JPH09241486A - Polyester composition, monofilament and woven fabric for industry - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain monofilaments, various kinds of woven fabrics such as drier canvases for making paper, wires for making paper, net conveyers for a process for thermally adhering non-woven fabrics by a thermal bonding method and filters, and further various kinds of industrial parts, etc., excellent in water repellency, oil repellency, stain resistance and hydrolysis resistance, and having sufficient strengths and sufficient elongation. SOLUTION: This polyester composition for monofllaments, etc., contains polymer components comprising (A) 99.6-70wt.% of a polyester, (B) 0.2-29.8wt.% of a fluororesln, and (C) 0.2-29.8wt.% of a thermoplastic polymer not containing fluorine atoms, and further containing (D) 0.005-1.5wt.% of an unreacted carbodiimide compound. The monofilaments are used for industrial woven fabrics such as drier canvases for paper making, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an excellent antifouling property (difficulty in attaching dirt and easiness of cleaning dirt), and further, antifouling property and hydrolysis resistance (in the papermaking industry, when it is called steam heat resistance). The present invention relates to a polyester composition, a polyester monofilament, and an industrial fabric using the polyester monofilament.

[0002]

BACKGROUND OF THE INVENTION Polyester has been widely used in various industrial parts, textile materials for clothing and industry, various woven fabrics, etc. because it has excellent tensile strength, acid resistance and dimensional stability. For example, as a monofilament, a paper dryer canvas, a net conveyor for a thermal bonding non-woven fabric thermal bonding process, a filter, a papermaking wire, various brushes,
It has been used for brushes and printing screen gauze.

However, polyester products have problems that they are easily soiled and that they are prone to hydrolysis in a high temperature and high humidity atmosphere, and therefore various improvements have been conventionally made.

As an example of easily soiling, for example, polyester monofilament papermaking wire (woven fabric for pulp making process) and paper dryer canvas (woven fabric for paper drying process) were used for wood pitch and recovered waste paper. Paste, pulp, additives added to the papermaking stock solution,
Since dirt such as sizing agent, paper strengthening agent, and ink adheres and accumulates, it is unavoidable to wash these wires and canvas frequently. In addition, for example, in the case of a non-woven belt cloth for a heat-bonding process, there is a problem that fused polyethylene or the like adheres and accumulates on the belt cloth and adheres to another non-woven fabric product to deteriorate the product quality. Was. Further, when it is used for a filter, there is a problem that the peeling property of the cake is poor due to the adhesion of dirt and the filtration efficiency is lowered.

Therefore, in order to improve the drawback that the polyester is easily soiled, for example, a technique of post-treating the polyester fiber with a compound containing fluorine (Japanese Patent Laid-Open No. 52-5).
No. 400, JP-A-58-46123), a technique of adding a perfluoroalkyl sulfonate (monomer) to polyester (JP-A-59-66449), and a blend of ethylene and monochlorotrifluoroethylene with polyester. Technology (Japanese Patent Laid-Open No. 5-30221)
No. 2) is known.

On the other hand, as an example of easily hydrolyzing, for example, when polyester monofilament is used as a constituent material of a paper dryer canvas, the strength of the polyester monofilament decreases due to hydrolysis deterioration during use, so that it is used for a long period of time. Was difficult to withstand. Therefore, various proposals have been made to improve the hydrolysis resistance of this polyester monofilament.

As an example of means for improving the hydrolysis resistance of a polyester monofilament, a polyester monofilament in which a specific amount of polyethylene, polypropylene, polybutene, poly-4-methylpentene 1, polystyrene or the like is added (JP-A-51-136923). However, the filament obtained by this technique is not practical because it has low strength and a small effect of improving hydrolysis resistance.

A method is known in which an epoxy compound is added to improve the hydrolyzability of polyester.
For example, a method of adding glycidylphthalimide to polyester (Japanese Patent Publication No. 61-4843), a method of adding an epoxy compound to polyester in the presence of an alkali metal (Japanese Patent Publication No. 61-42728), and a method of adding oxazoline compound to polyester. (Japanese Patent Publication No. 63-8133, Japanese Patent Publication No. 61-48531, Japanese Patent Publication No. 61-5
No. 7182, Japanese Patent Publication No. 57-161122, Japanese Patent Publication No. 61-48532), a certain level of hydrolysis resistance improving effect can be obtained, but a high level of hydrolysis resistance currently required. You cannot be satisfied with your sex.

Also known is a method of improving the hydrolysis resistance of polyester by adding a carbodiimide compound. For example, a method in which a mono- or bis-carbodiimide compound is added and kneaded and spun in a short time to form a filament containing no unreacted carbodiimide (JP-A-50-95517), and having three or more carbodiimide groups in the molecule Method of adding polycarbodiimide compound (Japanese Examined Patent Publication No. 38-15220), carboxyl end group is capped by reaction with carbodiimide, free mono- and / or biscarbodiimide compound 30-200 ppm and free polycarbodiimide or still reactive Fibers and filaments containing at least 0.02% by weight of a reaction product containing a polycarbodiimide group having a hydroxyl group (JP-A-4-289221).
Has been proposed. Further, a method for producing an industrial polyester monofilament in which a specific carbodiimide compound is added to a polyester containing a specific amount of phosphorus (JP-A-57-57).
No. 205518) and a specific carbodiimide compound are left in a specific amount in an unreacted state, and polyester monofilament for papermaking canvas (Japanese Patent Laid-Open No. 58-2391).
Various improvements have been made such as the proposal of Japanese Patent No. 6).
Further, the inventors of the present application have found that the polymer component, which is one of the constituent requirements of the composition and monofilament of the present application, comprises a polyester having a terminal carboxyl group concentration of 10 equivalents / 10 ⁶ g or less, and a thermoplastic resin containing no fluorine atom. It is possible to provide a polyester composition and a polyester monofilament composed of a polymer, the polymer component containing a specific amount of a carbodiimide compound in an unreacted state, and to provide an extremely high level of hydrolysis-resistant polyester required in recent years. (Japanese Patent Laid-Open No. 7-258524). Further, as a technique for simultaneously exhibiting both excellent antifouling property and hydrolysis resistance in polyester, the terminal carboxyl group concentration is 10 equivalents / polyester 10 ⁶ g or less, and the carbodiimide compound in an unreacted state is 0. .005
~ 1.5% by weight and 0.01 ~ of fluorine-based polymer
A polyester monofilament containing 30% by weight (International Publication No. WO92 / 07126) has been proposed and widely used.

However, in recent years, from the viewpoint of resource conservation, the spread of recycling of recovered waste paper has increased the adherence of dirt from the waste paper to the papermaking wire and the papermaking dryer canvas, and the dryer accompanying the increase in the papermaking speed in order to increase the productivity of the paper. As the temperature has increased, there has been a strong demand to provide a polyester material having both excellent antifouling properties and an extremely high level of hydrolysis resistance as compared with conventional ones.

[0011]

In view of the above-mentioned demands, the present invention has a polyester composition, a polyester monofilament, and a polyester having a stain resistance superior to the conventional one and an extremely high level of hydrolysis resistance. The present invention relates to various industrial fabrics using monofilaments and dryer canvases for papermaking.

[0012]

The above-mentioned problems of the present invention are as follows. Polymer component is polyester (A) 70-99.6
% By weight, fluorine resin (B) 0.2 to 29.8% by weight, and fluorine atom-free thermoplastic polymer (C) 0.2 to
29.8% by weight, and the total amount of the fluororesin (B) and the polymer (C) is 0.4 to 30% by weight.
A polyester composition or a polyester monofilament containing 1.5% by weight.

2. The terminal carboxyl group concentration of the polyester (A) constituting the polyester composition is 10 equivalents / 1
The above polyester composition or polyester monofilament having an amount of 0 ⁶ g or less.

3. The above polyester composition or polyester monofilament in which the fluororesin (B) is a copolymer of tetrafluoroethylene, propylene hexafluoride and vinylidene fluoride.

4. The above polyester composition or polyester monofilament in which the thermoplastic polymer (C) containing no fluorine atom is at least one selected from polyolefins, polystyrenes and polymethacrylate polymers.

5. Polyolefins have the following (C1)
To the polyester composition or polyester monofilament which is at least one cyclic olefin polymer selected from (C2).

(C1) C2 having ethylene as a main component
The above α-olefin and the following general formula [I] or [I
A random copolymer with at least one kind of cyclic olefin represented by I].

[0018]

Embedded image (In the general 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, chlorine Represents an atom or a group selected from the group consisting of an atom, a bromine atom and a hydrocarbon group, wherein R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and May have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.)

Embedded image (In the above general 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 each independently represent a hydrogen atom, a chlorine atom,
Represents an atom or a group selected from the group consisting of a bromine atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, wherein a carbon atom to which R ⁹ is bonded and R ¹³ are bonded And the carbon atom to which R ¹⁰ is bonded and the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. = M = 0 when R ¹⁵ and R ¹² or R ¹⁵
And R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. (C2) A ring-opening polymer or ring-opening copolymer of at least one cyclic olefin represented by the following general formula [III] or [IV], or a hydrogenated product thereof.

[0019]

Embedded image [In the above general formula [III], 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 chlorine atom,
Represents an atom or group selected from the group consisting of a bromine atom and a hydrocarbon group, wherein R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, It may have a heavy bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group,
R ¹⁶ and R ¹⁷ each independently represent a group represented by the following formula;

Embedded image (R ^c in the above formula, R ^d, R ^e is a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group or a chlorine or bromine-substituted hydrocarbon group, W represents _{^{SiR g p D 3- p (R}} g Is carbon number 1 to 1
0 hydrocarbon group, D is chlorine atom, bromine atom or -OCOR
^h (R ^h is a hydrocarbon group having 1 to 10 carbon atoms) p is an integer of 0 to 3; ), X represents an integer of 0 to 10. ) And R
¹⁶ and R ¹⁷ may be represented by the following formula.

[0020]

Embedded image (R ^f in the above formula represents a hydrocarbon group having 1 to 20 carbon atoms.)]

Embedded image (In the general formula [IV], 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 each independently represent a hydrogen atom, a chlorine atom,
A bromine fiber, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an atom or group selected from the group consisting of an alkoxy group, wherein the carbon atom to which R ⁹ is bonded and R ¹³ are The carbon atom bonded or the carbon atom bonded to R ¹⁰ and the carbon atom bonded to R ¹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵
And R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ) 6. The above polyester composition or polyester monofilament, wherein the polyester is polyethylene terephthalate.

7. The polyester monofilament described above, wherein the cross section of the monofilament perpendicular to the fiber axis direction is circular or flat.

8. An industrial woven fabric in which the above polyester monofilament is used in at least part of the weft yarns or warp yarns constituting the woven fabric.

9. The industrial woven fabric as described above, wherein the industrial woven fabric is a papermaking dryer canvas, a papermaking wire, a thermal bonding non-woven fabric, a net conveyor for heat bonding process, or a filter. Can be achieved by

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The polyester (A) (hereinafter referred to as the polyester) constituting the polymer component in the polyester composition and the polyester monofilament of the present invention is a polyester composed of dicarboxylic acid and glycol. Examples of the dicarboxylic acid component include terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid and 1,4-cyclohexanedicarboxylic acid. Examples of the glycol component include ethylene glycol, propylene glycol, tetramethylene glycol, 1,4-cyclohexanedimethanol and the like. These dicarboxylic acid components and glycol components can be used in appropriate combination. In addition, a part of the above dicarboxylic acid component,
It may be replaced with adipic acid, sebacic acid, dimer acid, sulfonic acid metal salt-substituted isophthalic acid, or the like, and a part of the glycol component may be diethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, polyalkylene glycol, or the like. May be replaced with. Further, a small amount of a chain branching agent such as pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid, and boric acid can be used in combination.

Of these, 90% of the dicarboxylic acid component is used.
Polyethylene terephthalate (hereinafter referred to as PET), in which at least mol% is composed of terephthalic acid and 90 mol% of the glycol component is composed of ethylene glycol, is preferred.

The polyester includes various kinds of inorganic particles such as titanium oxide, silicon oxide, calcium carbonate, silicon nitride, clay, talc, kaolin, zirconic acid, carbon black, etc., crosslinked polymer particles, and various metal particles. Besides, conventionally known antioxidants, sequestering agents, ion-exchange agents, anti-coloring agents, light-proofing agents, inclusion compounds,
Antistatic agents, various colorants, waxes, silicone oils, various surfactants, various reinforcing fibers and the like may be added.

The intrinsic viscosity of the polyester is usually 0.
It may be 6 or more, but is preferably 0.7 or more because the strength is excellent. Here, the intrinsic viscosity is the intrinsic viscosity obtained from the viscosity measured at 25 ° C. in an orthochlorophenol solution, and is represented by [η]. The polyester (A) having a terminal carboxyl group concentration of 10 equivalents / 10 ⁶ g or less is preferable because the hydrolysis resistance of the polyester composition and the polyester monofilament is further improved.
(Terminal carboxyl group concentration is according to Pohl, Anal. Chem.
, 24 1614 (1954). ) In order to obtain a polyester composition and a polyester monofilament having a terminal carboxyl group concentration of 10 equivalent / 10 ⁶ g or less, the terminal carboxyl group concentration is 10 equivalent / 10.
^The concentration of terminal carboxyl groups may be reduced to 10 equivalents / 10 ⁶ g or less by solid-phase polymerization of polyester in an amount of more than ⁶ g, and a mono- or diepoxy compound, a mono- or bisoxazoline compound, may be added to the molten polyester. Alternatively, an appropriate amount of a carbodiimide compound may be reacted, and above all, the polyester composition and the polyester monofilament of the present invention contain 0.005% by weight or more of the unreacted carbodiimide compound (D). It is advantageous to use.

As the carbodiimide compound (D), 1
Any compound may be used as long as it has one or more carbodiimide groups in the molecule.
N, N'-di-o-triylcarbodiimide, N, N '
-Diphenylcarbodiimide, N, N'-dioctyldecylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N, N'-di-2,6-diisopropyl Phenylcarbodiimide, N, N'-di-
2,6-di-tert.-butylphenylcarbodiimide,
N-triyl-N'-phenylcarbodiimide, N, N
′ -Di-p-nitrophenylcarbodiimide, N, N ′
-Di-p-aminophenylcarbodiimide, N, N'-
Di-p-hydroxyphenylcarbodiimide, N, N '
-Di-cyclohexylcarbodiimide, N, N'-di-
p-triylcarbodiimide, p-phenylene-bis-
Di-o-triylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, hexamethylene-bis-dicyclohexylcarbodiimide, ethylene-
Examples thereof include bis-diphenylcarbodiimide and aromatic polycarbodiimide represented by the following general formula.

[0029]

Embedded image (R in the formula represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 20) One or two or more compounds are arbitrarily selected from these carbodiimide compounds. Although it may be contained in the polyester, a compound having an aromatic skeleton tends to be advantageous in view of stability after addition to the polyester.
′ -Di-2,6-diisopropylphenylcarbodiimide, N, N′-di-2,6-di-tert.-butylphenylcarbodiimide, N, N′-di-2,6-dimethylphenylcarbodiimide, N, N ′ -Di-o-triylcarbodiimide and the like tend to be advantageous, and particularly N, N′-
Di-2,6-diisopropylphenylcarbodiimide (hereinafter referred to as TIC) is preferable.

The fluororesin (B) (hereinafter sometimes referred to as polymer (B)) contained in the polyester composition and polyester monofilament of the present invention means
Any polymer may be used as long as it has a fluorine atom in its molecule, for example, a copolymer of ethylene tetrafluoride, propylene hexafluoride and vinylidene fluoride (hereinafter, referred to as 4F / 6F / 2).
F copolymer), tetrafluoroethylene / ethylene copolymer (hereinafter referred to as ETFE), polychlorotrifluoroethylene (hereinafter referred to as PCTFE), chlorotrifluoroethylene / ethylene copolymer (hereinafter referred to as E)
CTFE), polyvinylidene fluoride (hereinafter referred to as PVdF), vinylidene fluoride / tetrafluoroethylene copolymer (hereinafter referred to as 2F / 4F), polytetrafluoroethylene (hereinafter referred to as PTFE), tetrafluoroethylene per Fluoroalkyl vinyl ether copolymers (hereinafter referred to as PFA), tetrafluoroethylene / hexafluoropropylene copolymers (hereinafter referred to as FEP), and other fluoropolymers having a fluorine atom mainly in the polymer molecule main chain and polyperfluoroalkyl Acrylates, polyperfluoroalkyl methacrylates, perfluoroalkyl acrylates and / or acrylates including those containing perfluoroalkyl methacrylates and hydroxyalkyl groups and Or a fluorine having a fluorine atom in the side chain of a polymer molecule such as a random or block copolymer with methacrylate, a polyester or a polyether polyester containing o- or m-perfluorooxyisophthalic acid in at least a part of the dicarboxylic acid component. Resins may be mentioned.

It is possible to impart excellent antifouling properties to the polyester by arbitrarily selecting one or more compounds from these compounds and incorporating them into the polyester.
Among the above fluororesins, the 4F / 6F / 2F copolymer is
It is preferable because a particularly excellent antifouling effect can be obtained. 4
The F.6F.2F copolymer may have any copolymerization ratio of the three components as long as the three components of tetrafluoroethylene, propylene hexafluoride and vinylidene fluoride are copolymerized. A fluorine-based terpolymer comprising 5 to 80 mol% of ethylene, 2 to 35 mol% of propylene hexafluoride and 5 to 90 mol% of vinylidene fluoride is preferred, and 30 to 70 mol% of tetrafluoroethylene and 6 fluorinated Propylene 10-30 mol%
Further, a fluorine-based terpolymer comprising 10 to 50 mol% of vinylidene fluoride is more preferable. It may be a copolymer of other components in addition to the above three components.

Examples of the other copolymerization component include α-olefins such as ethylene, trifluoromonochloroethylene and trifluoroperfluorooxyethylene. The melting point of the fluorine-based terpolymer is in the range of about 70 ° C to 200 ° C, but 100 ° C.
Those exhibiting a melting point of ˜190 ° C. tend to be preferable.

The fluorine-based terpolymer can be produced by a known radical polymerization method such as an emulsion polymerization method, a suspension polymerization method or a solution polymerization method. Industrially, the emulsion polymerization method is used. The suspension polymerization method is preferred. The fluorine-based terpolymer is commercially available as THV ^™ (Sumitomo 3M Limited).
Product) is known.

The fluorine-free thermoplastic polymer (C) (hereinafter referred to as polymer (C)), which is contained in the polyester composition and polyester monofilament of the present invention, means the above-mentioned polyester and polymer (B). Thermoplastic polymers other than, for example, polyethylene, polypropylene, polymethylpentene, cyclic olefin polymers, polybutene-1, polypentene, poly-3-methylbutene-1, poly-4-methylpentene-
Polyolefins such as 1 and the like, polystyrene with atactic structure, polystyrene with isotactic structure, polystyrene with syndiotactic structure, poly-p-methylstyrene, copolymer of styrene and p-methylstyrene, poly-α-methylstyrene-based polymer Polystyrenes such as coalesce and polymethacrylates such as polymethylmethacrylate, polyethylmethacrylate, polyn-propylmethacrylate, polyn-butylmethacrylate, polyn-octylmethacrylate, polyn-decylmethacrylate, polyn-tetradecylmethacrylate Polymer,
Modified polyolefins such as copolymers of various α-olefins and unsaturated acid glycidyl esters, ionomers,
Ethylene / vinyl copolymers such as ethylene / vinyl chloride copolymer and ethylene / vinyl acetate copolymer, terpene resins and other petroleum resins, polyacetal resins, styrene / acrylonitrile copolymers, styrene / maleic anhydride Copolymer, styrene-maleimide anhydride copolymer,
Examples thereof include coumarone / indene copolymers, polyphenylene ethers, polyphenylene sulfides, polycarbonates, polyamides such as nylon 6 and nylon 6.6. By using one of these polymers alone or in combination of two or more, it is possible to impart excellent hydrolysis resistance to the polyester.

Among the above-mentioned polymers (C), polyolefins, polystyrenes and polymethacrylate polymers are more preferable, and among the polyolefins, cyclic olefin polymers are preferably used.

As the cyclic olefin polymer, at least one polymer selected from the following (C1) to (C2) can be used.

(C1) C2 having ethylene as a main component
The above α-olefin and the following general formula [I] or [I
A random copolymer with at least one cyclic olefin represented by I] (hereinafter referred to as an ethylene / cyclic olefin random copolymer).

[0038]

Embedded image (In the general 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, chlorine Represents an atom or a group selected from the group consisting of an atom, a bromine atom and a hydrocarbon group, wherein R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and May have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.)

Embedded image (In the above general 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 each independently represent a hydrogen atom, a chlorine atom,
Represents an atom or a group selected from the group consisting of a bromine atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, wherein a carbon atom to which R ⁹ is bonded and R ¹³ are bonded And the carbon atom to which R ¹⁰ is bonded and the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. = M = 0 when R ¹⁵ and R ¹² or R ¹⁵
And R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. The α-olefin having 2 or more carbon atoms constituting the ethylene / cyclic olefin random copolymer includes ethylene alone or ethylene as a main component, 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-
Penten, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc., alone or in combination Can be used in a small amount mixed with ethylene.

The cyclic olefin represented by the above general formula [I] or [II], which constitutes the ethylene / cyclic olefin random copolymer, may include the following compounds.

Bicyclo [2.2.1] hept-2-ene derivative, tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative, tricyclo [4.3.0.1 ^2,5 ]. -3-Undecene derivative, tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene derivative, pentacyclo [6.
6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene derivative, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 .
0 ^9,13] -4-hexadecene derivative, pentacyclo [7.4.0.1 ^{2,5. 19,12} . 0 ^8,13 ] -3-pentadecene derivative, pentacyclopentadecadiene derivative,
Pentacyclo [8.4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ]
-3-pentadecene derivative, hexacyclo [6.6.
1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene derivatives, heptacyclo [8.7.0.1 ^3,6. 1
^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16] -4-eicosene derivatives, heptacyclo [8.7.0.1 ^3,6. 1
^10,17 . 1 ^{12,1 7} . 0 ^2,7 . 0 ^11,16] -5-eicosene derivatives, heptacyclo [8.8.0.1 ^4,7. 1
^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5- ^heneicosene derivative, heptacyclo [8.8.0.1 ^2,9 . 1
^4,7 . 1 ^11,18 . 0 ^3,8 . 0 ^12,17 ] -5- ^heneicosene derivative, octacyclo [8.8.0.1 ^2,9 . 1
^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5
Docosene derivative, nonacyclo [10.9.1.1 ^4,7 .
1 ^13,20 . 1 ^15,18 . 0 ^3,8 . 0 ^2,10 . 0 ^12,21 . 0
^14,19] -5-pentacosene derivatives, Nonashikuro [1
0.10.1.1.1 ^5,8 . 1 ^14,21 . 1 ^16,19 . 0 ^2,11 .
0 ^4,9 . 0 ^13,22 . 0 ^15,20] -5-hexacosenoic derivatives, 1,4-methano -1,4,4a, 9a- tetrahydrofluorene derivatives, 1,4-methano -1,4,4a,
5,10,10a-hexahydroanthracene derivative,
Cyclopentadiene-acenaphthylene adduct.

Further, the following compounds can be mentioned as these specific compounds.

Embedded image Bicyclo [2.2.1] hept-2-ene and 6-methylbicyclo [2.2.1] hept-2-ene, 5,6
-Dimethylbicyclo [2.2.1] hept-2-ene,
1-methylbicyclo [2.2.1] hept-2-ene,
6-ethylbicyclo [2.2.1] hept-2-ene,
6-n-butylbicyclo [2.2.1] hept-2-ene, 6-isobutylbicyclo [2.2.1] hept-2
-Ene, 7-methylbicyclo [2.2.1] hept-2
A bicyclo [2.2.1] hept-2-ene derivative such as -ene,

Embedded image Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and 8-methyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8
-Propyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] -3-dodecene, 8-butyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene, 8-
Isobutyl tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8-hexyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Cyclohexyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene, 8-stearyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 5,
10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene, 2,10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-Dimethyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8-ethyl-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 11,12-Dimethyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 2,7,9-trimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene, 9-ethyl-2,7-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 9
-Isobutyl-2,7-dimethyltetracyclo [4.
4.0.1 ^2,5 . ^1,7,10 ] -3-dodecene, 9,11,
12-trimethyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 9-ethyl-11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-
3-dodecene, 9-isobutyl-11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 5,8,9,10-tetramethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Ethylidene-9-methyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-Dodecene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] -3-dodecene, 8-ethylidene-9-ethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethylidene-9-isopropyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethylidene-9-
Butyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ]-
3-dodecene, 8-n-propylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
n-Propilidene-9-methyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-propylidene-9-ethyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8-n-propylidene-9-isopropyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-propylidene-9-butyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, 8-isopropylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-isopropylidene-9-methyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropylidene-9-ethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropylidene-9-isopropyltetracyclo [4.4.0.
^12.5 . ^1,7,10 ] -3-dodecene, 8-isopropylidene-9-butyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene, 8-chlorotetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-bromotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8,9-dichlorotetracyclo [4.4.0.
^12.5 . 1 ^7,10] -3-dodecene tetracyclo such [4.4.0.1 ^{2, 5. 1,7,10} ] -3-dodecene derivative, and

Embedded image Hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 .
0 ^2,7 . 0 ^9,14] -4-heptadecene, and 12-methyl hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0
^2,7 . 0 ^9,14] -4-heptadecene, 12-ethylhexanoate cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0
^9,14] -4-heptadecene, 12-isobutyl hexamethylene cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 .
0 ^9,14] -4-heptadecene, 1,6,10- trimethyl-12-isobutyl hexamethylene cyclo [6.6.1.1
^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene hexacyclo such as [6.6.1.1 ^3,6. 1 ^10,13 .
0 ^2,7 . 0 ^9,14] -4-heptadecene derivatives, and

Embedded image Octacyclo [8.8.0.1 ^2,9 . ^14,7 .
1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene, and 15-methyloctacyclo [8.8.0.1
^{2, 9} . ^14,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 .
0 ^12,17 ] -5-docosene, 15-ethyloctacyclo [8.8.0.1 ^2,9 . ^14,7 . 1 ^11,18 . 1 ^13,16 .
0 ^{3, 8} 0 ^12,17 ] -5-dococene and other octacyclo [8.8.0.1 ^2,9 . 1 ^{4, 7} . 1 ^11,18 . 1 ^13,16 .
0 ^3,8 . 0 ^12,17 ] -5-docosene derivative, and

Embedded image Pentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ]
-4-hexadecene, and 1,3-dimethylpentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-Hexadecene, 1,6-dimethylpentacyclo [6.6.
1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,14 ] -4-hexadecene, 1
5,16-Dimethylpentacyclo [6.6.1.
^13-6 . 0 ^2,7 . 0 ^9,14] -4-hexadecene pentacyclo such as [6.6.1.1 ^3,6. 0 ^2,7 . 0 ^9,14 ] −
4-hexadecene derivative, and

[Chemical 21] Such as heptacyclo [8.7.0.1 ^2,9 . ^14,7 . 1
^11,17 . 0 ^3,8 . 0 ^{12,1 6} ] -5-eicosene derivative or heptacyclo [8.7.0.1 ^2,9 . 1 ^{4, 7} . 1
^11,17 . 0 ^3,8 . 0 ^12,16 ] -5-heneicosene derivative, and

Embedded image Tricyclo [4.3.0.1 ^2,5 ] -3-decene and 2-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene, 5-methyltricyclo [4.3. 0.1 ^2,5 ]-
Tricyclo [4.3.0.1 ^2,5 ]-such as 3-decene
3-decene and 2-methyltricyclo [4.3.0.
1 ^2,5 ] -3-decene derivative, and

Embedded image Tricyclo [4.4.0.1 ^2,5 ] -3-undecene and 10-methyltricyclo [4.4.0.1 ^2,5 ]-
3-undecene derivative, and

Embedded image Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ]
-4-pentadecene and 1,3-dimethylpentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 1,6-dimethylpentacyclo [6.5.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 1
4,15-dimethylpentacyclo [6.5.1.
^13-6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene pentacyclo such as [6.5.1.1 ^3,6. 0 ^2,7 . 0 ^9,13 ] −
4-pentadecene derivative, and

Embedded image Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ]
A diene compound such as 4,10-pentadecadiene, and

Embedded image Pentacyclo [7.4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ]
-3-Pentadecene and methyl-substituted pentacyclo [7.4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ] -3-Pentadecene and other derivatives, and

Embedded image Heptacyclo [8.7.0.1 ^3,6 . 1 ^10,17 . 1
^12,15 . 0 ^2,7 . 0 ^11,16 ] -4-eicosene, and dimethyl-substituted heptacyclo [8.7.0.1 ^3,6 . 1
^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ] -4-derivatives such as eicosene, and

Embedded image Nonacyclo [10.9.1.1 ^4,7 . 1 ^13,20 . 1
^15,18 . 0 ^3,8 . 0 ^2,10 . 0 ^12,21 . 0 ^14,19 ] −5
Pentacocene, and trimethylnonacyclo [10.
9.1.1 ^4,7 . 1 ^13,20 . 1 ^15,18 . 0 ^3,8 .
0 ^2,10 . 0 ^12,21 . 0 ^14,19] -5-derivatives such pentacosene, and

Embedded image Pentacyclo [8.4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ]
-3-hexadecene, and 11-methylpentacyclo [8.4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ] -3-Hexadecene and other derivatives, and

Embedded image Heptacyclo [8.8.0.1 ^4,7 . 1 ^11,18 . 1
^13,16 . 0 ^3,8 . 0 ^12,17 ] -5- ^heneicosene , and 15-methylheptacyclo [8.8.0.1 ^4,7 .
1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5- ^heneicosene and other derivatives, and

Embedded image Nonacyclo [10.10.1.1 ^5,8 . 1 ^14,21 . 1
^16,19 . 0 ^2,11 . 0 ^4,9 . 0 ^13,22 . 0 ^15,20 ] -6-
Hexacocene and its derivatives, and

Embedded image 5-Phenyl-bicyclo [2.2.1] hept-2-ene and 5-methyl-5-phenyl-bicyclo [2.
2.1] hept-2-ene, 5-tolyl-bicyclo [2.2.1] hept-2-ene, 5- (ethylphenyl) -bicyclo [2.2.1] hept-2-ene, 5 −
(Isopropylphenyl) -bicyclo [2.2.1] hept-2-ene, 5-biphenyl-bicyclo [2.2.
1] 5-phenyl-bicyclo [2.2.1] hept-2-ene derivatives such as hept-2-ene, and

Embedded image 5-benzyl-bicyclo [2.2.1] hept-2-ene, and

Embedded image 5- (β-naphthyl) -bicyclo [2.2.1] hept-2-ene, and

Embedded image 5- (α-naphthyl) -bicyclo [2.2.1] hept-2-ene, and

Embedded image 5- (anthracenyl) -bicyclo [2.2.1] hept-2-ene, and

Embedded image Cyclopentadiene-acenaphthylene adduct of cyclopentadiene, and

Embedded image 11,12-benzo-pentacyclo [6.5.1.1
^3,6 . 0 ^2,7 . 09, ¹³ ] -4-pentadecene, and

Embedded image 11,12-benzo-pentacyclo [6.5.1.1
^3,6 . 0 ^2,7 . 09, ¹⁴ ] -4-hexadecene, and

Embedded image 11-phenyl-hexacyclo [6.6.1.1 ^3,6 .
1 ^10,13 . 0 ^2,7 . 09, ¹⁴ ] -heptadecene, and

Embedded image 14,15-Benzo-heptacyclo [8.7.0.1
^2,9 . ^14,7 . 1 ^11,17 . 0 ^3,8 . 0 ^12,16 ] -5-Eicosen.

Further, as the cyclic olefin represented by the above general formula [I] or [II], in addition to the above compounds, for example, 1,4,5,8-dimethano-1,2,3,4,4a , 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,
4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,
4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4, 4a, 5,
8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5, 8,
8a- Octahydronaphthalene, 2-methyl-3-ethyl-1,
4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4, 4a, 5,8,
8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,
3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene,
2-n-butyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano- Octahydronaphthalenes such as 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, pentacyclopentadecadiene (hereinafter referred to as PCDE), dicyclopentadiene (hereinafter referred to as DCP) and the like Can be mentioned.

The cyclic olefin represented by the general formula [I] or [II] can be obtained by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by the Diels-Alder reaction. The ethylene / cyclic olefin random copolymer, the copolymerization ratio of the α-olefin containing ethylene as a main component and the cyclic olefin is not particularly limited. Mole%,
The cyclic olefin component is in the range of 20 to 60 mol%.

The ethylene / cyclic olefin random copolymer is usually an amorphous heavy polymer obtained by reacting in a solvent with a catalyst composed of a vanadium compound soluble in a reaction solvent and an organoaluminum compound. It is united.

(C2) The following general formula [III] or [IV]
Or a hydrogenated product thereof (hereinafter referred to as a cyclic olefin ring-opened polymer or ring-opened copolymer or a hydrogenated product thereof).

[0046]

Embedded image [In the above general formula [III], 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 chlorine atom,
Represents an atom or group selected from the group consisting of a bromine atom and a hydrocarbon group, wherein R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, It may have a heavy bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group,
R ¹⁶ and R ¹⁷ each independently represent a group represented by the following formula;

Embedded image (R ^c in the above formula, R ^d, R ^e is a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group or a chlorine or bromine-substituted hydrocarbon group, W represents _{^{SiR g p D 3- p (R}} g Is carbon number 1 to 1
0 hydrocarbon group, D is chlorine atom, bromine raw thread, -OCOR
^h (R ^h is a hydrocarbon group having 1 to 10 carbon atoms) p is an integer of 0 to 3; ), X represents an integer of 0 to 10. ) And R
¹⁶ and R ¹⁷ may be represented by the following formula.

[0047]

Embedded image (R ^f in the above formula represents a hydrocarbon group having 1 to 20 carbon atoms.)]

Embedded image (In the general formula [IV], 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 each independently represent a hydrogen atom, a chlorine atom,
A bromine fiber, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an atom or group selected from the group consisting of an alkoxy group, wherein the carbon atom to which R ⁹ is bonded and R ¹³ are The carbon atom bonded or the carbon atom bonded to R ¹⁰ and the carbon atom bonded to R ¹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵
And R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ) The above-mentioned general formula [III] or [I
V], the above-mentioned α-
In addition to the cyclic olefins constituting the olefin / cyclic olefin random copolymer, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene and 5-ethoxycarbonylbicyclo [2.2.1] hept- 2-ene, 5-propoxycarbonylbicyclo [2.2.1]
Hept-2-ene, 5-isopropoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5
-(2-methylpropoxy) carbonylbicyclo [2.
2.1] Hept-2-ene, 5- (1,2-dimethylethoxy) carbonylbicyclo [2.2.1] hept-2
-Ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5- (4'-t-butylcyclohexyloxy) carbonylbicyclo [2.
2.1] Hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-
5-propoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-isopropoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-butoxycarbonylbicyclo [2.2.1]
Hept-2-ene, 5-methyl-5- (2-methylpropoxy) carbonylbicyclo [2.2.1] hept-2
-Ene, 5-methyl-5- (1,2-dimethylethoxy) carbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-cyclohexyloxycarbonylbicyclo [2.2.1] hept -2-ene, 5-methyl-5- (4'-t-butylcyclohexyloxy) carbonylbicyclo [2.2.1] hept-2-ene, 5-
Methyl-5-phenoxycarbonylbicyclo [2.2.
1] hept-2-ene, 5-cyanobicyclo [2.2.
1] hept-2-ene, 5-methyl-5-cyanobicyclo [2.2.1] hept-2-ene, 8-methoxycarbonyltetracyclo [4.4.0 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propoxycarbonyltetracyclo [4.4.0 ^2,5 . 1
^7,10] dodeca-3-ene, 8-isopropoxycarbonyl tetracyclo [4.4.0 ^{2, 5.} 1 ^7,10 ] dodeca-3
-Ene, 8-butoxycarbonyltetracyclo [4.
4.0 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-methylpropoxy) carbonyltetracyclo [4.4.0]
^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (1-methylpropoxy) carbonyltetracyclo [4.4.0 ^2,5 .
1 ^7,10 ] dodec-3-ene, 8- (2,2-dimethylethoxy) carbonyltetracyclo [4.4.0 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-cyclohexyloxycarbonyltetracyclo [4.4.0 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (4'-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-phenoxycarbonyltetracyclo [4.4.0 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0 ^2,5 . ^1,7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.
0 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-
Isopropoxycarbonyltetracyclo [4.4.0
^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-propoxycarbonyltetracyclo [4.4.0 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-methyl-8-butoxycarbonyltetracyclo [4.4.0 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2-methylpropoxy) carbonyltetracyclo [4.4.0 ^2,5 .
1 ^7,10 ] dodec-3-ene, 8-methyl-8- (1-methylpropoxy) carbonyltetracyclo [4.4.0
^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-
(2.2-Dimethylethoxy) carbonyltetracyclo [4.4.0 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyclohexyloxycarbonyltetracyclo [4.4.0 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
Methyl-8- (4'-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0 ^2,5 .
1 ^{7, 10]} dodeca-3-ene, 8-methyl-8-phenoxycarbonyl tetracyclo [4.4.0 ^2,5. 1 ^7,10 ]
Dodeca-3-ene, 8-cyanotetracyclo [4.4.
0 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-
Cyanotetracyclo [4.4.0 ^2,5 . [ ^1,7,10 ] dodec-3-ene and the like. These cyclic olefins can be used alone or in combination.

The ring-opening polymer or ring-opening copolymer of a cyclic olefin or a hydrogenated product thereof is obtained by converting the above-mentioned cyclic olefin into a halide of a metal such as ruthenium, rhodium, palladium, osmium, indium, platinum or tungsten. A catalyst consisting of nitrates of these metals or acetylacetonates of these metals and a reducing agent, and halides of metals such as titanium, palladium, zirconium and molybdenum or acetylacetonates of these metals, and organoaluminum. It was polymerized in the presence of a catalyst consisting of

The intrinsic viscosity of the above ethylene / cyclic olefin random copolymer, cyclic olefin ring-opening (co) polymer, and hydrogenated product of cyclic olefin ring-opening (co) polymer measured in decalin at 135 ° C. η] is usually 0.01 to
It is 20 dl / g, preferably 0.05 to 10 dl / g, more preferably 0.08 to 8 dl / g.

The above ethylene / cyclic olefin random copolymer, cyclic olefin ring-opening (co) polymer, and hydrogenated product of cyclic olefin ring-opening (co) polymer are commercially available products,
Apel ^TM (product of Mitsui Petrochemical Industries, Ltd.), Zeonex ^TM
It is known as (Zeon Corporation product), Arton ^TM (Nippon Synthetic Rubber product), etc.

In the polymer component of the polyester composition and polyester monofilament of the present invention, the compounding ratio of the polyester (A) to the fluororesin (B) and the polymer (C) is 70 to 99.6% by weight of the polyester (A). , 0.2 to 29.8 wt% of the fluororesin (B) and 0.2 to 29.8 wt% of the polymer (C), and the total amount of the fluororesin (B) and the polymer (C) is 0. 4-30% by weight
It is. If the compounding ratio of the polyester (A) is higher than the above range (that is, the compounding ratio of the fluororesin (B) and the polymer (C) is less than the above range), antifouling property and hydrolysis resistance are insufficient. It is not preferable because On the other hand, if the compounding ratio of the polyester (A) is less than the above range (that is, the compounding ratio of the fluororesin (B) and the polymer (C) is more than the above range), the strength becomes insufficient, which is not preferable.

The polyester (A) is 72 to 99% by weight, the fluororesin (B) is 0.5 to 27.5% by weight, and the polymer (C) is 0.5 to 27.5% by weight, and the fluororesin is The total of (B) and polymer (C) is 1.0 to 28% by weight.
Is more preferable, 74 to 98% by weight of polyester (A), 1 to 25% by weight of fluororesin (B) and polymer (C)
More preferably, it is 1 to 25% by weight, and the total amount of the fluororesin (B) and the polymer (C) is 2 to 26% by weight.

The polyester composition or polyester monofilament of the present invention contains the carbodiimide compound (D) in an unreacted state in an amount of 0.005% by weight or more and 1.5% or more.
Contains less than or equal to wt%. The content of the unreacted carbodiimide compound is 0.01% by weight or more and 1.2
It is more preferable that the content is not more than wt%. When the content of the carbodiimide compound in the unreacted state is less than 0.005% by weight, the effect of further improving the hydrolysis resistance is small, and when it is more than 1.5% by weight, the physical properties tend to be deteriorated.
It is not preferable because the polyester composition or the polyester monofilament is more likely to bleed out than the polymer during the production.

The content of the unreacted carbodiimide compound in the polyester composition or polyester monofilament referred to in the present invention is measured by the following method. (1) Weigh about 200 mg of a sample in a 100 ml volumetric flask. (2) Add 2 ml of hexafluoroisopropanol / chloroform (volume ratio 1/1) to dissolve the sample. (3) When the sample is dissolved, add 8 ml of chloroform. (4) Acetonitrile / chloroform (volume ratio 9/1)
Is gradually added to make 100 ml while precipitating the polymer. (5) The sample solution is filtered through a 0.45 μm disk filter and quantitatively analyzed by HPLC. HPLC analysis conditions are as follows. Column: Inertsil ODS-2 4.6 mm
× 250 mm Mobile phase: acetonitrile / water (volume ratio 94/6) Flow rate: 1.5 ml / min. Sample amount: 20 μl Detector: UV (280 nm) To make the polyester contain the carbodiimide compound in an unreacted state of 0.005% by weight or more and 1.5% by weight or less, the terminal carboxyl group concentration of the raw material polyester and Depending on the reaction conditions, the unreacted residual carbodiimide compound in the polyester after the reaction is 0.0
The carbodiimide compound may be added to the polyester in an amount to achieve a concentration of from 05% by weight to 1.5% by weight and reacted. The excellent hydrolysis resistance of the polyester composition and the polyester monofilament of the present invention is that the presence of the above-mentioned polymer (C) suppresses the deactivating side reaction of the carbodiimide compound in the polyester, and the residual amount of the unreacted carbodiimide compound. It is considered that the expression is caused by an increase in.

Polyester and fluororesin (B) of the present invention
The mixing of the polymer (C) and the carbodiimide compound (D) is usually carried out by mixing the polyester and the fluororesin (B) with the polymer (C) and the carbodiimide compound (D), and then stirring and reacting in a reaction vessel. Or the polymer (C) and the carbodiimide compound (D) are melt-mixed in advance, and then the polyester and the fluororesin (B) are mixed.
And a fluororesin (B), a polymer (C) and a carbodiimide compound (D) are melt-mixed in advance and then melt-mixed with polyester. In this method, at least the polymer (C) and the carbodiimide compound (D) are melt-kneaded in advance before melting or in the process thereof, and then melt-kneaded with polyester. Although the reason is not clear, for example, by pre-melt mixing the polymer (C) and the carbodiimide compound (D),
With the hydroxyl end group of the polyester, which occurs when the carbodiimide compound (D) is contained in the polymer (C) and stored, and then the polyester and the carbodiimide compound (D) are directly mixed for melt mixing with the polyester. It is presumed that the side reaction with the carbodiimide compound (D) is suppressed and the carboxyl end group blocking reaction is efficiently performed.

This preferable manufacturing method will be specifically described. The preferred production method is to add the required amount of carbodiimide compound (D) to polymer (C) or mixed pellets of fluororesin (B) and polymer (C), and heat and melt in an extruder or a mixing can to stir and mix. Then, after the mixture is taken out and cooled, a pelletized master polymer is melt-mixed with polyester and then extruded to be processed into a polyester composition or a polyester monofilament, or the softening point of the polymer (C) is the melting point of the polyester. If it is lower than the above, the polyester, the fluororesin (B), the polymer (C), and the carbodiimide compound (D) are each supplied in a predetermined amount to an extruder and stirred to heat and melt the mixture to a temperature not lower than the melting point of the polyester. , Then extruded polyester composition or polyester monofilament Method for processing are preferred (hereinafter, referred to as an extruder method). In this case, at least the polymer (C) among the polyester, the fluororesin (B), the polymer (C) and the carbodiimide compound (D) which are supplied to the extruder and moved to the heating zone while being sheared by the screw is used. The phenomenon in which the carbodiimide compound (D) and the carbodiimide compound (D) are melt-mixed first occurs in the extruder due to heat insulation and heating.
A composition in which the polymer (C) and the carbodiimide compound (D) are substantially melt-kneaded in advance is formed. Next, or in the process, the polyester (A) is melted, and the polyester (A) and the melt-kneaded composition of the polymer (C) and the carbodiimide compound (D) are melt-kneaded. This method is suitable for producing the polyester composition or polyester monofilament of the present invention because it does not require any special equipment such as a melt-kneading can and a pelletizing equipment. Further, in the above method, the fluororesin (B)
And polyester or fluororesin (B) and polymer (C)
It is possible to use mixed polymer pellets prepared by melt-kneading and.

In order to efficiently bring out the effects of the present invention, a phosphorus compound is used as a phosphorus atom in the polyester.
It can be contained in an amount of 0 ppm or less and within the range of the following general formula. 5 × 10 ⁻³ ≦ P ≦ M + 8 × 10 ⁻³ (P in the formula is mol% of phosphorus atom with respect to dibasic acid constituting polyester, M is a metal in the polyester resin, Group II of the periodic table, It is the mol% of one or more metal atoms selected from Group VII and VIII and selected from the 3rd and 4th cycles with respect to the dibasic acid constituting the polyester, and even when M = 0. The polyester composition of the present invention thus obtained is superior in both antifouling properties and hydrolysis resistance to the conventional ones, and is an electrical connector used under conditions where it is easily soiled and under a high temperature and high humidity atmosphere. It can be preferably used for machine parts such as gears, gears and bearings, resin molded products such as various structural members, and monofilaments.

When the polymer (C) in the polyester composition of the present invention is a cyclic olefin polymer or polystyrene or polymethacrylate polymer, the polyester composition of the present invention has excellent hydrolysis resistance. And tends to have excellent water and oil repellency. The polymer (C) in the polyester composition of the present invention is polyethylene, polypropylene, polymethylpentene, polybutene-1, polypentene, poly-3.
In the case of polyolefins such as -methylbutene-1 and poly-4-methylpentene-1, the polyester composition of the present invention tends to have excellent hydrolysis resistance and excellent water repellency. .

As described above, the polyester monofilament of the present invention is produced by adding a predetermined amount of the carbodiimide compound (D) to the polyester, the fluororesin (B) and the polymer (C), and kneading them with an extruder, for example. Extruded from the spinneret through a polymer streamline interchanger installed at the tip of the extruder, a filtration layer, etc., and then cooled.
It can be produced by a known method such as stretching and heat setting.

The polyester monofilament of the present invention is a core-sheath composite monofilament comprising a monofilament composed of the composition of the present invention, a core of the composition of the present invention, and a core of the composition of the present invention. Is also good.

The monofilament of the present invention is a continuous yarn consisting of one single yarn, and the shape of the cross section perpendicular to the fiber axis direction of the monofilament (hereinafter referred to as cross sectional shape or cross section) is circle, flattened, square, half-moon. It may have any cross-sectional shape such as a shape, a triangle, a polygon with five or more sides, a multileaf shape, a dog bone shape, or a cocoon shape. When the monofilament of the present invention is used as a constituent material of an industrial fabric, the monofilament preferably has a circular or flat cross section. In particular, when the monofilament is a warp yarn of a papermaking dryer canvas, a monofilament having a flat cross section is preferably used from the viewpoint of effectively exhibiting antifouling property and flatness of the canvas.

The term "flat" in the present invention means an ellipse, a square or a rectangle, but in addition to a mathematically defined exact ellipse, a square or a rectangle, a shape substantially similar to an ellipse, a square or a rectangle, for example, a square. Alternatively, it includes a shape in which the four corners of a rectangle are rounded. In the case of an ellipse, the length (LD) of the major axis and the length (SD) of the minor axis that intersect at a right angle at the center of the ellipse have a relationship satisfying the following expression, and in the case of a square or a rectangle, It is preferable that the long side length (LD) and the short side length (SD) of the square or rectangle have a relationship satisfying the following expression. 1.0 ≦ LD / SD ≦ 10 The length of the line segment passing through the center of gravity of the monofilament cross section can be appropriately selected depending on the application, but is preferably in the range of 0.05 to 2.5 mm. The required strength of the yarn varies depending on the application, but is preferably about 3.0 g / denier or more.

The polyester monofilament of the present invention thus obtained is superior in antifouling property and hydrolysis resistance to the conventional ones. It is also useful as a constituent yarn of various industrial fabrics such as a press felt base fabric for papermaking and a papermaking dryer canvas.

Here, the papermaking wire refers to various woven fabrics such as a single woven fabric, a double woven fabric and a triple woven fabric, and is a fabric used in a paper making process and used as a Fourdrinier or a round net. . Further, the papermaking dryer canvas is a woven fabric such as a single woven fabric, a double woven fabric and a triple woven fabric, which is used for drying the paper in the dryer of the papermaking machine. Further, the thermal bonding process net conveyor for thermal bonding non-woven fabric is a woven fabric for passing the non-woven fabric into a furnace in order to fuse the heat-adhesive fibers such as low melting point polyethylene constituting the non-woven fabric, Textiles such as single weave and double weave. The filter is a fabric used for filtering soy sauce, alcoholic beverages, sieving various powders such as wheat flour and starch, and is a fabric such as a single woven fabric or a double woven fabric.

The papermaking dryer canvas of the present invention is obtained by weaving the polyester monofilament of the present invention as at least a part of the weft yarn and / or the warp yarn constituting the dryer canvas. The weaving method of the dryer canvas can be appropriately selected depending on the application, and for example, known weaving methods such as plain weave, twill weave, double weave, triple weave, and spiral structure can be adopted.

The papermaking dryer canvas of the present invention is superior in antifouling property and hydrolysis resistance to the conventional one, and has less stains during use and is washed as compared with the conventional papermaking dryer canvas using the polyester monofilament. The cycle can be extended and dirt can be easily cleaned. Further, at the same time, since the deterioration of the strength of the canvas due to hydrolysis is suppressed, it has an excellent feature that the replacement cycle of the canvas can be greatly extended, which is useful.

The polyester composition of the present invention is superior in antifouling property and hydrolysis resistance to the conventional ones.
Fibers such as multi-filament, non-woven fabric, staple fiber and cotton-like, ski clothes, judo wear, training wear, sports clothes such as sports uniforms and clean work clothes, work clothes for food industry, apron, table cloth, non-woven fabric It can be preferably used for various filters and medical clothes and electronic parts, which are sterilized and disinfected in high temperature steam, automobile parts, bottles, films, sheets and the like.

[0068]

The present invention will be described in more detail with reference to the following examples. In the following examples, a monofilament, which is a preferred embodiment of the polyester composition of the present invention, and a paper-making dryer canvas, which is a preferred embodiment of an industrial fabric, will be specifically described.

The characteristic values of the polyester composition and polyester monofilament in the following examples are measured by the following methods unless otherwise specified.

1. Antifouling property (1) Preparation of contaminated liquid Talc 1 part by weight Alkyl ketene dimer 0.5 part by weight Acrylamide 0.5 part by weight Water 98 parts by weight The above contaminated liquid consists of dirt and water that are usually attached to a paper dryer canvas. It is close to the composition. (2) While stirring the adjusted contaminated liquid at 300 rpm,
An operation of immersing the weighed monofilament in a bath ratio of 1: 5000 for 5 seconds and drying at 70 ° C. for 1 minute was repeated 10 times to obtain a stain-adhered sample. (3) The sample with stains was weighed to determine the amount of stains. (4) The stain amount indicates that the smaller the index (hereinafter referred to as the stain index) when the stain amount of the PET monofilament not containing the fluororesin (B) is 100, the smaller the stain amount.

2. Evaluation of water and oil repellency (contact angle measurement) The water repellency and oil repellency were measured by the following method. The contact angle of a flat (substantially rectangular) cross-section monofilament was measured by the following method. The larger the contact angle, the higher the water / oil repellency. (1) Using a goniometer type contact angle measuring device manufactured by Elma Optical Co., Ltd. (2) Water contact angle: distilled water, oil contact angle: using decalin (3) Droplet amount: 5 μl (4) Measuring temperature: 20 ° C.

3. Tensile test of monofilament The test was performed according to JIS L1013-1992. (1) Sample gripping interval 25 cm (2) Tensile speed 30 cm / min. (3) Test temperature 20 ℃

4. Hydrolysis resistance test of monofilament The monofilament was put into a 100 liter autoclave and kept in 121 ° C. saturated steam for 10 days, 12 days, 15 minutes.
After the treatment for 22 days, the strength of the monofilament after the treatment was obtained by the tensile test of the above monofilament, and the strength retention ratio compared with the strength of the monofilament before the treatment was used as a measure of hydrolysis resistance (hereinafter referred to as "hydrolysis resistance"). The strong retention rate after decomposition). The higher the retention of strength after hydrolysis, the better the hydrolysis resistance.

Example 1 Intrinsic viscosity 0.93, terminal carboxyl group concentration 13 equivalents /
10 ⁶ g of PET dry chips were prepared (hereinafter referred to as PET
Called a chip).

About 6 parts of tetrafluoroethylene as the fluororesin (B)
A copolymer consisting of 0 mol%, about 20 mol% of propylene hexafluoride and about 20 mol% of vinylidene fluoride (THV ^™ 50
0G (Sumitomo 3M product), melting point approx. 175 ° C)
(Hereinafter referred to as THV500G) was prepared.

As the polymer (C), which is a kind of cyclic olefin polymer, the copolymerization components are ethylene and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene and ethylene-cyclic olefin random copolymer composed mainly of APEL ^TM 6015 (Mitsui Petrochemical Industries, Ltd., A
MF measured at 260 ° C according to STM D1238
R10g / 10min. ) (Hereinafter referred to as APEL6015) was prepared.

80 ° C. as carbodiimide compound (D)
A TIC (hereinafter, referred to as a liquid TIC) that was heated and melted in 1. was prepared.

The above PET chip, THV500G, A
The PEL6015 and the PEL6015 were weighed so as to have the weight ratios shown in Table 1, and supplied to the uniaxial extruder through the hopper of the uniaxial extruder and the polymer pipe below the hopper. At the same time, liquid TIC was supplied to the chip in the polymer pipe below the hopper while being weighed so that the weight ratio shown in Table 1 was obtained. PET chip, THV500G,
A molten polymer obtained by kneading APEL6015 and liquid TIC at about 285 ° C. for 3 minutes in a single-screw extruder,
Filtration layer in the spinning pack through the gear pump and streamline interchanger ("Static Mixer" by Chemix, USA)
Through a spinneret for flat cross section. After cooling the spun filament in a hot water bath at 80 ° C, it was stretched and heat-set to a total of 5.0 times and heat-set according to a conventional method, and the long side length was 0.56 m.
m, and a polyester monofilament having a substantially rectangular cross section (flat cross section) having a short side length of 0.28 mm was obtained.

The content of unreacted carbodiimide compound (D) (hereinafter referred to as unreacted TIC) and COOH end group concentration in the monofilament are shown in Table 1, and the strength and elongation characteristics,
Table 2 shows properties such as contact angle, stain index, and tenacity retention after hydrolysis.

Comparative Example 1 THV500G which is the fluororesin (B) in Example 1
Polymer composition of polyester monofilament, unreacted TIC content and COOH end obtained in the same manner as in Example 1 except that APEL6015 which is a polymer (C) was not added and PET chips corresponding to the weight loss were added. The group concentration is also shown in Table 1, and the characteristics are shown in Table 2.

Comparative Example 2 THV500G which is the fluororesin (B) in Example 1
Polymer composition, unreacted TIC content and C of polyester monofilament obtained in the same manner as in Example 1 except that the PET chip for the weight reduction was added without adding
The OOH end group concentration is also shown in Table 1, and the characteristics are also shown in Table 2.

Comparative Example 3 APEL6015 which is the polymer (C) in Example 1
Polymer composition, unreacted TIC content and C of polyester monofilament obtained in the same manner as in Example 1 except that the PET chip for the weight reduction was added without adding
The OOH end group concentration is also shown in Table 1, and the characteristics are also shown in Table 2.

Comparative Example 4 Polymer composition, unreacted TIC content and COOH end of a polyester monofilament obtained in the same manner as in Example 1 except that the liquid TIC which is the carbodiimide compound (D) in Example 1 was not added. The group concentration is also shown in Table 1, and the characteristics are shown in Table 2.

Examples 2 to 16 and Comparative Examples 5 to 10 Obtained in the same manner as in Example 1 except that the PET chip, THV500G and APLE6015 in Example 1 were changed in the ratio of the amounts as shown in Table 1. The polymer composition, unreacted TIC content and COOH end group concentration of the polyester monofilament are also shown in Table 1, and the properties are also shown in Table 2.

[0085]

[Table 1]

[Table 2] From the above results, it can be seen that the monofilament, which is one preferable example of the form of the polyester composition of the present invention, has both excellent antifouling property and hydrolysis resistance, and has sufficient strength and elongation. .

Example 17 THV500G which is the fluororesin (B) in Example 1
Is a copolymer of about 50 mol% of tetrafluoroethylene, about 20 mol% of propylene hexafluoride and about 30 mol% of vinylidene fluoride (THV ^™ 400G (Sumitomo 3M Co., Ltd. product), melting point about 155 ° C.) (Hereinafter, referred to as THV400G) Polymer composition of polyester monofilament and unreacted TI obtained in the same manner as in Example 1 except that the composition was changed to THV400G.
The C content and COOH end group concentration are shown in Table 3, and the properties are shown in Table 4. The contents and results of Example 1 are also shown in Tables 3 and 4 for reference.

Example 18 THV500G which is the fluororesin (B) in Example 1
Is a copolymer of about 40 mol% of tetrafluoroethylene, about 20 mol% of propylene hexafluoride and about 40 mol% of vinylidene fluoride (THV ^™ 200G (Sumitomo 3M Co., Ltd. product, melting point about 120 ° C.)). (Hereinafter, referred to as THV200G) Polymer composition of polyester monofilament obtained in the same manner as in Example 1 except that it was changed to unreacted TI
The C content and the COOH end group concentration are also shown in Table 3, and the properties are also shown in Table 4.

Example 19 THV500G which is the fluororesin (B) in Example 1
Was changed to a random copolymer of ethylene and tetrafluoroethylene (Neoflon ^TM EP-521 (manufactured by Daikin Industries, Ltd.) (hereinafter referred to as EP-521) in the same manner as in Example 1. Polymer composition, unreacted TIC content and COOH of the obtained polyester monofilament
The terminal group concentration is also shown in Table 3, and the properties are shown in Table 4.

Example 20 EP-521 which is the fluororesin (B) in Example 8
In the same manner as in Example 1 except that NEOFLON ^TM EP-610 (a product of Daikin Industries, Ltd.) (hereinafter referred to as EP-610), which is also a random copolymer of ethylene and tetrafluoroethylene, is changed. The polymer composition, unreacted TIC content and COOH end group concentration of the polyester monofilament thus obtained are also shown in Table 3, and the properties are also shown in Table 4.

[0090]

[Table 3]

[Table 4] From the above results, it can be seen that the monofilament, which is one preferable example of the form of the polyester composition of the present invention, has both excellent antifouling property and hydrolysis resistance, and has sufficient strength and elongation. .

Example 21 APEL6015, which is an ethylene / cycloolefin co-random polymer of the polymer (C) in Example 1, was replaced with APEL ^™ 6013 (Mitsui Petrochemical Co., Ltd.), which was also an ethylene / cycloolefin co-random polymer. (Product) (hereinafter referred to as APEL6013) except that the polymer composition, unreacted TIC content and COOH end group concentration of the polyester monofilament obtained in the same manner as in Example 1 are shown in Table 5, and the characteristics are shown in Table 6. It is also shown in. In addition,
For reference, the contents and results of Example 1 are also shown in Tables 5 and 6.

Example 22 APEL6015, which is an ethylene / cycloolefin random polymer of the polymer (C) in Example 1, was mixed with ZE.
Polymer composition and unreacted TIC content of a polyester monofilament obtained in the same manner as in Example 1 except that ONEX ^™ 280 (a cyclic olefin ring-opening polymer manufactured by Nippon Zeon Co., Ltd.) (hereinafter referred to as ZEONEX 280) was used. The COOH end group concentration is also shown in Table 5, and the characteristics are shown in Table 6.

Examples 23 to 29 APEL6015, which is an ethylene / cyclic olefin copolymer random polymer of the polymer (C) in Example 1, is
Methoxycarbonyltetracyclo [4.4.0 ^2,5 . 1
^7,10 ] Dodeca-3-ene ring-opening polymer (hereinafter referred to as PMTC
(Example 23), similarly,
APEL6015 which is the polymer (C) in Example 1
To high density polyethylene (hereinafter referred to as HDPE) (Example 24), similarly to polypropylene (hereinafter referred to as PP) (Example 25), and similarly atactic polystyrene (hereinafter referred to as PS). ) (Example 26), similarly to syndiotactic polystyrene (hereinafter referred to as SPS) (Example 27), similarly to polymethylpentene (hereinafter P).
Other than changing to MPT) (Example 28) and changing to Sumipex ^™ MH (Sumitomo Chemical Co., Ltd. product) (hereinafter referred to as PMMA) which is also a methacrylic resin (Example 29). The polymer composition, unreacted TIC content and COOH end group concentration of the monofilament obtained in the same manner as in Example 1 are also shown in Table 5, and the properties are also shown in Table 6.

[0094]

[Table 5]

[Table 6] From the above results, it can be seen that the monofilament, which is one preferable example of the form of the polyester composition of the present invention, has both excellent antifouling property and hydrolysis resistance, and has sufficient strength and elongation. .

Examples 30 to 33 and Comparative Examples 11 to 12 Unreacted substances shown in Table 7 were the same as in Example 1 except that the addition amount of the liquid TIC in Example 1 was changed as shown in Table 7. A monofilament containing the carbodiimide compound (D) was obtained. Polymer composition, unreacted TIC content and COOH end group concentration are shown in Table 7, and properties are shown in Table 8. The contents and results of Example 1 are shown in Table 7 for reference.
And also shown in Table 8.

[0096]

[Table 7]

[Table 8] From the above results, it can be seen that the monofilament, which is one preferable example of the form of the polyester composition of the present invention, has both excellent antifouling property and hydrolysis resistance, and has sufficient strength and elongation. .

Example 34 The flat-section yarn spinneret used for spinning the monofilament in Example 1 was changed to a circular-section yarn spinneret with a diameter of 0.
A monofilament having a circular cross section of 46 mm was produced.

Example 35 A twill canvas for a papermaking dryer (hereinafter referred to as canvas) was prepared by using the monofilament having a circular cross section obtained in Example 34 as a weft and the monofilament having a flat cross section obtained in Example 1 as a warp. . The canvas was attached to a dryer of a neutral paper machine, used for drying the paper at 140 ° C. for 1 year, and then the canvas was removed.
Table 9 shows the tenacity remaining ratio of the warp on the canvas after use to the tenacity of the warp on the canvas before use. Also, after cutting off a part of the canvas after this use, the weight is measured, ultrasonic cleaning is performed for 3 minutes in water containing 0.5% by weight of a neutral surfactant, and the plain fabric after cleaning is washed with water and dried. Table 9 also shows the stain adhesion rate obtained by the method of measuring the weight of the.

Example 36 A monofilament having a circular cross section with a diameter of 0.46 mm was produced by changing the spinneret for flat section yarn used for spinning the monofilament in Example 20 to a spinneret for circular section yarn.

Example 37 The weft yarn constituting the twill canvas for papermaking dryer in Example 35 was changed to the monofilament having the circular cross section obtained in Example 36, and the monofilament having the flat cross section obtained in Example 20 was used as the warp. Table 9 also shows the results of using the twill canvas for papermaking dryer, which was performed in the same manner as in Example 35 except for the above.

Example 38 A monofilament having a circular cross section with a diameter of 0.46 mm was produced by changing the spinneret for flat section yarn used for spinning the monofilament in Example 25 to a spinneret for circular section yarn.

Example 39 The weft yarn constituting the twill canvas for papermaking dryer in Example 35 was changed to the monofilament having the circular cross section obtained in Example 38, and the monofilament having the flat cross section obtained in Example 25 was used as the warp. Table 9 also shows the results of using the twill canvas for papermaking dryer, which was performed in the same manner as in Example 35 except for the above.

Example 40 A monofilament having a circular cross section with a diameter of 0.46 mm was produced by changing the spinneret for flat cross section used in the spinning of monofilament in Example 27 to a spinneret for circular cross section.

Example 41 The weft yarn constituting the twill canvas for papermaking dryer in Example 35 was changed to the monofilament having a circular cross section obtained in Example 40, and the monofilament having a flat cross section obtained in Example 27 was used as a warp. Table 9 also shows the results of using the twill canvas for papermaking dryer, which was performed in the same manner as in Example 35 except for the above.

Comparative Example 13 A monofilament having a circular cross section with a diameter of 0.46 mm was produced by changing the flat section yarn spinneret used for spinning the monofilament in Comparative Example 5 to a circular cross section yarn spinneret.

Comparative Example 14 The weft yarn constituting the twill canvas for papermaking dryer in Example 35 was changed to the monofilament having a circular cross section obtained in Comparative Example 13, and the monofilament having a flat cross section obtained in Comparative Example 5 was used as a warp. Example 3 except that it was used
Table 9 also shows the results of using the twill canvas for papermaking dryer, which was performed in the same manner as in No. 5.

[0107]

[Table 9] From the above examples, it is understood that the papermaking dryer canvas, which is a preferred example of the industrial woven fabric of the present invention, has excellent antifouling properties and hydrolysis resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D21F 1/10 D21F 1/10 7/08 7/08 A // D04H 1/54 D04H 1/54 Z (C08L 67/00 27:12 25:00) (C08L 67/00 27:12 23:00) (C08L 67/00 27:12 33:10) (C08L 67/00 27:12 23:04) ( 72) Inventor Kei Horii 4845 Mishima City, Shizuoka Prefecture Toray Co., Ltd. Mishima Plant (72) Inventor Akira Kinoshita 1 Kawara, Showa Town, Aichi Prefecture Toray Monofilament Co., Ltd.

Claims (10)

[Claims] 1. The polymer component is polyester (A) 70.
~ 99.6% by weight, and fluororesin (B) 0.2-29.8
% By weight and 0.2 to 29.8% by weight of a fluorine-free thermoplastic polymer (C), and the total amount of the fluororesin (B) and the polymer (C) is 0.4 to 30% by weight. A polyester composition containing 0.005 to 1.5% by weight of the carbodiimide compound (D) in which the polymer component is unreacted. 2. The polyester (A) constituting the polyester composition has a terminal carboxyl group concentration of 10 equivalent / 10.
The polyester composition according to claim 1, which is ⁶ g or less. 3. The polyester composition according to claim 1, wherein the fluororesin (B) is a copolymer of ethylene tetrafluoride, propylene hexafluoride and vinylidene fluoride. 4. The thermoplastic polymer (C) containing no fluorine atom is at least one selected from polyolefins, polystyrenes and polymethacrylate polymers. Polyester composition. 5. The polyolefins are the following (C1) to
The polyester composition according to claim 4, which is at least one cyclic olefin polymer selected from (C2). (C1) A random copolymer of an α-olefin having 2 or more carbon atoms containing ethylene as a main component and at least one cyclic olefin represented by the following general formula [I] or [II]. Embedded image (In the general 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, chlorine An atom or a group selected from the group consisting of an atom, a bromine atom and a hydrocarbon group, wherein R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic May have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.) (In the above general 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 each independently represent a hydrogen atom, a chlorine atom,
Represents an atom or a group selected from the group consisting of a bromine atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, wherein a carbon atom to which R ⁹ is bonded and R ¹³ are bonded And the carbon atom to which R ¹⁰ is bonded and the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. = M = 0 when R ¹⁵ and R ¹² or R ¹⁵
And R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. (C2) A ring-opening polymer or ring-opening copolymer of at least one cyclic olefin represented by the following general formula [III] or [IV], or a hydrogenated product thereof. Embedded image [In the above general formula [III], 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 chlorine atom,
Represents an atom or group selected from the group consisting of a bromine atom and a hydrocarbon group, wherein R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, It may have a heavy bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group,
R ¹⁶ and R ¹⁷ each independently represent a group represented by the following formula: (R ^c in the above formula, R ^d, R ^e is a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group or a chlorine or bromine-substituted hydrocarbon group, W represents _{^{SiR g p D 3- p (R}} g Is carbon number 1 to 1
0 hydrocarbon group, D is chlorine atom, bromine atom or -OCOR
^h (R ^h is a hydrocarbon group having 1 to 10 carbon atoms) p is an integer of 0 to 3; ), X represents an integer of 0 to 10. ) And R
¹⁶ and R ¹⁷ may be represented by the following formula. Embedded image (R ^f in the above formula represents a hydrocarbon group having 1 to 20 carbon atoms.)] (In the general formula [IV], 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 each independently represent a hydrogen atom, a chlorine atom,
A bromine fiber, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an atom or group selected from the group consisting of an alkoxy group, wherein the carbon atom to which R ⁹ is bonded and R ¹³ are The carbon atom bonded or the carbon atom bonded to R ¹⁰ and the carbon atom bonded to R ¹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵
And R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ) 6. The polyester (A) according to claim 1, which is polyethylene terephthalate.
Item 7. The polyester composition according to Item 1. 7. A polyester monofilament comprising the composition according to any one of claims 1 to 6. 8. The polyester monofilament according to claim 7, wherein the cross section of the monofilament perpendicular to the fiber axis direction is circular or flat. 9. An industrial woven fabric using the polyester monofilament according to claim 7 or 8 as at least a part of a weft or a warp constituting a woven fabric. 10. The industrial woven fabric is a paper making dryer canvas, a paper making wire, a net bond for thermal bonding non-woven fabric thermal bonding process, or a filter.
The industrial textile described.