JP2001226862A - Nonwoven fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nonwoven fabric excellent in stiffness, recoverability to a compression (elastic recovery factor), heat resistance, water resistance, oil absorbability and a touch feeling with a good balance. SOLUTION: This nonwoven fabric is characterized in that the nonwoven fabric is formed by a fiber composed of a specific cyclic hydrocarbon-based polymer. The nonwoven fabric may be formed by using the fiber composed of the specific cyclic hydrocarbon-based polymer and other fibers as combination.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to nonwoven fabrics. More specifically, the present invention relates to a nonwoven fabric formed using a specific cyclic hydrocarbon-based polymer and having excellent elastic recovery, heat resistance, water resistance, oil absorption, and texture.

[0002]

BACKGROUND OF THE INVENTION Conventionally, nonwoven fabrics formed from polypropylene fibers, polyethylene fibers, etc. have been used for sanitary goods,
Although widely used for medical devices and the like, these nonwoven fabrics have room for improvement in terms of rigidity and recovery from compression.

The present applicant has proposed a nonwoven fabric using a cyclic olefin resin to solve such a problem (see JP-A-6-158420 and JP-A-8-144165). However, there has been a demand for a nonwoven fabric which is more excellent in rigidity and recovery from compression.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a nonwoven fabric which is excellent in rigidity, compressive recovery (elastic recovery), heat resistance, water resistance, oil absorption and texture.

[0005]

SUMMARY OF THE INVENTION The nonwoven fabric of the present invention comprises the following (I) and (I)
It is characterized by being formed from fibers of at least one kind of cyclic hydrocarbon polymer selected from the group consisting of I), (III), (IV) and (V). (I) a (co) polymer of a vinyl monocyclic alicyclic hydrocarbon compound, or a copolymer of a vinyl monocyclic alicyclic hydrocarbon compound and a monomer copolymerizable therewith, or (II) a hydrogenated product of a (co) polymer of a vinyl aromatic hydrocarbon compound or a copolymer of a vinyl aromatic hydrocarbon compound and a monomer copolymerizable therewith; A hydrogenated product of a polymer, wherein at least 30% of an aromatic hydrocarbon ring is hydrogenated; (III) a (co) polymer of a monocyclic monoolefin compound, or a monocyclic monoolefin A copolymer of an olefin compound and a monomer copolymerizable therewith; (IV) a hydrogenated product of a (co) polymer of a monocyclic conjugated diene compound, or a monocyclic conjugated diene compound. , A hydrogenated product of a copolymer thereof with a copolymerizable monomer; (V) At least one cyclic hydrocarbon polymer selected from the group consisting of the above (I), (II), (III) and (IV) is obtained by using an α, β-unsaturated carboxylic acid, an anhydride thereof or a derivative thereof. Modified product obtained by graft modification.

[0006] The nonwoven fabric of the present invention may be a nonwoven fabric formed by combining a fiber comprising the above-mentioned cyclic hydrocarbon polymer with other fibers. Such a nonwoven fabric is, in a preferred embodiment, other fibers are polyamide fiber, polyester fiber, polyethylene fiber, polypropylene fiber, polycarbonate fiber, glass fiber,
Desirably, at least one fiber selected from boron fiber, silicon carbide fiber, and carbon fiber is used.

[0007]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically. The nonwoven fabric of the present invention is formed from fibers made of a specific cyclic hydrocarbon-based polymer and, if necessary, other fibers.

Fibers Made of Cyclic Hydrocarbon Polymers The cyclic hydrocarbon polymers forming fibers made of the cyclic hydrocarbon polymer used in the present invention include the following (I) and (I)
It is at least one kind of cyclic hydrocarbon polymer selected from the group consisting of I), (III), (IV) and (V). (I) a (co) polymer of a vinyl monocyclic alicyclic hydrocarbon compound, or a copolymer of a vinyl monocyclic alicyclic hydrocarbon compound and a monomer copolymerizable therewith, or (II) a hydrogenated product of a (co) polymer of a vinyl aromatic hydrocarbon compound or a copolymer of a vinyl aromatic hydrocarbon compound and a monomer copolymerizable therewith; A hydrogenated product of a polymer, wherein at least 30% of an aromatic hydrocarbon ring is hydrogenated; (III) a (co) polymer of a monocyclic monoolefin compound, or a monocyclic monoolefin A copolymer of an olefin compound and a monomer copolymerizable therewith; (IV) a hydrogenated product of a (co) polymer of a monocyclic conjugated diene compound, or a monocyclic conjugated diene compound. , A hydrogenated product of a copolymer thereof with a copolymerizable monomer; (V) At least one cyclic hydrocarbon-based polymer selected from the group consisting of the above (I), (II), (III) and (IV) is treated with an α, β-unsaturated carboxylic acid, anhydride or derivative thereof. Modified product obtained by graft modification.

The cyclic hydrocarbon polymers (I), (II), (III), (IV) and (V) which can be used in the present invention will now be described. The polymer of (I) is (I) a vinyl-based monocyclic alicyclic hydrocarbon compound (co)
It is a polymer, a copolymer of a vinyl-based monocyclic alicyclic hydrocarbon compound and a monomer copolymerizable therewith, or a hydrogenated product thereof.

The vinyl monocyclic alicyclic hydrocarbon compound is
A compound having a structure in which a monocyclic cycloalkyl group or a monocyclic cycloalkenyl group is bonded to a vinyl group or an α-alkyl-substituted vinyl group. Here, the monocyclic cycloalkyl group and cycloalkenyl group may have a substituent such as an alkyl group.

Examples of such compounds include vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, and those compounds in which the α-position of the vinyl group is substituted with an alkyl group such as methyl, ethyl, or propyl. Compounds can be exemplified. Also, 4-vinylcyclohexene, 4-isopropenylhexene, 1-methyl-4-vinylcyclohexene, 1-methyl-4-isopropenylcyclohexene,
2-methyl-4-vinylcyclohexene, 2-methyl-
Examples thereof include vinylcyclohexene derivatives such as 4-isopropenylhexene.

When the polymer (I) is a (co) polymer of a vinyl monocyclic alicyclic hydrocarbon compound, these vinyl monocyclic alicyclic hydrocarbon compounds are polymerized alone. Or a copolymer obtained by copolymerizing two or more kinds.

In the case where the polymer (I) is a copolymer of a vinyl monocyclic alicyclic hydrocarbon compound and a monomer copolymerizable therewith, The copolymer is a copolymer obtained by combining a monocyclic alicyclic hydrocarbon compound with another compound copolymerizable with the compound within a range that does not impair the purpose of the present invention.

As the monomer copolymerizable with the vinyl monocyclic alicyclic hydrocarbon compound, any copolymerizable monomer can be used, and propylene, butene, acrylonitrile, acrylic acid, methacrylic acid, Maleic anhydride, acrylic acid ester, methacrylic acid ester, maleimide, vinyl acetate, vinyl chloride and the like can be exemplified. Among these monomers, it is preferable to use an α-olefin, and particularly, it is preferable to use a monomer such as propylene or butene because flexibility and impact resistance can be imparted. Such a monomer copolymerizable with the vinyl-based monocyclic alicyclic hydrocarbon compound is 0 to 9 based on the total amount of the monomer.
It is desirable to use 5 mol%, more preferably 0 to 90 mol%.

There is no particular limitation on the polymerization method for obtaining these polymers or copolymers, and any known radical polymerization,
Coordination anionic polymerization (Ziegler polymerization), cationic polymerization,
A polymerization method such as anionic polymerization can be applied.

The polymer of the above (I) may be a hydrogenated product of these polymers or copolymers. In particular, when a vinyl-based monocyclic alicyclic hydrocarbon compound used as a monomer forming these polymers or copolymers is substituted with a vinyl group or an α-alkyl-substituted vinyl group, a monocyclic (alkyl-substituted) cyclo In the case of a compound having a structure in which an alkenyl group is bonded, the above-mentioned polymer or copolymer is preferably a hydrogenated product. As such a hydrogenated product, 30% or more, preferably 60% or more, more preferably 90% or more of the optionally substituted cycloalkenyl group in the polymer or copolymer is hydrogenated. A polymer consisting of

The polymer (II) is a hydrogenated product of a (co) polymer of a vinyl aromatic hydrocarbon compound or a vinyl aromatic hydrocarbon compound and a monomer copolymerizable therewith. Which is a hydrogenated product of at least 30% of the aromatic hydrocarbon ring.

The vinyl aromatic hydrocarbon compound used as a monomer for forming the polymer (II) is a compound in which an aromatic substituent is bonded to a vinyl group or an α-alkyl-substituted vinyl group. . Such compounds include styrene, α-methylstyrene, α-ethylstyrene, α
-Propylstyrene, α-isopropylstyrene, α-
t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methyl Examples thereof include styrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, 4-phenylstyrene, vinylnaphthalene, and vinylanthracene.

When the polymer (II) is a hydrogenated (co) polymer of a vinyl aromatic hydrocarbon compound, such a vinyl aromatic hydrocarbon compound is polymerized alone. It may be a hydrogenated product of a polymer or a hydrogenated product of a copolymer obtained by copolymerizing two or more kinds.

In the case where the polymer (II) is a hydrogenated product of a copolymer of a vinyl aromatic hydrocarbon compound and a monomer copolymerizable therewith, It is a hydrogenated product of a copolymer in which a vinyl aromatic hydrocarbon compound and a monomer copolymerizable with the compound are copolymerized in a range that does not impair the gist of the present invention. As the monomer copolymerizable with such a vinyl aromatic hydrocarbon compound, any copolymerizable monomer can be used, and propylene, butene, acrylonitrile, acrylic acid, methacrylic acid, and maleic anhydride can be used. Acrylate, methacrylate, maleimide, vinyl acetate, vinyl chloride and the like. Among these monomers, it is preferable to use an α-olefin, and particularly, it is preferable to use a monomer such as propylene or butene because flexibility and impact resistance can be imparted. Such a monomer copolymerizable with the vinyl aromatic hydrocarbon compound is used in a proportion of 0 to 95 mol%, more preferably 0 to 90 mol%, based on the total amount of the monomers. desirable.

Such a polymer or copolymer of the above (II) can be obtained by polymerizing in the same manner as the polymer of the above (I) and hydrogenating it by a known method.

Examples of the method of hydrogenation include, for example, methods described in JP-A-7-247321 and US Pat. No. 5,612,422. The hydrogenation rate of the aromatic hydrocarbon ring contained in the polymer (II) is 30% or more, preferably 60% or more, more preferably 90% or more.

The polymer (III) is a (co) polymer of a monocyclic cyclic monoolefin compound or a copolymer of a monocyclic cyclic monoolefin compound and a monomer copolymerizable therewith. It is.

The monocyclic monoolefinic compound used as a monomer for forming the polymer of (III) is a monocyclic monoolefin which may have a substituent, and may be cyclobutene or cyclopentene. , Cyclohexene,
Cyclooctene and the like can be mentioned.

When the polymer of the above (III) is a (co) polymer of a monocyclic monoolefin compound, it is a polymer obtained by polymerizing such a monocyclic monoolefin compound alone. Alternatively, a polymer obtained by copolymerizing two or more kinds may be used.

In the case where the polymer (III) is a copolymer of a monocyclic monoolefin compound and a monomer copolymerizable therewith, the above monocyclic monoolefin may be used. The copolymer is a copolymer in which a system compound and another compound copolymerizable with the compound are combined in a range that does not impair the purpose of the present invention.

As the monomer copolymerizable with the monocyclic monoolefin compound, any copolymerizable monomer can be used, and ethylene, propylene, butene,
Examples thereof include acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, acrylic ester, methacrylic ester, maleimide, vinyl acetate, and vinyl chloride. Such a monomer copolymerizable with the monocyclic monoolefin compound is used at a ratio of 0 to 95 mol%, more preferably 0 to 90 mol%, based on the total amount of the monomers. desirable.

The polymerization method for obtaining these polymers or copolymers is not particularly limited, and can be obtained by a known method in which a monomer containing a cyclic monoolefin-based compound is subjected to addition polymerization.

The polymer (IV) is a hydrogenated product of a (co) polymer of a monocyclic conjugated diene compound or a monocyclic conjugated diene compound and a monomer copolymerizable therewith. Is a hydrogenated product of the copolymer

The monocyclic conjugated diene compound used as a monomer for forming the polymer (IV) is a monocyclic conjugated diene which may have a substituent, and may be cyclopentadiene, cyclopentadiene or cyclopentadiene. Hexadiene, cycloheptadiene, cyclooctadiene and the like can be mentioned.

When the polymer (IV) is a hydrogenated product of a (co) polymer of a monocyclic conjugated diene compound, such a monocyclic conjugated diene compound is polymerized alone. It may be a hydrogenated product of a polymer or a hydrogenated product of a copolymer obtained by copolymerizing two or more kinds.

In the case where the polymer (IV) is a hydrogenated product of a copolymer of a monocyclic conjugated diene compound and a monomer copolymerizable therewith, It is a hydrogenated product of a copolymer obtained by combining a monocyclic conjugated diene compound and a monomer copolymerizable with the compound in a range that does not impair the gist of the present invention.

As the monomer copolymerizable with such a monocyclic conjugated diene compound, any copolymerizable monomer can be used, and ethylene, propylene, butene, acrylonitrile, acrylic acid, Examples thereof include methacrylic acid, maleic anhydride, acrylic acid ester, methacrylic acid ester, maleimide, vinyl acetate, and vinyl chloride. Such a monomer copolymerizable with the monocyclic conjugated diene-based compound is preferably used in a ratio of 0 to 95 mol%, more preferably 0 to 90 mol%, based on the total amount of the monomers. .

Such a polymer or copolymer of the above (IV) is subjected to addition polymerization of a monomer containing the above-mentioned monocyclic conjugated diene compound by a known method, and hydrogenated by a known method. Can be obtained by:

Specifically, for example, polycyclohexadiene and a hydrogenated product thereof can be obtained by using the method disclosed in JP-A-11-106571. The hydrogenation rate of the double bond in the hydrocarbon ring contained in the polymer or copolymer of the above (IV) is 30.
% Or more, preferably 60% or more, more preferably 90%
It is desirable that this is the case.

The cyclic hydrocarbon-based polymer (I), (II), (III) or (IV) has a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) in terms of polystyrene. Usually 5,000 ~
1,000,000, preferably 10,000-50
0000, more preferably 50,000-300,
000 is desirable. Also, the molecular weight distribution Mw / M
n is desirably 10 or less, preferably 5.0 or less, more preferably 3.0 or less, and the glass transition temperature is 50 to 300 ° C, preferably 60 to 280.
° C, more preferably in the range of 70 to 250 ° C, and the crystallinity is preferably 20% or less, preferably 10% or less, more preferably 5% or less. The density is 1.5 g / cm ³ or less, preferably 1.0 g / cm ³
Or less, more preferably 0.95 g / cm ³ or less.

The polymer of (V) is the above (I), (II),
A modified product obtained by graft-modifying at least one cyclic hydrocarbon polymer selected from the group consisting of (III) and (IV) with an α, β-unsaturated carboxylic acid, an anhydride thereof or a derivative thereof; is there.

The polymer (V) is a polymer obtained by graft-modifying such a cyclic hydrocarbon polymer before modification with a graft monomer. As the graft monomer,
For example, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid and nadic acid, or acid anhydrides or derivatives thereof Can be used. As the derivative, for example,
Acid halides, amides, imides, esters and the like. Specific examples of such anhydrides or derivatives include maleenyl chloride, maleenyl imide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and the like. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferable.

In the preparation of the polymer (V), the graft ratio of the graft monomer is 0.00 to 1 g of the cyclic hydrocarbon polymer selected from (I) to (IV).
1 to 0.04 mg equivalent, preferably 0.005 to 0.03
Desirably, it is in the range of mg equivalent.

As the graft monomer, a modifier used in epoxy modification, such as glycidyl methacrylate (GMA), allyl glycidyl ether, vinyl glycidyl ether, glycidyl, instead of the above-mentioned α, β-unsaturated carboxylic acid, etc. A glycidyl compound such as itaconate can also be used.

Using such a graft monomer,
In order to produce the polymer (V), various conventionally known methods can be used. As such a method, for example, a method in which a cyclic hydrocarbon-based polymer selected from the above (I) to (IV) is melted by heating and a graft monomer is added to carry out graft copolymerization, or the above-described (I) )
And a method of dissolving a cyclic hydrocarbon polymer selected from (IV) in a solvent, adding a graft monomer, and performing graft copolymerization.

The graft copolymerization reaction is preferably performed in the presence of a radical initiator because of high reaction efficiency. Examples of the radical initiator used in the graft copolymerization reaction include organic peroxides, organic peresters, and other azo compounds. Among these radical initiators, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,
Dialkyl peroxides such as 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred. Such radical initiators are described in (I) to (I) above.
It is desirable to use 0.001 to 1 part by weight based on 100 parts by weight of the cyclic hydrocarbon polymer selected from V).

Such a graft copolymerization reaction is usually carried out by 6
It is performed in a temperature range of 0 to 380 ° C. Such (V)
Has a weight average molecular weight of 10,000 to 50.
0000, preferably 20,000 to 300,
000, more preferably 50,000 to 300,000
Desirably.

In the present invention, the fibers made of the cyclic hydrocarbon-based polymer include the above-mentioned fibers (I), (II), (III) and (I).
1 selected from the cyclic hydrocarbon polymers of V) and (V)
Fibers formed from different kinds of polymers may be used, or fibers formed from a resin composition comprising two or more polymers selected from these cyclic hydrocarbon polymers may be used. Moreover, you may use the fiber formed from the resin composition which mix | blended another resin with at least 1 type polymer selected from these cyclic hydrocarbon type polymers.

In the case where the fiber made of the cyclic hydrocarbon polymer used in the present invention is a fiber formed from a resin composition of the above-mentioned cyclic hydrocarbon polymer and another polymer, the above-mentioned fiber is used. A fiber obtained by blending another polymer with a cyclic hydrocarbon-based polymer to form a so-called polymer alloy in which the polymers are finely dispersed, and then spinning this, is desirable. Examples of other polymers that can be used by blending with the cyclic hydrocarbon-based polymer include the following (A) to (Q).

(A) A polymer derived from a hydrocarbon having one or two unsaturated bonds. Specifically, polyethylene, polypropylene, polymethylbutene-1, poly4-
Polyolefins such as methylpentene-1, polybutene-1 and polystyrene. In addition, these polyolefins may have a crosslinked structure.

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

(C) Polymers derived from α, β-unsaturated acids and their derivatives. Specifically, polyacrylate, polymethacrylate, polyacrylamide, polyacrylonitrile, or a copolymer with a monomer constituting the polymer, for example, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer,
An acrylonitrile / styrene / acrylic acid ester copolymer may be used.

(D) Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals. Specifically, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate,
Polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, or a copolymer with a monomer constituting the polymer, for example, ethylene,
And copolymers with vinyl acetate.

(E) A polymer derived from an epoxide.
Specific examples include a polymer derived from polyethylene oxide or bisglycidyl ether. (F) Polyacetal. Specific examples include polyoxymethylene, polyoxyethylene, and polyoxymethylene containing ethylene oxide as a comonomer.

(G) Polyphenylene oxide. (H) Polycarbonate. (I) Polysulfone.

(J) Polyurethane and urea resins. (K) 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, nylon 12, and the like.

(L) Polyesters derived from dicarboxylic acids and dialcohols and / or oxycarboxylic acids or the corresponding lactones. Specifically, polyethylene terephthalate, polybutylene terephthalate, poly
-1,4-dimethylol and cyclohexane terephthalate.

(M) A polymer having a crosslinked structure derived from aldehyde and phenol, urea or melamine. Specifically, phenol / formaldehyde resin, urea /
Formaldehyde resin, melamine / formaldehyde resin and the like can be mentioned.

(N) Alkyd resin. Specific examples include glycerin / phthalic acid resin. (O) Unsaturated polyester resins and halogen-containing modified resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and obtained using vinyl compounds as crosslinking agents.

(P) Natural polymer. Specific examples include cellulose, rubber, protein, and derivatives thereof such as cellulose acetate, cellulose propionate, and cellulose ether.

(Q) Soft polymer. In particular, there may be mentioned rubbery components selected from the groups (i) to (iv) described below. In addition, in the polymer alloy of the cyclic hydrocarbon-based polymer used in the present invention and these rubber-like components, a crosslinking reaction may be performed in the presence of an organic peroxide.
In the present invention, when a crosslinkable polymer alloy is used, expandable polymer particles and a foam having better rigidity and impact resistance can be provided.

Α-Olefin copolymer (i) The α-olefin copolymer (i) used as the soft polymer is an amorphous or low-crystalline copolymer comprising at least two α-olefins. It is a polymer. Examples of the low crystallinity copolymer include an ethylene / α-olefin copolymer and a propylene / α-olefin copolymer.

The α-olefin constituting the ethylene / α-olefin copolymer usually has 3 carbon atoms.
Α-olefins of up to 20 are used, specifically, for example, propylene, 1-butene, 4-methyl-1-butene, 1-hexene, 1-octene, 1-decene and mixtures thereof. Of these, α-olefins having 3 to 10 carbon atoms are particularly preferred.

In the ethylene / α-olefin copolymer, the molar ratio of the repeating unit derived from ethylene to the repeating unit derived from α-olefin (ethylene / ethylene)
α-olefin) varies depending on the type of α-olefin, but is preferably in the range of 40/60 to 95/5. Furthermore, when the α-olefin used is propylene, the molar ratio is 40/60 to 90 /
10, preferably 50/50 when the α-olefin is an α-olefin having 4 or more carbon atoms.
９５95/5 is preferred.

As the α-olefin constituting the propylene / α-olefin copolymer, it is common to use an α-olefin having 4 to 20 carbon atoms, and specifically, for example, 1-butene, 4-Methyl-1-pentene, 1-hexene, 1-octene, 1-decene and mixtures thereof are used. Among them, α-olefins having 4 to 10 carbon atoms are particularly preferred.

In the propylene / α-olefin copolymer as described above, the molar ratio of the repeating unit derived from propylene to the repeating unit derived from α-olefin (propylene / α-olefin) is α-olefin. Depending on the type of olefin, it varies from 50/50 to 95/5
Is preferably within the range.

Α-Olefin / Diene Copolymer (ii) As the α-olefin / diene copolymer (ii) used as the soft polymer, ethylene / α-olefin /
Diene copolymer rubber and propylene / α-olefin / diene copolymer rubber are used.

As the α-olefin constituting such a copolymer rubber, an α-olefin having 3 to 20 carbon atoms (4 to 20 in the case of propylene / α-olefin) is usually used. Examples include propylene, 1-butene, 1-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 particularly preferred.

The diene component constituting these copolymer rubbers includes, for example, 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,
Chain non-conjugated dienes such as 5-heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2 -
Norbornene, 5-isopropylidene-2-norbornene, 6
Cyclic non-conjugated dienes such as 2-chloromethyl-5-isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2, 2-norbornadiene and the like.

In the ethylene / α-olefin / diene copolymer rubber, the molar ratio (ethylene / α-olefin) of the repeating unit derived from ethylene to the repeating unit derived from α-olefin is α-olefin. , But generally varies from 40/60 to 90/1.
It is preferably in the range of 0.

The content of the repeating unit derived from diene in these copolymer rubbers is usually from 1 to 1.
It is in the range of 20 mol%, preferably 2 to 15 mol%. Aromatic vinyl hydrocarbon / conjugated diene soft copolymer (iii) Aromatic vinyl hydrocarbon used as soft polymer
As the conjugated diene-based soft copolymer (iii), an aromatic vinyl-based hydrocarbon, a conjugated diene-based random copolymer, a block copolymer, or a hydride thereof is used.

Specific examples include 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 copolymers, hydrogenated styrene / isoprene / styrene block copolymer rubbers, styrene / butadiene random copolymer rubbers and the like can be mentioned.

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

Other soft polymer or copolymer (iv) Other soft polymer soft polymer or copolymer (iv)
Specific examples thereof include polyisobutylene rubber, polyisoprene rubber, polybutadiene rubber, and isobutylene / isoprene copolymer rubber.

The properties of the soft polymers (i) to (iv) are as follows: the intrinsic viscosity [η] measured in decalin at 135 ° C. is usually 0.01 to 10 dl / g. It is preferably in the range of 0.08 to 7 dl / g, and the glass transition temperature (Tg) is usually 0 ° C or lower, preferably -10 ° C or lower, particularly preferably -20 ° C or lower.
The crystallinity measured by the X-ray diffraction method is usually 0 to 2
0%, preferably 0 to 10%, particularly preferably 0 to 5%
Is desirably within the range.

Such a soft polymer can be used as it is, or can be mixed with a cyclic hydrocarbon resin after forming a crosslinked structure. Further, after being mixed with the above-mentioned cyclic hydrocarbon-based resin, a crosslinked structure can be formed.

In such a polymer alloy containing a rubber-like component and a crosslinkable polymer alloy treated with an organic peroxide, various types (i) to (iv) of soft polymer are added to 100 parts by weight of the cyclic hydrocarbon polymer. The total amount of the polymer is 5 to 150 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 1 to 100 parts by weight.
It is present at 0 to 80 parts by weight. By satisfying such a compounding ratio, a polymer alloy having a balanced impact strength, rigidity, heat deformation temperature and hardness can be obtained. The melt flow index (MFR; ASTM D1238 condition) of these polymer alloys is preferably 0.1 to 100 g / 10 minutes.

In forming a crosslinked structure in the present invention, an organic peroxide is usually used. Here, as the organic peroxide in the case of crosslinking polymerization, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis (t-butylperoxy) cyclohexane and 2,2-bis (t- Butyl peroxy)
Peroxyketals such as octane; t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxy peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide Hydroperoxides; di-t-butyl peroxide, 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane, 2,5-dimethyl
Dialkyl peroxides such as -2,5-di (t-butylperoxy) hexine-3; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; t-butylperoxyacetate, t-butylperoxybenzoate; Peroxyesters such as 2,5-dimethyl-2,5-di (benzoylperoxy) hexane and the like can be mentioned.

The amount of the above organic peroxide component is usually 0.01 to 1 part by weight, preferably 0.0 to 1 part by weight, based on 100 parts by weight of the total amount of the cyclic hydrocarbon polymer and the soft polymer.
5 to 0.5 parts by weight.

When the composition is treated with an organic peroxide, a polymer alloy having excellent impact resistance can be obtained by further adding a compound having two or more radically polymerizable functional groups in the molecule. That is, the crosslinking efficiency is improved by performing a crosslinking reaction using a compound having two or more radically polymerizable functional groups in the molecule.

Examples of the compounds having two or more radically polymerizable functional groups in the molecule include divinylbenzene, vinyl acrylate and vinyl methacrylate. These compounds are used in an amount of usually 1 part by weight or less, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the cyclic hydrocarbon polymer and the soft polymer.
Used in an amount of 0.5 parts by weight.

The fiber comprising the cyclic hydrocarbon-based polymer used in the present invention does not impair the object of the present invention, in addition to the above-mentioned cyclic hydrocarbon-based polymer and other resin components to be blended if necessary. In the range, conventionally known heat stability, weather stability, antistatic agent, slip agent, antiblocking agent, antifogging agent, lubricant, dye, pigment, natural oil, synthetic oil, wax and the like are included as optional components. You may.

For example, stabilizers to be added as optional components include tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane,
β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Phenolic antioxidants such as propionate, fatty acid metal salts such as zinc stearate, calcium stearate, calcium 1,2-hydroxystearate, glycerin monostearate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate And polyhydric alcohol fatty acid esters such as pentaerythritol tristearate. These may be blended alone or in combination. For example, tetrakis [methylene-3
-(3.5-di-t-butyl-4-hydroxyphenyl) propionate] A combination of methane, zinc stearate and glycerin monostearate can be exemplified. 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 balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dowamite, calcium sulfate , Potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, calcium silicate, montmorillonite, pentonite, graphite, aluminum powder, molybdenum sulfide and the like.

The cyclic hydrocarbon polymer and other components can be mixed using a known method. For example, each component can be mixed simultaneously. The fiber composed of the cyclic hydrocarbon-based polymer used in the present invention can be obtained from the above-described cyclic hydrocarbon-based polymer or a composition to which other components as described above are added, if necessary, by a conventionally known fiberization method. Can be.

Examples of the spinning method for fiberization include dry spinning, wet spinning, melt spinning, and emulsion spinning. Among these spinning methods, the melt spinning method is particularly preferred. In this melt spinning method, a cyclic hydrocarbon-based resin (or composition) is heated to a temperature equal to or higher than a melting point (or softening point) and lower than a decomposition temperature, preferably at a temperature of 120 to 300 ° C., and is melted. This is a method of extruding and winding the extruded resin while cooling it. In this method, various types of nozzles can be used.
A nozzle having a value of D 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.
/ min. The winding speed of the monofilament extruded at the above speed is usually 10 to 10,0.
00 m / min, preferably 100 to 5,000 m / min. Therefore, the monofilament extruded from the nozzle is usually stretched during winding. The stretching ratio at this time is usually 10 to 10,000, preferably 100 to 5.0.
00.

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

Other Fibers The nonwoven fabric of the present invention may be formed by combining the above-mentioned fibers made of the cyclic hydrocarbon polymer with other fibers.

As other fibers that can be used in the present invention, conventionally known various fibers can be used, and natural fibers or synthetic fibers, organic fibers and inorganic fibers can be used. There may be. Further, the fiber may be a fiber having a single composition or a fiber formed from a mixture.

As such other fibers, at least one kind selected from polyamide fibers, polyester fibers, polyethylene fibers, polypropylene fibers, polycarbonate fibers, glass fibers, boron fibers, silicon carbide fibers, and carbon fibers. Preferably it is a fiber.
Of these, organic fibers are more preferable, and polyamide fibers, polyester fibers, polyethylene fibers, and polypropylene fibers are more preferably used.
Such other fibers may be used alone or in combination of two or more.

The non-woven fabric according to the present invention comprises the above-mentioned fiber composed of the cyclic hydrocarbon polymer and, if necessary, other fibers.
It can be manufactured by a conventionally known method.

For example, in the case of producing a non-woven fabric only from fibers made of a cyclic hydrocarbon-based polymer, short fibrous cyclic hydrocarbon-based polymer fibers are formed into a sheet and joined by fusion or adhesive. It can be manufactured by the following.

In the case of producing a non-woven fabric composed of a fiber composed of a cyclic hydrocarbon polymer and other fibers,
It can be produced by mixing short fiber-like cyclic hydrocarbon-based polymer fibers with other short fiber-like fibers, forming a sheet, and fusing or bonding with an adhesive or the like.

More specifically, for example, a short fibrous cyclic hydrocarbon resin fiber blended with other short fiber fibers (eg, polyamide fiber) by a cotton blender as required is used.
It is made into a sheet (web) by a carding machine for spinning. The web is usually arranged substantially parallel to the length of the fibers, strong in the length and weak in the cross direction. Therefore,
Usually, another parallel arrangement web is superimposed on the web so that the longitudinal direction of the fiber intersects (orthogonally) with the web, and is arranged so that there is no difference in strength depending on the direction. Then, by adding an adhesive to the cross-aligned web and bonding, or by mechanically tangling the web with a needle punch and joining the short fibers together, it is possible to produce a nonwoven fabric that does not cause a difference in strength depending on the direction. it can.

Further, a random web obtained by scattering and lowering a fiber made of a short fibrous cyclic hydrocarbon resin together with other short fibrous fibers as required by an air flow by the above-described method. They may be joined (dry method). Also,
The short-fibrous cyclic hydrocarbon-based resin may be dispersed in water or an adhesive together with other short-fibrous fibers as necessary, and then may be formed by a paper machine (wet process). Further, a web may be formed and fused simultaneously with melt-spinning of the cyclic hydrocarbon-based resin and, if necessary, a resin forming other fibers (direct method).

[0092] Here, the case where the fibers made of the cyclic hydrocarbon resin and other fibers used as necessary are in the form of short fibers has been described in detail, but these fibers forming the nonwoven fabric of the present invention are described. May be in the form of short fibers or long fibers.

Since the nonwoven fabric of the present invention is formed using fibers made of a cyclic hydrocarbon resin, the nonwoven fabric has excellent mechanical properties such as rigidity and tensile strength, and excellent chemical resistance such as acid resistance and oil resistance. And excellent properties inherent to cyclic hydrocarbon resins.

In the nonwoven fabric of the present invention, the content of the fiber composed of the cyclic hydrocarbon resin is not particularly limited, but is usually 5% by weight or more, preferably 1% by weight of the whole nonwoven fabric.
The content is desirably 0% by weight or more, more preferably 30% by weight or more.

For example, cyclic hydrocarbon resin fibers 10 to 9
0% by weight and polyamide fiber 90 to 10% by weight (total 10%).
0% by weight), the nonwoven fabric obtained by the above method retains the same tensile strength as the cyclic hydrocarbon resin originally had even after being immersed in an acid, an alkali or the like for a long time, Even if soaked in a hydrocarbon such as kerosene for a long time, the same tensile strength as the polyamide originally had is maintained, such as rigidity, compression recovery, strength, and elastic modulus. , Heat resistance, water resistance, chemical resistance,
It is excellent in various properties such as solvent resistance and texture in a well-balanced manner and can be suitably used as, for example, an oil-absorbing cloth (oil mat), clothing for acid and alkali resistance, cloth material, various reinforcing agents, and the like.

[0096]

According to the present invention, the nonwoven fabric according to the present invention is formed of fibers made of a specific cyclic hydrocarbon-based polymer. Therefore, according to the present invention, rigidity, resilience to compression (elastic recovery rate), heat resistance, It is possible to provide a nonwoven fabric which is excellent in water resistance, oil absorbency and texture in a good balance.

[0097]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0098]

[Preparation Example 1] Preparation of cyclic hydrocarbon polymer In a stainless steel autoclave having an internal volume of 5 liters, a weight average molecular weight (Mw) was 130,000, a number average molecular weight (Mn) was 110,000, and Mw / Mn was 240 g of 1.18 polystyrene, 100 g of cyclohexane, and 36 g of a hydrogenation catalyst (manufactured by Nippon Chemical Industry Co., Ltd., silica / alumina catalyst supporting 40% nickel) are charged, and the system is purged with nitrogen. Next, a hydrogenation reaction was performed at 230 ° C. and a hydrogen pressure of 45 kg / cm ² for 8 hours while stirring the inside of the system at a speed of 1000 rpm.

After the completion of the hydrogenation reaction, the reaction solution was filtered, 4000 g of cyclohexane was added, and a large excess of methanol was added to precipitate a polymer. This polymer was separated by filtration, and dried under reduced pressure to obtain a cyclic hydrocarbon polymer (a) which was a hydrogenated product of polystyrene.

The physical properties of the obtained cyclic hydrocarbon polymer (a) were such that Tg was 140 ° C., density was 0.95 g / cm ³ , hydrogenation ratio was 100%, and weight average molecular weight (Mw) in terms of polystyrene was 100%. 87,000, number average molecular weight (Mn) is 4
3,000, Mw / Mn was 1.85.

[0101]

Example 1 The cyclic hydrocarbon-based polymer (a) obtained in Preparation Example 1 was heated at a cylinder temperature of 230 ° C. and a die hole diameter of 1 m.
m, was wound at a rate of 0.1 mm / min and stretched to obtain a monofilament of a cyclic hydrocarbon polymer having a fiber diameter of 30 μm.

Next, the obtained monofilament was
mm, and the fibers were entangled with each other using a carding machine to prepare a nonwoven fabric. About the obtained nonwoven fabric, the elastic recovery rate (recovery to compression) was evaluated. Table 1 shows the results
Shown in

The elastic recovery was evaluated by the following method. Elastic recovery rate: The prepared nonwoven fabric is 10 cm long and 10 cm wide.
cm and overlaid to a thickness of 10 mm. A load of 1 kg is placed on it, and a load condition of 10 g / cm ² is set.
The thickness when left at room temperature for 24 hours was measured. Thereafter, the load was removed, and after allowing to stand for 1 hour, the thickness of the nonwoven fabric was measured, and the degree of restoration of the thickness was defined as the elastic recovery rate.

[0104]

Example 2 Polyamide-6 (CM1 manufactured by Toray Industries, Inc.)
021-TM) and fed to a single-screw extruder having a cylinder temperature of 280 ° C. and a die hole diameter of 1 mm, wound and stretched at a speed of 0.1 mm / min to obtain a fiber diameter of 30 μm.
m of polyamide-6 monofilament was obtained.

The obtained polyamide-6 monofilament was cut into a length of 50 mm and the monofilament (having a fiber diameter of 30) of the cyclic hydrocarbon polymer used in Example 1.
μm and a fiber length of 50 mm) were mixed at a weight ratio of 1/1, and the fibers were entangled with each other using a carding machine to produce a nonwoven fabric.

The elastic recovery of the obtained nonwoven fabric was evaluated in the same manner as in Example 1. Table 1 shows the results.

[0107]

In Comparative Example 1 Example 1, instead of using cyclic hydrocarbon polymer obtained in Preparation Example 1 (a), ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (MF measured at 260 ° C. under a load of 2.16 kg)
A monofilament (fiber diameter 30 μm, fiber length 50 mm) was prepared in the same manner as in Example 1 except that R: 7 g / 10 min, glass transition temperature: 140 ° C., to prepare a nonwoven fabric. About the obtained nonwoven fabric, the elastic recovery rate was evaluated like Example 1. Table 1 shows the results.

[0108]

Comparative Example 2 Polyamide-6 monofilament (fiber diameter 30 μm, fiber length 50 mm) used in Example ² and ethylene and tetracyclo [4.4.0.1 2,5.1 used in Comparative Example 1
^7,10 ] -3-Dodecene and a random copolymer monofilament (fiber diameter 30 μm, fiber length 50 mm) are mixed at a weight ratio of 1/1, and the fibers are entangled using a card machine to form a nonwoven fabric. It was created.

The elastic recovery of the obtained nonwoven fabric was evaluated in the same manner as in Example 1. Table 1 shows the results.

[0110]

Comparative Example 3 In Example 1, instead of using the cyclic hydrocarbon polymer (a) obtained in Preparation Example 1, homopolypropylene (density: 0.91 g / cm ³ , 260 ° C., 2.1
A monofilament (fiber diameter 30 μm, fiber length 50 mm) was prepared in the same manner as in Example 1 except that MFR measured at a load of 6 kg: 5 g / 10 min) was used to prepare a nonwoven fabric. About the obtained nonwoven fabric, the elastic recovery rate was evaluated like Example 1. Table 1 shows the results.

[0111]

[Table 1]

From the examples and the comparative examples, it was found that the nonwoven fabric of the present invention formed from the fiber composed of the specific cyclic hydrocarbon-based polymer was particularly excellent in recovery from compression.

Claims (3)

[Claims] 1. A fiber formed of at least one type of cyclic hydrocarbon polymer selected from the group consisting of the following (I), (II), (III), (IV) and (V): Nonwoven fabric characterized by: (I) a (co) polymer of a vinyl monocyclic alicyclic hydrocarbon compound or a vinyl monocyclic alicyclic hydrocarbon compound and a monomer copolymerizable therewith (II) a hydrogenated product of a (co) polymer of a vinyl aromatic hydrocarbon compound, or a hydrogenated product of the vinyl aromatic hydrocarbon compound; (III) a (co) polymer of a monocyclic monoolefin-based compound, which is a hydrogenated product of a copolymer with a monomer, wherein at least 30% of an aromatic hydrocarbon ring is hydrogenated; Or a monocyclic cyclic monoolefin compound and a monomer copolymerizable therewith (IV) a hydrogenated product of a (co) polymer of a monocyclic conjugated diene compound, or a copolymer of a monocyclic conjugated diene compound and a monomer copolymerizable therewith (V) at least one cyclic hydrocarbon-based polymer selected from the group consisting of the above (I), (II), (III) and (IV) with an α, β-unsaturated carboxylic acid , A modified product obtained by graft modification with an anhydride or a derivative thereof. 2. A nonwoven fabric formed by combining a fiber comprising the cyclic hydrocarbon-based polymer according to claim 1 with another fiber. 3. Other fibers are polyamide fiber, polyester fiber, polyethylene fiber, polypropylene fiber,
The nonwoven fabric according to claim 2, wherein the nonwoven fabric is at least one kind of fiber selected from polycarbonate fiber, glass fiber, boron fiber, silicon carbide fiber, and carbon fiber.