulus, creep resistance, heat resistance, water resistance, solvent resistance, texture, etc. The present invention has been completed by finding that it can be suitably used for a wider range of applications than a non-woven fabric or a woven fabric made of only one kind of fiber.

Regarding this cyclic olefin resin, for example, JP-A-60-168708, 63-243111, 63-3
It is described in various publications such as 05111 and 63-223013. Further, the applicant of the present application has found out that such a fiber made of a cyclic olefin-based resin has unique properties, touch, texture, and the like, and can be used as a non-woven fabric, and the like, as Japanese Patent Application No. 4-299782. I have already proposed.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a new mixed fabric having a wide range of properties which can cope with the recent diversification of non-woven fabrics or woven fabrics, and its use.

More specifically, the present invention relates to strength, elastic modulus,
Creep resistance, heat resistance, water resistance, chemical resistance, solvent resistance,
The purpose of the present invention is to provide a new mixed fabric having excellent overall characteristics such as texture and its use.

[0009]

SUMMARY OF THE INVENTION The cycloolefin resin mixed cloth according to the present invention comprises two or more kinds of fibers, one of which is [A] the following [I-1], [I-2], [I- 3] and [I-4], which is a cyclic olefin resin fiber selected from the group consisting of: (In this specification, for example, a non-woven fabric or a woven fabric composed of two or more kinds of fibers, such as a non-woven fabric or a woven fabric composed of a cyclic olefin resin fiber and a polyamide fiber, is also simply referred to as a “mixed fabric”. [I-1] An ethylene / cyclic olefin random copolymer obtained by copolymerizing ethylene with a cyclic olefin represented by the following formula [I] or [II]:

[0010]

Embedded image

(In the formula [I], n is 0 or 1, and m is
Is 0 or a positive integer, q is 0 or 1, and R
^{1 to} R ¹⁸ and R ^a and R ^b are each independently
A hydrogen atom, a halogen atom or a hydrocarbon group, R ¹⁵
To R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group. ),

[0012]

[Chemical 4]

(In the 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,
It is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ¹³ (or R ¹⁰ ) is bonded to the carbon atom to which R ¹³ or R ¹¹ is bonded. It may be bonded to the carbon atom 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 ¹⁹ are bonded to each other. It may form a monocyclic or polycyclic aromatic ring. ), [I-
2] A ring-opening polymer or copolymer of the cyclic olefin represented by the above formula [I] or [II], [I-3] above [I-2]
Hydrogenated ring-opening polymer or copolymer, and [I-4]
The graft modified product of the above [I-1], [I-2] or [I-3].

In a preferred embodiment of the present invention, the cyclic olefin resin mixed cloth is composed of two or more kinds of fibers,
One of the fibers is the above [A]: cyclic olefin resin fiber, and the other fiber is [B]: polyamide fiber,
One or more fibers selected from organic fibers such as polyester fibers, polyethylene fibers, polypropylene fibers, and polycarbonate fibers, and inorganic fibers such as glass fibers, boron fibers, silicon carbide fibers, and carbon fibers. preferable.

The cyclic olefin resin composite fiber according to the present invention is composed of two or more kinds of fibers, one of which is the above [A] cyclic olefin resin fiber. In the present specification, the "composite fiber" refers to a fiber (composite filament) obtained by a method in which two or more kinds of fibers (filaments and fibrin) are fused or twisted together. In a preferred embodiment of the present invention, the cyclic olefin-based resin composite fiber is composed of two or more kinds of fibers, one of which is the [A] cyclic olefin-based resin fiber and the other fiber is [ B] It is desirable to select from organic fibers such as polyamide fibers, polyester fibers, polyethylene fibers, polypropylene fibers and polycarbonate fibers, or glass fibers, boron fibers, silicon carbide fibers and carbon fibers.

The cyclic olefin resin mixed cloth of the present invention is comprehensively excellent in properties such as strength, elastic modulus, creep resistance, heat resistance, water resistance, chemical resistance, solvent resistance, and texture. It is possible to widely meet diversified needs.

The above-mentioned mixed cloth is preferably used as an oil absorbing cloth (oil mat).

[0018]

DETAILED DESCRIPTION OF THE INVENTION The cyclic olefin resin mixed cloth and the cyclic olefin resin composite fiber according to the present invention will be specifically described below.

[Cyclic olefin resin mixed cloth] The cyclic olefin resin mixed cloth of the present invention comprises two or more kinds of fibers, and one kind of the fibers is [A] the following [I-1],
It is a cyclic olefin resin fiber selected from the group consisting of [I-2], [I-3] and [I-4].

The cyclic olefin resin forming the cyclic olefin resin fiber [A] (hereinafter, also referred to as [A] cyclic olefin resin) will be described below. [A] Cyclic olefin resin In the present invention, as the cyclic olefin resin [A], [I-1]: a random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II], [I-2]: Ring-opening polymer or copolymer of cyclic olefin represented by the following formula [I] or [II], [I-3]: Above-mentioned [I-2] ring-opening polymer or copolymer At least one selected from the combined hydride and [I-4] a graft modified product of the above [I-1], [I-2] or [I-3] is used.

The cyclic olefin resin [A] used in the present invention has a crystallinity measured by an X-ray diffraction method.
It is usually 20% or less, preferably 10% or less.

The cyclic olefin resin [A] is 13
The intrinsic viscosity [η] measured in decalin at 5 ° C is 0.
It is desirable that it is 01 to 20 dl / g, preferably 0.03 to 10 dl / g, and more preferably 0.05 to 8 dl / g.

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

Cyclic olefin

[0025]

Embedded image

In 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, R ^a and R ^b are each independently the following atoms or hydrocarbon groups, and when q is 0, each bond is bonded to form a 5-membered ring. Form.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon group includes, independently of each other, 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, and a cycloalkyl 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 (cooperatively with each other) to form a monocycle or polycycle, and the monocycle or polycycle thus formed has a double bond. Good. The monocyclic or polycyclic rings formed here are specifically exemplified below.

[0030]

[Chemical 6]

In the formula [II], p and q are 0 or a positive integer, and m and n are 0, 1 or 2. Also R
^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom,
It is 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, an alkyl group having 1 to 20 carbon atoms,
Examples thereof include halogenated alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. More specifically, as the alkyl group,
Examples include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group, and cycloalkyl groups include cyclohexyl group and 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, a phenylethyl group and the like.

Examples of the alkoxy group include methoxy group, ethoxy group and propoxy group.
These hydrocarbon group and alkoxy group 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 bound and the carbon atom to which R ¹³ is bound or the carbon atom to which R ¹¹ is bound are either directly or have 1 to 10 carbon atoms.
It may be bonded via the alkylene group of 3. That is, when the above 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 combine with each other to form a monocyclic or polycyclic aromatic ring. In this case, as the monocyclic or polycyclic aromatic ring, for example, n = m = 0 as shown below.
In this case, a group in which R ¹⁵ and R ¹² further form an aromatic ring can be mentioned.

[0036]

[Chemical 7]

Here, q has the same meaning as q in the formula [II]. Specific examples of the cyclic olefin represented by the above formula [I] or [II] are shown below.

[0038]

Embedded image

The bicyclo [2.2.1] -2-heptene (= norbornene) represented by (in the above general formula, the numbers 1 to 7 represent carbon position numbers) and the compound has a hydrocarbon group. Substituted derivatives are mentioned.

As this 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- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- (anthracenyl), 5 An example is 6,6-diphenyl.

As other derivatives, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-
Tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a
-Bicyclo [2.2.1] such as hexahydroanthracene-
A 2-heptene derivative 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
- tricyclo [4.3.0.1 ^2,5] -3- decene derivatives such as methyl tricyclo [4.3.0.1 ^2,5] -3- decene, tricyclo [4.4.0.1 ^2,5] -3- undecene, 10-methyl Tricyclo [4.4.0.1 ^2,5 ] -3-undecene and other tricyclo [4.4.
0.1 ^2,5 ] -3-undecene derivatives,

[0043]

[Chemical 9]

Tetracyclo [4.4.0.1 ^2,5 .1 represented by the [0044]
^7,10 ] -3-dodecene and derivatives in which a hydrocarbon group is substituted are included. As the hydrocarbon group, 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,
Examples thereof include 8- (biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8- (anthracenyl) and 5,6-diphenyl.

Further, a tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene derivative such as an adduct of (cyclopentadiene-acenaphthylene adduct) and cyclopentadiene, 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 derivatives thereof, 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, Nonashikuro [10.9.1.1 ^4,7 .1 ^{13, 20} .1 ^{15 and 18} .0
^2,10 .0 ^3,8 .0 ^12,21 .0 ^14,19] such as 5-pentacosene and derivatives thereof.

Specific examples of the cyclic olefin represented by the above formula [I] or formula [II] which can be used in the present invention are as described above. , Japanese Patent Application No. 5-196475 filed by the applicant of the present application, paragraph number [00
32] to [0054], and those exemplified here also in the present invention can be used as the cyclic olefin of the present invention.

The cyclic olefin represented by the above general formula [I] or [II] can be produced by subjecting cyclopentadiene and olefins having a corresponding structure to a Diels-Alder reaction.

These cyclic olefins may be used alone or in combination of two or more. The cyclic olefin resin 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 and JP-A-61-120816.
-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.

[I-1] Ethylene / Cyclic Olefin Lander
The copolymer [I-1] ethylene / cyclic olefin random copolymer usually has a constitutional unit derived from ethylene from 20 to 9
It contains structural units derived from cyclic olefins in amounts of usually 5 to 80 mol%, preferably 10 to 70 mol%, in amounts of 5 mol%, preferably 30 to 90 mol%.
The composition ratio of ethylene and cyclic olefin is ¹³ C-
Measured by NMR.

In this [I-1] ethylene / cyclic olefin random copolymer, the structural units derived from ethylene and the structural units derived from cyclic olefin as described above are randomly arranged and bonded, It has a substantially linear structure. The fact that this copolymer is substantially linear and does not have a substantially gel-like crosslinked structure means that when this copolymer is dissolved in an organic solvent, this solution contains insoluble components. Can be confirmed by not. For example, when the intrinsic viscosity [η] is measured, this copolymer is
It can be confirmed by being completely dissolved in decalin at 5 ° C.

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

[0052]

[Chemical 10]

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].

[0054]

[Chemical 11]

In the formula [IV], n, m, p, q and R ^{1 to} R ¹⁹ have the same meanings as in the formula [II]. Further, the [I-1] ethylene / cyclic olefin random copolymer used in the present invention has a structural unit derived from another copolymerizable monomer as needed within a range not to impair the object of the present invention. May be.

Examples of such other monomer include ethylene and olefins other than the above-mentioned cyclic olefins. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 3- 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- with 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 -1 H-indene and other cycloolefins, 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 can be mentioned.

These other monomers can be used alone or in combination. [I-1] ethylene
In the cyclic olefin random copolymer, the constitutional unit derived from the other monomer as described above is usually 20
It may be contained in an amount of not more than mol%, preferably not more than 10 mol%.

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

In this copolymerization reaction, a solid group IVB metallocene catalyst can be used. Where solid IV
The Group B metallocene catalyst is a catalyst composed of a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organoaluminum oxy compound, and an organoaluminum compound to be blended if necessary. Here, the group VI transition metal is zirconium, titanium or hafnium, and these transition metals have at least one ligand having a cyclopentadienyl skeleton. here,
Examples of the ligand containing a cyclopentadienyl skeleton include a cyclopentadienyl group which may be substituted with an alkyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group. These groups may be bonded via another group such as an alkylene group. Further, ligands other than the ligand having a cyclopentadienyl skeleton include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like.

Further, as the organoaluminum oxy compound and the organoaluminum compound, those generally used for the production of olefin resins can be used. Such a solid group IVB metallocene catalyst is described in, for example, JP-A-61-221206, JP-A-64-106, and JP-A-2-173112.

[I-2] Ring-opening polymer of cyclic olefin
In the ring-opening polymer or ring-opening copolymer of the copolymer 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 the repeating unit represented.

[0062]

[Chemical 12]

In the formula [V], n, m, q and R ¹
R ¹⁸ and R ^a and R ^b have the same meaning as in formula [I].

[0064]

[Chemical 13]

In the formula [VI], n, m, p, q and R ^{1 to} R ¹⁹ have the same meanings as in the formula [II]. Such a ring-opening polymer or a ring-opening copolymer can be produced by the production method disclosed in the above-mentioned gazette. It can be produced by polymerization or copolymerization below.

As such a ring-opening polymerization catalyst, a catalyst comprising a metal halide, nitrate or acetylacetone compound selected from ruthenium, rhodium, palladium, osmium, indium or platinum and a reducing agent, or titanium, A catalyst composed of a halide of a metal selected from palladium, zirconium, molybdenum or the like or an acetylacetone compound and an organoaluminum compound can be used.

[I-3] Hydrogen of Ring-Opening Polymer or Copolymer
The hydride of the ring-opening polymer or copolymer [I-3] used in the present invention is obtained by using the ring-opening polymer or copolymer [I-2] obtained as described above with a conventionally known hydrogen atom. It is obtained by hydrogenation in the presence of an added catalyst.

In the hydride of the [I-3] ring-opening polymer or copolymer, at least a part of the cyclic olefin represented by the formula [I] or [II] is represented by the following formula [VII]
Alternatively, it is considered to have a repeating unit represented by [VIII].

[0069]

Embedded image

In the formula [VII], n, m, q and R ¹
R ¹⁸ and R ^a and R ^b have the same meaning as in formula [I].

[0071]

[Chemical 15]

In the formula [VIII], n, m, p, q, R
^{1 to} R ¹⁹ have the same meaning as in formula [II]. [I-4] Graft-modified product The graft-modified product of the cyclic olefin resin is the above-mentioned [I-
1] Ethylene / cyclic olefin random copolymer, [I-
2] A ring-opening polymer or copolymer of a cyclic olefin, or a graft modified product of a hydride of [I-3] ring-opening polymer or copolymer.

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

Specific examples of the unsaturated carboxylic acid derivative include maleic anhydride, citraconic anhydride, maleenyl chloride, maleimide, monomethyl maleate, dimethyl maleate, and glycidyl maleate.

Among these modifiers, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic acid 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 ratio of the graft-modified cycloolefin resin used in the present invention is usually preferably 10 mol% or less. Such a graft modified product of a cyclic olefin-based resin can be produced by blending a cyclic olefin-based resin with a modifying agent so as to have a desired modification ratio and then graft-polymerized. It can also be produced by preparing and then mixing this modified product with an unmodified cyclic olefin resin.

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

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

A modified product having a modification ratio as described above can be obtained directly by a graft reaction between a cyclic olefin resin and a modifier, and a modified product having a high modification ratio can be obtained beforehand by a graft reaction between the cyclic olefin resin and a modifier. It is also possible to obtain the modified product by diluting the modified product with an unmodified cyclic olefin resin so as to obtain a desired modification ratio.

In the present invention, the cyclic olefin resin [A]
As the above, any one of the above [I-1], [I-2], [I-3] and [I-4] can be used alone, or these can be used in combination.

Of these, ethylene / cyclic olefin random copolymer [I-1] is preferably used. The cyclic olefin resin fiber of the present invention can be produced by heating the above cyclic olefin resin [A] to a temperature lower than the thermal decomposition temperature to melt it, and spinning it by a usual method. However, this cyclic olefin resin [A]
In addition, a resin composition obtained by further blending another resin can be spun.

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

Other resin components that can be added (1) A polymer derived from a hydrocarbon having one or two unsaturated bonds. Specific examples include polyolefins such as polyethylene, polypropylene, polymethylbutene-1, poly-4-methylpentene-1, polybutene-1 and polystyrene. Note that these polyolefins may have a crosslinked structure. (2) A 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.

Specifically, polyacrylate, polymethacrylate, polyacrylamide, polyacrylonitrile, or a copolymer with a monomer constituting the above-mentioned polymer, for example, acrylonitrile / butadiene / styrene copolymer or acrylonitrile / styrene copolymer. , Acrylonitrile / styrene / acrylic acid ester copolymers and the like. (4) Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals.

Concretely, polyvinyl alcohol, polyvinyl acetate, polyvinyl thraphosphate, vinyl polybenzoate, vinyl polymaleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, or a copolymer of the above-mentioned monomers is used. Examples include coalesced products such as ethylene and vinyl acetate copolymers. (5) Polymers derived from epoxides.

Specific examples include polymers derived from polyethylene oxide or bisglycidyl ether. (6) Polyacetal.

Specific examples include polyoxymethylene, polyoxyethylene, and polyoxymethylene containing ethylene oxide as a comonomer. (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.

Specific examples include nylon 6, nylon 66, nylon 11 and nylon 12. (12) Polyesters derived from dicarboxylic acids and dialcohols and / or oxycarboxylic acids or the corresponding lactones.

Specifically, polyester terephthalate,
Polybutylene terephthalate, poly-1,4-dimethylol
Examples thereof include cyclohexane terephthalate. (13) A polymer having a crosslinked structure derived from aldehyde and phenol, urea or melamine.

Specific examples include phenol / formaldehyde resins, urea / formaldehyde resins, and melamine / formaldehyde resins. (14) Alkyd resin.

Specific examples thereof 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 polymer.

Specific examples include cellulose, rubber, proteins, and derivatives thereof such as cellulose acetate, cellulose propionate, and cellulose ether. (17) Soft polymer.

The soft polymer will be described below in (i).
Rubbery components selected from the group of (v) to (v). The cycloolefin resin fiber (filament) composed of the cycloolefin resin [A] and these rubber-like components is particularly excellent in impact strength. These rubber-like components may be further subjected to a crosslinking reaction in the presence of an organic peroxide, and when a rubber-like component cross-linked with such an organic peroxide is used, a cyclic compound excellent in impact resistance is obtained. It is preferable because an olefin resin mixed cloth or a cyclic olefin resin composite fiber can be obtained.

[Soft Polymer Containing Cyclic Olefin Component (i)] The soft polymer containing a cyclic olefin component is a cyclic olefin of the same kind as that used in the preparation of the ethylene component and the cyclic olefin resin (the formula [ I] or a copolymer obtained by copolymerizing with the component of the formula [II]). The soft polymer (i) contains a cyclic olefin component and an ethylene component as essential components, and α
-The olefin component can be used within a range that does not impair the object of the present invention.

Examples of the α-olefin include propylene, 1-butene, 4-methyl-1-butene, 1-hexene, 1
-Octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-Hexadecene, 1-octadecene, 1-eicosene and the like. Among these, α having 3 to 20 carbon atoms
-Olefins are preferred. Further, cyclic olefins and cyclic dienes such as norbornene, ethylidene norbornene and dicyclopentadiene are also preferable.

In the soft polymer (i) containing the 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 the range of mol%.

Unlike the cyclic olefin resin, 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. The 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 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5% as measured by an X-ray diffraction method.

The soft polymer (i) is described in JP-A-60-168.
708, JP 61-120816, JP 61-115912, and JP 61-11591.
6, JP-A-61-271308, JP-A-6-6
It can be produced by appropriately selecting the conditions according to the method proposed by the present applicant in JP-A 1-272216, JP-A-62-252406, JP-A-62-252406 and the like.

[Α-Olefin Copolymer (ii)] α-Olefin Copolymer (i) Used as a Soft Polymer
i) is an amorphous to low crystalline copolymer composed of at least two α-olefins. Specific examples include ethylene / α-olefin copolymers and propylene / α-olefin copolymers.

The α-olefin constituting the ethylene / α-olefin copolymer is usually one having 3 to 20 carbon atoms, and specific examples include propylene, 1-butene, and 4-methyl.
Examples include -1-butene, 1-hexene, 1-octene and 1-decene, etc., or a mixture thereof. Among them, α-olefins having 3 to 10 carbon atoms are particularly preferable.

The molar ratio of ethylene / α-olefin copolymer (ethylene / α-olefin) is generally 40/60 to 95/5, though it varies depending on the kind of α-olefin. Further, the above molar ratio is preferably 40/60 to 90/10 when the α-olefin is propylene, and 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, those having 4 to 20 carbon atoms are usually used, and specifically, 1-butene and 4-methyl-1-
Butene, 1-hexene, 1-octene and 1-decene, etc.
Alternatively, a mixture thereof may be used. Of these, α-olefins having 4 to 10 carbon atoms are particularly preferable.

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

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

The α-olefin constituting these copolymer rubbers is usually an α-olefin having 3 to 20 carbon atoms (4 to 20 in the case of propylene / α-olefin), for example, propylene, 1-butene, 1 Examples include -pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and mixtures thereof. Of these, α-olefins having 3 to 10 carbon atoms are preferable.

Further, the diene component constituting these copolymer rubbers is 1,4-hexadiene, 1,6-octadiene, 2-
Linear non-conjugated dienes such as methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene and 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene,
Methyl tetrahydroindene, 5-vinyl norbornene,
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 ethylene / α-olefin / diene copolymer rubber, the molar ratio of ethylene to α-olefin (ethylene / α-olefin) varies depending on the type of α-olefin, but is generally 40 / 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-based hydrocarbon / conjugated diene-based soft copolymer (iv)] The aromatic vinyl-based hydrocarbon / conjugated diene-based soft copolymer used as the soft polymer is an aromatic vinyl-based hydrocarbon or conjugated It is a diene-based random copolymer, a block copolymer, or a hydride 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 rubber, hydrogenated styrene / isoprene / styrene block A copolymer rubber, a styrene / butadiene random copolymer rubber, or a rubber obtained by graft-polymerizing styrene, methyl acrylate or the like on these rubbers is used.

In these copolymer rubbers, the hydrogenated copolymer rubber is a copolymer rubber obtained by hydrogenating some or all of the double bonds remaining in the above copolymer rubber. When it is necessary to increase the impact strength of the cyclic olefin resin mixed cloth or the cyclic olefin resin composite fiber, it is preferable to use these copolymer rubbers.

[Soft Polymer or Copolymer (v) Comprising Isobutylene or Isobutylene / Conjugated Diene] The isobutylene-based soft polymer or copolymer (v) used as the soft polymer is Examples thereof include isobutylene rubber, polyisoprene rubber, polybutadiene rubber, and isobutylene / isoprene copolymer rubber.

In the present invention, the soft polymer (17)
Etc. can be kneaded with the cyclic olefin resin [A] as it is and used for spinning. For example, first, a kneaded product in which the above-mentioned soft polymer or the like is dispersed in the cyclic olefin resin is prepared, Further, the kneaded product may be treated with an organic peroxide to form a crosslinked structure between the cyclic olefin resin and the soft polymer in the kneaded product.

Examples of the organic peroxide used here include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, 1,1-bis (t-butylperoxy) cyclohexane 2,2- Peroxyketals such as bis (t-butylperoxy) octane, t-butylhydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide
Oxides, hydroperoxides such as 1,1,3,3-tetramethylbutylhydroperoxide, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy)
Hexane (trade name: Perhexa 25B), 2,5-dimethyl
-Dialkyl peroxides such as -2,5-di (t-butylperoxy) hexyne-3, diacyl peroxides such as lauroyl peroxide, benzoyl peroxide, t-butylperoxyacetate, t-butylperoxybenzoate And peroxyesters such as 2,5-dimethyl-2,5-di (benzoylperoxy) hexane.

The amount of the above-mentioned organic peroxide component is 10 in total of the cyclic olefin resin [A] and the soft polymer component.
It is generally 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 0 part by weight.

When the compound is further treated with an organic peroxide for the purpose of further increasing the crosslinking efficiency, a compound having two or more radically polymerizable functional groups in the molecule is further contained,
A cycloolefin resin mixed cloth or cycloolefin resin composite fiber having excellent impact resistance can be obtained, which is preferable.

Examples of the compound having two or more radically polymerizable functional groups in the molecule include divinylbenzene, vinyl acrylate, vinyl methacrylate and the like. The amount of these compounds is usually 1 part by weight or less, preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the total amount of the cyclic olefin resin [A] and the soft polymer (17). Used in.

Such a soft polymer (soft (co) polymers (i) to (v)) is a cyclic olefin resin [A] 10
By using the total amount thereof in an amount of usually 0.01 to 40 parts by weight, preferably 0.05 to 30 parts by weight, particularly preferably 0.1 to 20 parts by weight, relative to 0 parts by weight,
A cycloolefin resin mixed cloth or cycloolefin resin composite fiber having a good balance of properties such as light transmittance, diffusivity, strength, rigidity, heat distortion temperature and hardness can be obtained.

[Other Additives] The cycloolefin-based resin mixed cloth and the cycloolefin-based resin composite fiber according to the present invention include the above-mentioned cycloolefin-based resin [A] and the above-mentioned “other resin component” which is blended as necessary. However, in addition to these components, within the range that does not impair the object of the invention, conventionally known heat stability, weather resistance stability, antistatic agent, slip agent, antiblocking agent, antifog agent, lubricant, Dyes, pigments, natural oils, synthetic oils, waxes, etc. may be added.

For example, as a stabilizer compounded as an optional component, 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'-oxamide bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Phenol type antioxidants such as propionate, zinc stearate, calcium stearate, fatty acid metal salts such as calcium 1,2-hydroxystearate, glycerin monostearate, glycerin distearate, pentaerythritol Examples thereof include polyhydric alcohol fatty acid esters such as rumonostearate, pentaerythritol distyrate, and pentaerythritol tristearate. These may be blended alone or in combination. For example, tetrakis [methylene-3
Examples include a combination of-(3.5-di-t-butyl-4-hydroxyphenyl) propionate] methane, zinc stearate, and glycerin monostearate. These stabilizers can be used alone or in combination of two or more.

As the organic or inorganic filler, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balun, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dowamite, Examples thereof include calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, calcium silicate, montmorillonite, pentonite, graphite, aluminum powder and molybdenum sulfide.

The cyclic olefin polymer and the other components are
Mixing can be performed using a known method. For example, each component can be mixed simultaneously. Production of Cyclic Olefin Resin Fiber for Mixing Cloth The cyclic olefin resin fiber used in the present invention is obtained by converting a composition obtained by adding the above-mentioned cyclic olefin resin or, if necessary, other components as described above into a conventionally known fiber. It can be obtained by the method.

Examples of the spinning method in fiberization include a dry spinning method, a wet spinning method, a melt spinning method and an emulsion spinning method. Among these spinning methods, the melt spinning method is particularly preferable.

In this melt spinning method, the cyclic olefin-based resin (or composition) is heated to a temperature not lower than the melting point (or softening point) and lower than the decomposition temperature, preferably 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. Although various types of nozzles can be used in this method, 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 usually 0.01 to 100 m / min, preferably 0.05 to 10 m / min.
It is a degree. 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. At this time, the draw ratio is usually 10 to 10,000, preferably 100 to 5,000.

The raw yarn obtained by spinning in this way can be subjected to a post-treatment process for the purpose of removing impurities, tension drawing, heat treatment, refining, dyeing and the like.

[B] Other Fibers The cyclic olefin resin mixed fabric and the cyclic olefin resin composite fiber according to the present invention are composed of two or more kinds of fibers (fibers), one of which is as described above. [A] Cyclic olefin resin fiber, but as the other fiber, various conventionally known fibers can be used, and [B] organic fiber such as polyamide fiber, polyester fiber, polyethylene fiber, polypropylene fiber and polycarbonate fiber. Inorganic fibers such as glass fiber, boron fiber, silicon carbide fiber and carbon fiber.

Of these, organic fibers are preferred, and polyamide fibers, polyester fibers, polyethylene fibers and polypropylene fibers are more preferred. Production of Cycloolefin Resin Mixed Cloth and Cycloolefin Resin Composite Fiber The cycloolefin resin mixed fabric (that is, woven fabric and non-woven fabric) according to the present invention can be produced by a conventionally known method.

For example, in order to produce a nonwoven fabric for an oil absorbing cloth (oil mat) using [A] cyclic olefin resin fiber and [B] other fiber (eg polyamide fiber), short fiber The [A] cyclic olefin resin and the short fiber [B] other fibers may be formed into a sheet and fused or bonded with an adhesive or the like. More specifically, for example, the short fibrous [A] cyclic olefin resin fibers and the short fibrous [B] other fibers are blended with a cotton blending machine to form a sheet (web) with a spinning card machine. )
To This web is usually aligned approximately parallel to the length of the fiber, being strong in the length and weak in the cross. Therefore, in general, another parallel array web is overlaid on the web so that the longitudinal direction of the fibers intersects (orthogonal to) the web, and is arrayed so that there is no difference in strength depending on the direction. Then, an adhesive may be added to the cross-arranged web for adhesion, or the web may be mechanically entangled with a needle punch to join the short fibers together. In addition,
A short web [A] cyclic olefin-based resin and a short fiber [B] other fiber may be joined by a method as described above by scattering and dropping by an air flow. Dry method). In addition, the short fibrous [A] cyclic olefin resin fibers and the short fibrous other [B] other fibers (example:
Polyamide fiber) and dispersed in water or adhesive,
It may be strained with a paper machine (wet method). Further, the [A] cyclic olefin resin fiber and the [B] other fiber may be melt-spun and at the same time a web may be formed and fused (direct method).

For example, 10 to 50% by weight of [A] cyclic olefin resin fiber and the above [B] polyamide fiber 90 to 5
0% by weight ([A] + [B] = 100% by weight) and the non-woven fabric or woven fabric obtained by the above-mentioned method are acid,
Even after soaking in alkali for a long time, it retains the same tensile strength as the cyclic olefin resin originally had, and even after being soaked in hydrocarbon such as kerosene for a long time, it has the same polyamide originally as it had. The above-mentioned various properties such as the tensile strength of the product are retained, that is, strength, elastic modulus, creep resistance,
It has excellent properties such as heat resistance, water resistance, chemical resistance, solvent resistance, and texture in a well-balanced manner and can be suitably used, for example, as an oil absorbing cloth (oil mat).

[A] Cyclic olefin resin fiber 9
A mixed fabric using 0 to 10% by weight and the above [B] other fiber: for example, 10 to 90% by weight of polyamide fiber ([A] + [B] = 100% by weight) is used for acid resistance and alkali resistance. It can be suitably used as clothing, rag, and the like.

The cyclic olefin resin composite fiber of the present invention can also be produced by a conventionally known method. For example, the above-mentioned [A] cyclic olefin resin fiber,
[B] It can be obtained by fusion bonding or twisting with other fibers according to a conventional method. Such a cyclic olefin resin composite fiber (composite filament) of the present invention
Can be used for clothes, ropes, fishing lines, non-woven fabrics, reinforcing agents for compounds of various resins, and the like. The [A] cyclic olefin resin fiber and the [B] other fiber used at this time may be in the form of short fibers or long fibers.

In the present invention, the cyclic olefin resin composite fiber may be used in place of the above-mentioned [A] cyclic olefin resin fiber in the production of the cyclic olefin resin mixed fabric. .

[0132]

Industrial Applicability The cycloolefin resin composite fiber of the present invention has sufficient strength, elastic modulus, creep resistance, heat resistance, water resistance, chemical resistance, solvent resistance and texture while maintaining sufficient moldability. Is excellent. Further, the cyclic olefin resin mixed cloth of the present invention also has the same excellent properties as the above-mentioned conjugate fiber.

[0133]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

The polymer used as a raw material was prepared by the following method, molded into a nonwoven fabric, and various physical properties were examined. The methods for measuring and evaluating various physical properties are shown below. (1) Heat resistance: The sample was left in an air oven for 5 hours, and the temperature at which the shape was not retained was taken as the heat resistant temperature of the sample. (2) Chemical resistance: Each test solution was immersed in 80 ° C. for 7 days, and the retention rate of tensile strength was examined.

[0135]

EXAMPLE 1 Ethylene and tetracyclo [4.4.0.1 ^{2, 5} .1
^7,10 ] -3-dodecene (hereinafter simply referred to as “tetracyclododecene”
May be described as)) [Cryogenic olefin-based random copolymer (ethylene content 62 mol%, intrinsic viscosity [η] measured in decalin at 135 ° C .: 0.61 dl / g, DS
Glass transition temperature (Tg) measured by C method: 138
℃] using a single-screw extruder, cylinder temperature 230 ℃
Then, extrude at a speed of 0.1 m / min with a die having a diameter of 1 mmφ and extrude the resin for 300 m while air cooling
The monofilament of a cyclic olefin random copolymer having a diameter of about 30 μmφ was obtained by winding and stretching at a winding speed of 1 / min.

The obtained monofilament was made to have a length of about 50.
It was cut into mm (monofilament [A]). On the other hand, polyamide-6 (CM1021-TM manufactured by Toray Industries, Inc.) was spun at a molding temperature of 280 ° C. in the same manner as the above cyclic olefin random copolymer and then cut to have a diameter of about 30 μmφ,
A monofilament [B] having a length of about 50 mm was obtained.

The above-mentioned two kinds of monofilaments [A] and [B] thus obtained were mixed in a weight ratio of 1/1, and both fibers were entangled with a card machine to prepare a mixed woven nonwoven fabric.

Table 1 shows the evaluation results of the obtained non-woven fabric.

[0139]

Comparative Example 1 A nonwoven fabric was prepared in the same manner as in Example 1 except that the cyclic olefin random copolymer monofilament [A] obtained in Example 1 was used alone.

Table 1 shows the evaluation results of the obtained nonwoven fabric.

[0141]

Comparative Example 2 Example 1 was repeated except that the monofilament [B] of polyamide-6 (CM1021-TM manufactured by Toray Industries, Inc.) obtained in Example 1 was used alone.
A non-woven fabric was prepared in the same manner as in.

Table 1 shows the evaluation results of the obtained nonwoven fabric.

[0143]

[Table 1]

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08F 283/14 MQW C08G 61/08 NLG D01F 6/30 8/06 D03D 15/00 A

Claims (4)

[Claims] 1. A group consisting of two or more kinds of fibers, one of which is [A] a group consisting of [I-1], [I-2], [I-3] and [I-4] below. A cyclic olefin resin mixed fabric characterized by being a cyclic olefin resin fiber selected from: [I-1] ethylene and a cyclic olefin represented by the following formula [I] or [II] are copolymerized: Obtained ethylene / cyclic olefin random copolymer: (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: A hydrogen atom, a halogen atom or a hydrocarbon group, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond; R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.), (In the 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, or an aliphatic carbon atom. A hydrogen atom, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein the carbon atom to which R ⁹ (or R ¹⁰ ) is bonded and the carbon atom to which R ¹³ or R 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 ¹⁹ are bonded to each other to form a monocyclic ring or A polycyclic aromatic ring may be formed), [I-2] a ring-opening polymer or copolymer of the cyclic olefin represented by the above formula [I] or [II], [I-3 ] The above [I-2] hydride of a ring-opening polymer or copolymer, and [I-4] above [I-
1], [I-2] or [I-3] graft modified product. 2. A group consisting of two or more kinds of fibers, one of which is [A] the group consisting of [I-1], [I-2], [I-3] and [I-4] above. A cyclic olefin resin fiber selected from the other fibers, and the other fiber is [B] polyamide fiber, polyester fiber, polyethylene fiber, polypropylene fiber, polycarbonate fiber,
A cyclic olefin resin mixed cloth, which is selected from glass fiber, boron fiber, silicon carbide fiber, and carbon fiber. 3. An oil absorbing cloth made of the mixed cloth according to claim 1. 4. A group consisting of two or more kinds of fibers, one of which is [A] the group consisting of [I-1], [I-2], [I-3] and [I-4] above. A cyclic olefin resin composite fiber, which is a cyclic olefin resin fiber selected from