JP4939097B2 - Polyester compositions, monofilaments and industrial fabrics - Google Patents

Description

  The present invention is a polyester composition excellent in hydrolysis resistance, and further excellent in oxidative degradation resistance, a polyester monofilament, a papermaking dryer canvas using the polyester monofilament, a belt fabric for a heat bonding process of a nonwoven fabric, and a heat treatment furnace. The present invention relates to various industrial fabrics used in at least one selected from fabrics for conveyor belts.

Since polyester has excellent physical properties, it has been used for various industrial parts, clothing and industrial fiber materials, various textiles, and the like. For example, as polyester monofilament, various belts such as paper dryer canvas, paper making wire, nonwoven fabric belt fabric for thermal bonding process, fabric for conveyor belt in heat treatment furnace, various brushes, brush, printing screen kite, fishing line, rubber reinforcement It has been widely used as a constituent material for various industrial fabrics such as fiber materials.
However, when used as a constituent material of a paper-making dryer canvas such as high temperature and high humidity, the polyester monofilament causes a decrease in strength due to hydrolysis degradation. It was difficult to withstand use.

  Various proposals have heretofore been made in order to improve the hydrolysis resistance, which is a drawback of such polyester monofilaments.

  For example, a polyester monofilament (for example, see Patent Document 1) to which a specific amount of polyolefin such as polyethylene, polypropylene, polybutene, poly-4-methylpentene 1, and polystyrene is added is known. The monofilament made of polyethylene terephthalate to which polyethylene is added has a small effect of improving hydrolysis resistance and is not practical.

  Moreover, the method of improving the hydrolysis resistance of polyester by adding a carbodiimide compound is known. For example, a method of forming a filament not containing unreacted carbodiimide by adding a mono- or biscarbodiimide compound and kneading and spinning in a short time (see, for example, Patent Document 2), having 3 or more carbodiimide groups in the molecule A method of adding a polycarbodiimide compound (see, for example, Patent Document 3), wherein the carboxyl end group is capped by reaction with carbodiimide, and 30 to 200 ppm of free mono and / or biscarbodiimide compound and free polycarbodiimide or still reactive Polyester fibers and filaments containing at least 0.02% by weight of a reaction product containing polycarbodiimide groups are proposed (see, for example, Patent Document 4).

Furthermore, the manufacturing method (for example, refer patent document 5) of the industrial polyester monofilament which adds a specific carbodiimide compound to the polyester containing a specific amount of phosphorus, terminal carboxyl group concentration is 10 equivalents / polyester 10 ⁶ g or less, Polyester monofilament containing 0.005 to 1.5% by weight of a carbodiimide compound in an unreacted state and 0.01 to 30% by weight of a fluoropolymer (see, for example, Patent Document 6), unreacted mono Polycarbodiimide compound (B) containing 230 ppm to 1.5% by weight of carbodiimide compound (A), partially reacting with carboxyl end groups of unreacted polycarbodiimide compound and / or polyester, and having unreacted carbodiimide groups Containing 0.05 to 1.5% by weight of polyester Bruno filaments (e.g., see Patent Document 7), a polymer component, terminal carboxyl group concentration of 10 eq / 10 ⁶ g or less of the polyester (A) from 99.8 to 60 wt% and a thermoplastic polymer containing no fluorine atom ( B) Polyester monofilament comprising 0.2 to 40% by weight and containing 0.005 to 1.5% by weight of the carbodiimide compound (C) in an unreacted state of the polymer component (for example, see Patent Document 8), Shinji A monofilament (for example, see Patent Document 9) comprising a polyester composition containing a specific amount of polystyrene having an unreacted state such as an tactic structure and an unreacted monocarbodiimide compound and polycarbodiimide compound, and an ethylene / acrylate copolymer Polyester monophyll with a specific amount of carbodiimide compound added Instrument (e.g., see Patent Document 10), etc. have been proposed, various improvements have been made.

However, even polyester monofilaments that have improved hydrolysis resistance by the above-described methods are intended to be used as a constituent material of a papermaking dryer canvas in a process that requires dry pyrolysis resistance, for example, in a process where the drying temperature of the papermaking dryer is high. Used for papermaking dryer canvas used for papermaking dry parts where the drying temperature is higher than before for the purpose of improving paper productivity and used as a constituent material for ears exposed to higher temperatures without contact with wet paper When trying to do so, the hydrolysis resistance is still not enough, but the problem of dry thermal decomposition resistance is still insufficient, and it was forced to use expensive polyphenylene sulfide monofilaments. Is the actual situation.
JP 51-136923 A (pages 1 to 5) JP 50-95517 A (pages 1 to 4) Japanese Examined Patent Publication No. 38-15220 (pages 1-6) JP-A-4-289221 (pages 1-7) JP-A-57-205518 (pages 1 to 9) Republished International Publication Number WO 92/07126 (pages 1 to 11) JP-A-7-216647 (pages 1-7) JP-A-7-258524 (pages 1 to 43) JP-A-10-168661 (pages 1 to 11) Japanese Patent Laid-Open No. 14-20931 (pages 1-7)

  The present invention was made as a result of investigations to solve the above-described problems in the prior art, has a hydrolysis resistance superior to that of the conventional one, and is further excellent in oxidative degradation resistance, Polyester composition useful as a constituent material for various industrial fabrics, polyester monofilaments comprising this polyester composition, paper-making dryer canvas using this polyester monofilament, belt fabric for thermal bonding process of nonwoven fabric, fabric for conveyor belt in heat treatment furnace, etc. The purpose is to provide various industrial fabrics.

  In order to achieve the above object, according to the present invention, with respect to 100 parts by weight of a polyester (A) comprising a polyethylene phthalate component of 70 to 99% by weight and a polyethylene naphthalate component of 30 to 1% by weight. And a polyester composition (first invention) comprising 0.01 to 1.5 parts by weight of an unreacted monocarbodiimide compound (B), and a polyethylene terephthalate component of 70 to 99 parts by weight. %, Polyester (A) 70 to 99.8 parts by weight of a polyethylene naphthalate component 30 to 1% by weight, and thermoplastic resin polymer (C) other than the polyester (A) 0.2 to 30 parts by weight. The unreacted monocarbodiimide compound (B) 0 with respect to the composition in which the total of (A) and (C) is 100 parts by weight Polyester composition from 01 to 1.5 by incorporating parts by weight, characterized by comprising (a second invention) is provided.

In the polyester composition of the present invention,
The polycarbodiimide compound (D) is further contained in an amount of 0.02 to 1.5 parts by weight with respect to a total of 100 parts by weight of the polyester (A) and the thermoplastic resin polymer (C). Compound (D) is one molecule in the total [(D1) + (D2)] of the unreacted carbodiimide group (D1) and the carbodiimide group (D2) reacted with the carboxyl end group and droxyl end group of the polyester. An alkyl-substituted aromatic polycarbodiimide compound containing 5 to 50 of them. ],
The thermoplastic resin polymer (C) is at least one selected from polystyrenes, polyolefins and polymethacrylate polymers;
The polystyrenes are polystyrene-based polymers having a syndiotactic structure;
The polyolefin is at least one selected from a cyclic olefin polymer, polypropylene, polyethylene and polymethylpentene;
The monocarbodiimide compound (B) is N, N′-di-2,6-diisopropylphenylcarbodiimide,
The polycarbodiimide compound (D) is an aromatic polycarbodiimide compound in which the ortho position of the phenyl group is substituted with an isopropyl group with respect to the carbodiimide group,
The antioxidant (E) is further contained in an amount of 0.02 to 1.0 part by weight with respect to a total of 100 parts by weight of the polyester (A) and the thermoplastic resin polymer (C), and the antioxidant ( E) is tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, both of which are preferred polyester compositions, By satisfying at least one condition, it can be expected to obtain a better effect.

  The polyester monofilament of the present invention is characterized by comprising the above-mentioned polyester composition, and in particular, it is a preferable condition that the shape of the cross section perpendicular to the fiber axis direction is a circle or a flat.

  Furthermore, the industrial fabric of the present invention is characterized in that the polyester monofilament described above is used as at least a part of a weft or a warp. Among them, a papermaking dryer canvas, a belt fabric for a thermal bonding process of a nonwoven fabric, and a heat treatment furnace When used for at least one selected from fabrics for conveyor belts, it exhibits excellent effects.

  According to the present invention, as will be described below, this polyester composition has excellent hydrolysis resistance compared to conventional ones, and also has excellent oxidation resistance (hereinafter referred to as dry heat resistance), and this polyester. Various industrial fabrics represented by polyester monofilaments composed of the composition and paper-making dryer canvas using the polyester monofilaments, belt fabrics for heat bonding processes of nonwoven fabrics, and fabrics for transport belts in heat treatment furnaces can be obtained.

  Hereinafter, the present invention will be described in detail.

  In the polyester (A) constituting the polyester composition of the present invention, polyethylene terephthalate (hereinafter referred to as PET) means that 90 mol% or more of the dicarboxylic acid component consists of terephthalic acid and 90 mol% or more of the glycol component. What consists of ethylene glycol is suitable.

In order to efficiently express the effect of the present invention, the phosphorus compound can be contained in PET in an amount of 50 ppm or less as a phosphorus atom and within the range of the following general formula 1.
5 × 10 ⁻³ ≦ P ≦ M + 8 × 10 ⁻³ Formula 1
(In the formula, P is the mol% of the phosphorus atom with respect to the dibasic acid constituting PET, M is a metal in the PET resin, and is Group II, Group VII, Group VIII, and It is the mol% with respect to the dibasic acid which comprises the polyester of the 1 type (s) or 2 or more types of metal atom selected from the period. M may be 0.)

  PET is a part of the terephthalic acid component described above, such as 2,6-naphthalenedicarboxylic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, dimer acid, sulfonic acid metal salt-substituted isophthalic acid, etc. It may be replaced with. In addition, a part of the ethylene glycol component is replaced with, for example, propylene glycol, tetramethylene glycol, 1,4-cyclohexanedimethanol, diethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, polyalkylene glycol, and the like. There may be. Furthermore, a small amount of chain branching agents such as pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid and boric acid can be used in combination.

  PET includes various inorganic particles such as titanium oxide, silicon oxide, calcium carbonate, silicon nitride, clay, talc, kaolin, zirconic acid, carbon black, and other particles such as crosslinked polymer particles and various metal particles. In addition, conventionally known sequestering agents, ion exchangers, anti-coloring agents, light-proofing agents, inclusion compounds, antistatic agents, various coloring agents, waxes, silicone oils, various surfactants, and the like may be added. .

The intrinsic viscosity of the PET used in the present invention is usually 0.6 or more, but is preferably 0.7 or more. Increasing the intrinsic viscosity of PET increases the strength of the monofilament and is effective. The upper limit of the intrinsic viscosity is about 1.5 or less that can be produced. Further, the polyester composition of the present invention preferably has a carboxyl end group (hereinafter referred to as COOH end group) concentration of 10 equivalents / 10 ⁶ g or less in terms of hydrolysis resistance and dry heat resistance. The COOH end group concentration is preferably as low as possible. For that purpose, it is effective to reduce the COOH end group concentration at the stage of melt polycondensation, such as low-temperature polycondensation, and to perform solid-phase polycondensation subsequent to melt polycondensation in addition to the COOH end group blocking technique described later. is there. Solid phase polycondensation is suitable not only for reducing the COOH end group concentration but also for improving the intrinsic viscosity. The COOH end group concentration of PET may be 40 equivalents / 10 ⁶ g or less, more preferably 30 equivalents / 10 ⁶ g or less, and even more preferably 25 equivalents / 10 ⁶ g or less.

  Further, in the polyester (A) constituting the polyester composition of the present invention, the other polyethylene naphthalate (hereinafter referred to as PEN) is that 90 mol% or more of the dicarboxylic acid component is composed of 2,6-naphthalenedicarboxylic acid. In addition, 90 mol% or more of the glycol component is preferably composed of ethylene glycol.

  In order to efficiently express the effects of the present invention, the phosphorus compound can be contained in PEN in an amount of 50 ppm or less as a phosphorus atom in the same manner as PET and in the range of the above formula 1.

  PEN is a part of the above 2,6-naphthalenedicarboxylic acid component such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, dimer acid, sulfonic acid metal salt-substituted isophthalic acid, etc. It may be replaced with. In addition, a part of the ethylene glycol component is replaced with, for example, propylene glycol, tetramethylene glycol, 1,4-cyclohexanedimethanol, diethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, polyalkylene glycol, and the like. There may be. Furthermore, a small amount of chain branching agents such as pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid and boric acid can be used in combination.

  PEN includes various types of inorganic particles such as titanium oxide, silicon oxide, calcium carbonate, silicon nitride, clay, talc, kaolin, zirconium acid, carbon black, and other particles such as crosslinked polymer particles and various metal particles. Known sequestering agents, ion exchangers, anti-coloring agents, light-proofing agents, inclusion compounds, antistatic agents, various coloring agents, waxes, silicone oils, various surfactants and the like may be added.

The intrinsic viscosity of PEN used in the present invention is usually 0.50 or more, but is preferably 0.55 or more. Increasing the intrinsic viscosity of PEN increases the strength of the monofilament and is effective. The upper limit of the intrinsic viscosity is about 1.0 or less that can be produced. Moreover, since the polyester composition of the present invention preferably has a COOH end group concentration of 10 equivalents / 10 ⁶ g or less in terms of hydrolysis resistance and dry heat resistance, the COOH end group concentration of PEN is within a possible range. A low one is preferable. For that purpose, in addition to the COOH end group blocking technique described later, a method of reducing the COOH end group concentration at the stage of melt polycondensation, such as low-temperature polycondensation, or solid phase polycondensation was performed following melt polycondensation. It is preferable. The COOH end group concentration of PEN is preferably 40 equivalents / 10 ⁶ g or less, more preferably 30 equivalents / 10 ⁶ g or less, and even more preferably 25 equivalents / 10 ⁶ g or less.

  The ratio of PET component / PEN component in the polyester (A) consisting of 100 parts by weight of PET and PEN constituting the polyester composition of the present invention is in the range of 70 to 99% by weight / 30 to 1% by weight. It is necessary. Furthermore, the ratio of the PET component / PEN component is more preferably in the range of 80 to 97% by weight / 20 to 3% by weight. If the PEN component is less than 1% by weight, it is not possible to obtain a polyester composition having excellent hydrolysis resistance and dry heat resistance. On the other hand, if it exceeds 30% by weight, the strength of the polyester monofilament adapted from the polyester composition tends to be insufficient due to poor compatibility with PET.

  In the second invention of the present invention, the polyester (A) comprising the PET and PEN of the present invention, the thermoplastic resin polymer (C) other than the polyester (A), the (A) and (C) The content of the thermoplastic resin polymer (C) in the composition having a total of 100 parts by weight needs to be in the range of 0.2 to 30 parts by weight. The polyester monofilament adapted from the polyester composition containing 0.2 to 30 parts by weight of the thermoplastic resin polymer (C) is more excellent in hydrolysis resistance without causing a decrease in strength. Furthermore, the content of the thermoplastic resin polymer (C) is preferably 0.5 to 20 parts by weight.

  If the content of the thermoplastic resin polymer (C) is less than 0.2 parts by weight, excellent hydrolysis resistance cannot be obtained, and if it exceeds 30 parts by weight, the strength of the polyester monofilament adapted from the polyester composition Tends to be insufficient.

  Examples of the thermoplastic resin polymer (hereinafter referred to as polymer) (C) other than the polyester (A) in the polyester composition of the present invention include polystyrenes such as polystyrene and poly-p-methylstyrene, and cyclic olefin-based heavy polymers. Polyolefins such as polymers, polyethylene, polypropylene, polymethylpentene, polymethacrylate polymers, modified polyolefins such as copolymers of various α-olefins and unsaturated acid glycidyl esters, ionomers, ethylene / vinyl chloride copolymer Copolymers and ethylene / vinyl copolymers such as ethylene / vinyl acetate copolymers, terpene resins and other petroleum resins, polyacetal resins, polymethacrylates, styrene / acrylonitrile copolymers, styrene / maleic anhydride copolymers , Coumaron Inde Copolymers, polyphenylene ethers, polyphenylene sulfides, may be mentioned polycarbonates, polyamides such as nylon 6 and nylon 6 · 6. One of these polymers can be used alone, or two or more can be used in combination.

  Among the polymers (C) described above, it is preferable to use polystyrenes, polyolefins and polymethacrylate polymers because a polyester composition having excellent hydrolysis resistance and dry heat resistance can be obtained.

  Styrene polymers which are polystyrenes are polymers obtained by polymerizing styrene monomers by a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization. For example, styrene or p-methylstyrene, m-methylstyrene, alkyl styrenes such as o-methyl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,4-dimethyl styrene, p-tert-butyl styrene, p-chloro styrene, m-chloro styrene, o Halogenated styrenes such as chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, p -Chloromethylstyrene, m-chloromethylstyrene, etc. Atactic structural polystyrene, isotactic structural polystyrene, syndiotactic structural polystyrene (hereinafter referred to as SPS) composed of one or more styrene monomers selected from halogen-substituted alkylstyrenes, alkoxystyrenes such as p-methoxystyrene, and the like. And so on.

  Among these styrenic polymers, use of a styrenic polymer in which 50% by weight or more of the polymer has a syndiotactic structure not only can improve hydrolysis resistance and dry heat resistance, but also has good processability during production. This is preferable. Further, it is more preferable that the styrene polymer has 90% by weight or more of the polymer having a syndiotactic structure.

  SPS is a method described in JP-A No. 62-104818, that is, polymerization is carried out in the presence of a catalyst comprising a combination of a titanium compound such as titanium halide or alkoxytitanium and an alkylaluminoxane using a styrene monomer as a raw material. Can be obtained. It can also be purchased as a commercial product. As SPS, a polymer composed of 85% by mole or more of styrene as a monomer component is preferable because the heat resistance of the polyester composition or monofilament of the present invention is further improved. Moreover, the polymer which copolymerized less than 15 mol% p-methylstyrene in styrene can also be used preferably.

  The molecular weight of SPS is generally preferably in the range of 100,000 to 500,000 in terms of weight average molecular weight.

  A styrene polymer having a syndiotactic structure of 50% by weight or more can also be obtained by melt-kneading SPS and atactic structure polystyrene.

  Polyolefin polymers which are polyolefins are polymers polymerized from known olefin monomers, such as cyclic olefin polymers, polyethylene, polypropylene, poly-4-methylpentene-1, polybutene-1, polypentene, poly-3. -Methylbutene-1, etc. can be mentioned. Among the above-mentioned polyolefins, cyclic olefin polymers, polyethylene, polypropylene, and polymethylpentene are preferable, and it is particularly preferable to use cyclic olefin polymers.

  The above-mentioned cyclic olefin polymer is a random copolymer of an α-olefin having 2 or more carbon atoms and having one kind of cyclic olefin (hereinafter referred to as ethylene / cyclic olefin random copolymer). The α-olefin having 2 or more carbon atoms constituting the ethylene / cyclic olefin random copolymer may be propylene, 1-butene, 1-pentene in addition to ethylene alone or ethylene as a main component. 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl -1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1- Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like can be used alone or in combination with ethylene in a small amount.

  Moreover, the following compound can be mentioned as a cyclic olefin which comprises an ethylene * cyclic olefin random copolymer.

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. 1 ^9,12 . 0 ^8,13 ] -3-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo [8.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13] -3-pentadecene derivatives, hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene derivatives, heptacyclo [8.7.0.1 ^3,6. 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16] -4-eicosene derivatives, heptacyclo [8.7.0.1 ^3,6. 1 ^10,17 . 1 ^12,17 . 0 ^2,7 . 0 ^11,16] -5-eicosene derivatives, heptacyclo [8.8.0.1 ^1,7. 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 [10.10.1.1 ^5,8. 1 ^14,21 . 1 ^16,19 . 0 ^2,11 . 0 ^4,9 . 0 ^13,22 . 0 ^15,20] -5-hexacosenoic derivatives, 1,4-methano -1,4,4a, 9a- tetrahydrofluorene derivatives, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene Derivative, cyclopentadiene-acenaphthylene adduct.

  The cyclic olefin can be obtained by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by Diels-Alder reaction. The copolymerization ratio of the ethylene-cyclic olefin random copolymer between the α-olefin having ethylene as a main component and the cyclic olefin is not particularly limited, but is usually an α-olefin component 40-80 having ethylene as a main component. It is the range of 20% mol% and cyclic olefin component 20-60 mol%.

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

Further, it constitutes one kind of cyclic olefin ring-opening polymer or ring-opening copolymer or hydrogenated product thereof (hereinafter referred to as cyclic olefin ring-opening polymer or ring-opening copolymer or hydrogenated product thereof). Examples of the cyclic olefin include 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonylbicyclo, in addition to the cyclic olefins constituting the α-olefin / cyclic olefin random copolymer described above. [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-methoxy Carbonylbicyclo [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-butoxycarbonylbis B [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 ] dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0 ^2,5 . 1 ^7,10 ] dodec-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 ] dodec-3-ene, 8-methyl-8- (4′-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-phenoxycarbonyltetracyclo [4.4.0 ^2,5 . 1 ^7,10 ] dodec-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.

  A ring-opening polymer or ring-opening copolymer of a cyclic olefin, or a hydrogenated product thereof is obtained by converting the above-mentioned cyclic olefins into metal halides such as ruthenium, rhodium, palladium, osmium, indium, platinum, and tungsten, and these metals. And a catalyst comprising a reducing agent and a metal halide such as titanium, palladium, zirconium, molybdenum or the like, and a catalyst comprising an acetylacetonate of these metals and an organoaluminum. Polymerized in the presence of

  The intrinsic viscosity (hereinafter referred to as [η]) of the hydrogenated product of the ethylene / cyclic olefin random copolymer, cyclic olefin ring-opening (co) polymer, and cyclic olefin ring-opening (co) polymer is 135 ° C. [Η] measured in decalin is usually 0.01 to 20 dl / g, particularly preferably 0.05 to 10 dl / g, more preferably 0.08 to 8 dl / g. The hydrogenated products of the above ethylene / cyclic olefin random copolymer, cyclic olefin ring-opening (co) polymer, and cyclic olefin ring-opening (co) polymer are commercially available as “Apel” (registered trademark) (Mitsui Petrochemical) Industrial products), “ZEONEX” (registered trademark) (product of ZEON Corporation), “ARTON” (registered trademark) (product of Nippon Synthetic Rubber), etc.

  Examples of polymethacrylate polymers include polymethyl methacrylate, polyethyl methacrylate, poly n-propyl methacrylate, poly n-butyl methacrylate, poly n-octyl methacrylate, poly n-decyl methacrylate, and poly n-tetradecyl methacrylate. Can be mentioned. Among these polymethacrylate polymers, polymethyl methacrylate is particularly preferable.

  For example, polyester amide, epoxy resin, silicone resin, polyurethane resin, and the like may be blended with the polyester composition and polyester monofilament of the present invention as necessary. In addition, these resin can be added to content of the said polymer (C).

Since the polyester monofilament and the industrial fabric using the polyester monofilament adapted from the polyester composition of the present invention are required to have hydrolysis resistance and dry heat resistance, the COOH end group concentration in the polyester composition can be reduced. Is effective. In order to make the polyester composition excellent in hydrolysis resistance and dry heat resistance, the COOH end group concentration is particularly preferably 10 equivalents / 10 ⁶ g or less. Furthermore, it is preferable that it is 7 equivalent / 10 < ⁶ > g or less. If the COOH end group concentration exceeds 10 equivalents / 10 ⁶ g, the hydrolysis resistance of the polyester composition and the polyester monofilament applied from the polyester composition will be insufficient, and further, the heat resistance tends to be inferior.

In order to obtain a polyester composition having a COOH end group concentration of 10 equivalents / 10 ⁶ g or less, solid phase polycondensation of the polyester (A) in the polyester composition of the present invention, 100 parts by weight of the polyester (A), or It is necessary to contain the unreacted monocarbodiimide compound (B) in the range of 0.01 to 1.5 parts by weight with respect to 100 parts by weight of the total of the polyester (A) and the polymer (C). The content is more preferably 0.02 to 1.5 parts by weight. If the content of the unreacted monocarbodiimide compound (B) is less than 0.01 parts by weight, the hydrolysis resistance decreases. On the other hand, when the amount is more than 1.5 parts by weight, the strength of the polyester monofilament adapted from the polyester composition becomes low.

  As the unreacted monocarbodiimide compound (hereinafter referred to as unreacted MCD) (B) contained in the polyester composition of the present invention, one carbodiimide group (—N═C═N—) per molecule is used. Any compound may be used, for example, 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-diisopropylphenylcarbodiimide, N, N′-di-2,6-di-tert.-butyl Phenylcarbodiimide, 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, etc. Can be mentioned. One or two or more compounds may be arbitrarily selected from these monocarbodiimide compounds and contained in the polyester, but from the viewpoint of heat stability, compounds having an aromatic skeleton tend to be advantageous. Among them, N, N′-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 N, N′-di-2,6-diisopropylphenylcarbodiimide (hereinafter referred to as TIC) is particularly preferable. TIC can be used by obtaining “Stabaxol” (registered trademark) I (Rhein-Chemie product) or “Stabilizer” (registered trademark) 7000 (Raschig AG product) as a commercial product.

  In addition to the carbodiimide compound, which reduces the COOH end group concentration in the polyester composition, a suitable amount of a mono- or diepoxy compound, a mono- or bisoxazoline compound, etc. can be added in combination.

  Moreover, when the polyester composition of this invention contains a polycarbodiimide compound (henceforth PCD) (D), since it will become what was excellent in hydrolysis resistance and dry heat resistance, it is preferable. It is particularly preferable that the polyester composition contains 0.02 to 1.5 parts by weight of PCD (D) with respect to 100 parts by weight in total of the polyester (A) and the polymer (C). Furthermore, it is preferable that it is 0.05-1.2 weight part. If the content of PCD (D) is less than 0.02 parts by weight, it tends to be inferior in dry heat resistance when exposed to high temperature and high humidity for a long time. On the other hand, when it exceeds 1.5 parts by weight, when melt-kneading with the polyester (A), it undergoes a cross-linking reaction with the polyester (A), thereby causing a significant increase in viscosity, resulting in a decrease in moldability and physical properties of the polyester monofilament. It tends to decrease.

  Here, PCD (D) is the sum of the unreacted carbodiimide group (D1) and the carbodiimide group (D2) reacting with the carboxyl end group and hydroxyl end group of the polyester [(D1) + (D2)]. And an alkyl-substituted aromatic polycarbodiimide compound containing 5 to 50 per molecule.

  PCD is a polycarbodiimide compound having an alkyl-substituted phenylcarbodiimide as a repeating unit, and the ortho position of the phenyl group with respect to the carbodiimide group is an alkyl group such as a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, Particularly preferably substituted with an isopropyl group, ie phenyl substituted in the 2,6- and / or 2,4,6-position and / or the 2,3-position and / or the 2,5-position with an isopropyl group Examples thereof include polycarbodiimide compounds having carbodiimide as a main repeating unit.

  PCD1 molecules are partially reacted with the COOH end groups and hydroxyl end groups of the polyester in the polyester composition of the present invention, but the total of unreacted carbodiimide groups (D1) and carbodiimide groups (D2) [( D1) + (D2)] and having 5 to 50.

  The average molecular weight of PCD (D) is 2,000 to 16,000, preferably 2,500 to 12,000.

  As PCD (D), “Stabaxol” (registered trademark) P (product of Rhein-Chemie) having an average molecular weight of 3,000 and “Stabaxol” (registered trademark) P100 (Rhein-Chemie) having an average molecular weight of 10,000 are commercially available. Product).

  PCD (D) can be used as a masterbatch containing polyester or an olefin polymer in a high concentration in advance. A master batch containing 1 to 8% by weight of polyethylene can be preferably used because the resulting polyester product tends to have better hydrolysis resistance. A PET masterbatch containing PCD (D) (hereinafter referred to as PCD-MB) is a commercially available product, “Stabaxol” (registered trademark) containing 15% by weight of “Stabaxol” (registered trademark) P100 having an average molecular weight of 10,000,000. KE7646 (Rhein-Chemie product) and 8% by weight of “Stabaxol” ® P with an average molecular weight of 3,000 and 7% by weight of “Stabaxol” ® P100 with an average molecular weight of 10,000 Stabaxol "(registered trademark) KE8059 (product of Rhein-Chemie) and the like can be obtained.

  Further, when the polyester composition of the present invention contains an antioxidant (E), it is preferably used since it has excellent dry heat resistance. In that case, the amount of the antioxidant (E) to be contained is preferably 0.02 to 1.0 part by weight with respect to a total of 100 parts by weight of the polyester (A) and the polymer (C), and is further preferably 0.00. By containing 0.5 to 0.7 parts by weight, the dry heat resistance is further improved. When the content of the antioxidant (E) is less than 0.02, it is difficult to obtain sufficient dry heat resistance when exposed to high temperature and high humidity for a long time. On the other hand, when the content exceeds 1.0 part by weight, the hydrolysis resistance tends to decrease.

  As the antioxidant (E), phenolic antioxidants are effective. For example, 2,6-di-t-butyl-p-cresol, butylhydroxyanisole, 2,6-di-t-butyl-4 -Ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3, 9-bis [1,1′-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-teto Raoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, bis [3,3 '-Bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, and 1,3,5-tris (3', 5'-di-t-butyl-4'-hydroxy Benzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and the like. However, there is no limitation to this.

  Of these phenolic antioxidants, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane is particularly preferred. Tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane is a commercially available product such as “Irganox” (registered trademark) 1010 (Ciba Specialty Chemicals). Product) is known and can be obtained and used.

  Production of the polyester composition of the present invention is carried out with respect to 100 parts by weight of the polyester (A) comprising the PET and PEN of the present invention, or 100 parts by weight of the total of the polyester (A) and the polymer (C), and a monocarbodiimide compound and It can be obtained by melting and kneading the required amount of PCD (D) and further antioxidant (E) and forming into any shape such as pellets, flakes, fibers, films, and molded products.

  The monocarbodiimide compound can be used as a master batch that is previously contained in the polymer (C) at a high concentration. Moreover, a monocarbodiimide compound and PCD (D) can be dissolved and used for each other. Furthermore, the polyester composition and polyester monofilament of the present invention contain various known fluororesins for the purpose of exhibiting antifouling properties (water and oil repellency) as functions other than hydrolysis resistance and dry heat resistance. Can do.

  As a specific production example of the polyester composition of the present invention, for example, a necessary amount of PET pellets and PEN pellets are charged into each hopper, or a necessary amount of PET pellets and PEN pellets are blended and the required amount is charged into the hopper. Alternatively, polyester (A) and a predetermined amount of polymer (C) supplied in a necessary amount to a biaxial extruder, PCD-MB containing a predetermined amount of PCD (D) at a high concentration as required, antioxidant (E) Are metered, and liquid monocarbodiimide compound is metered from the entrance of the extruder or from the middle of the barrel of the extruder, melted and kneaded, extruded, cooled if necessary, etc. to any shape The required amount is supplied to a molding method (hereinafter referred to as production method 1) or a uniaxial or biaxial extruder as described above. Polymer (C) master pellets containing a high concentration of polyester (A) and PCD (D), a predetermined amount of antioxidant (E) is metered as required, and the inlet of the extruder or the extruder A liquid monocarbodiimide compound is metered from the middle of the barrel, melted and kneaded, extruded, cooled as necessary, and shaped into an arbitrary shape (hereinafter referred to as production method 2), or 1 The polyester (A) and polymer (C) supplied in the required amount to the shaft or biaxial extruder in the same manner as described above, and a predetermined amount of antioxidant (E) as required are metered and supplied to the entrance of the extruder or the extruder. A mixture of a monocarbodiimide compound and PCD (D) melted and mixed at a predetermined concentration is metered in from the middle of the barrel. A method of forming after melting and kneading, extruding, cooling as necessary, etc. (hereinafter referred to as production method 3), or a polyester supplied in the same amount as above to a uniaxial or biaxial extruder (A), a polymer (C), a PCD compound (C), and an antioxidant (E) are weighed and a liquid monocarbodiimide compound is metered from the entrance of the extruder or the middle of the barrel of the extruder. And a method of forming into an arbitrary shape through extrusion after melting and kneading and cooling as necessary (hereinafter referred to as production method 4). Among these methods, the production methods 1 to 3 are industrially advantageous.

  In these series of production methods, the temperature at which a predetermined amount of PCD (D) and antioxidant (E) are melt-kneaded with polyester (A), monocarbodiimide compound and polymer (C) as required is The polyester (A) and the polymer (C) are preferably adjusted to have a melting point or higher and 290 ° C. or lower, and more preferably 280 ° C. to 288 ° C. Further, the residence time from melting to discharging is advantageously 7 minutes or less, more preferably 5 minutes or less. By adjusting the melt-kneading temperature and the residence time from melting to discharging within the above range, the polyester composition of the present invention excellent in hydrolysis resistance and dry heat resistance can be preferably produced.

  In addition to monofilaments, the polyester composition of the present invention thus obtained can be in any shape such as multifilaments, non-woven fabrics, fibers such as staple fibers and cotton, molded products such as connectors and automobile wipers, bottles, films and sheets. It can be preferably used for various industrial fabrics, electronic parts, automobile parts, bottles, films, sheets and the like.

  The production of the polyester monofilament of the present invention is performed by extruding from the spinneret through the polymer streamline changer, the filter layer, etc. installed at the tip of the extruder in the production methods 1 to 4, and cooling, stretching and heat setting are performed. It can manufacture by the method of performing.

The polyester monofilament adapted from the polyester composition of the present invention is a continuous yarn composed of one single yarn. The shape of the cross section perpendicular to the fiber axis direction of the polyester fiber and monofilament (hereinafter referred to as cross-sectional shape or cross-section) is a circle, flat, square, half moon shape, triangle, five or more polygons, multi-leaf shape, dog bone shape, It may have any cross-sectional shape such as a bowl. When the monofilament of the present invention is used as a constituent material for industrial fabrics, the cross-sectional shape of the monofilament is preferably a circle or a flat shape. In particular, when the monofilament is a warp yarn of a papermaking dryer canvas, a monofilament having a flat cross-sectional shape is preferably used from the viewpoint of effectively expressing antifouling properties and the flatness of the canvas. The flat in the present invention means an ellipse, a square or a rectangle. In addition to an exact ellipse, a square or a rectangle defined mathematically, a shape substantially similar to an ellipse, a square or a rectangle, for example, a square and a rectangle. It includes a shape with rounded four corners. In the case of an ellipse, the length of the major axis (LD) and the length of the minor axis (SD) intersecting at right angles at the center of the ellipse satisfy the following formula. It is preferable that the long side length (LD) and the short side length (SD) satisfy the following formula.
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. Further, the required strength of the yarn varies depending on the use, but is preferably approximately 3.0 cN / dtex or more. If the strength is less than 3.0 cN / dtex, there is a high possibility that the necessary minimum of the industrial fabric cannot be maintained, and the development to the industrial fabric tends to be difficult.

  In addition to the polyester monofilaments adapted from the polyester composition of the present invention thus obtained, the polyester composition of the present invention can be preferably used for fibers such as multifilaments, nonwoven fabrics, staple fibers, and cotton.

  The industrial fabric of the present invention is a paper dryer drier canvas using the polyester monofilament of the present invention as at least a part of the weft and / or warp of the fabric, a paper making wire (papermaking net), a belt for thermal bonding of a nonwoven fabric, This refers to fabrics for conveyor belts in heat treatment furnaces and various filters. Industrial fabrics using the polyester monofilament of the present invention as a constituent material of at least part of industrial fabrics are durable when exposed to high temperatures and high humidity. It is useful with excellent properties.

  Here, the papermaking wire is a woven fabric used in the paper winding process as various woven fabrics such as plain weave, double woven fabric, and triple woven fabric, and is used as a long mesh or a round mesh.

  The paper machine dryer canvas is a variety of fabrics such as plain weave, double weave, and triple weave (including spiral fabrics in which weft and weft yarns are connected by spiral monofilaments). The fabric used to dry the paper.

Further, the nonwoven fabric for the thermal bonding process of the nonwoven fabric is a fabric for allowing the nonwoven fabric to pass through a furnace in order to fuse the low-melting-point heat-bonding fibers such as polyethylene constituting the nonwoven fabric. Heavy woven fabrics.
Further, the fabric for the conveyor belt in the heat treatment furnace refers to a fabric that transports the semi-finished product in the high-temperature zone for drying, thermosetting, sterilizing, heating cooking, and the like of various semi-finished products.
Furthermore, various filters are fabrics that filter high-temperature liquids, gases, powders, and the like.

  Hereinafter, the present invention will be described in detail with reference to examples.

  The characteristic values in the following examples are measured by the following methods unless otherwise specified in each example.

1. Measurement of Intrinsic Viscosity of Polyester An intrinsic viscosity obtained from a viscosity measured at 25 ° C. in an orthochlorophenol solution, which is a value represented by [η].

2. Measurement of Polyester COOH End Group Concentration This was measured by the method described in ANALYTICAL CHEMISTRY Vol. 26, page 1614 by Pohi.

3. Measurement of content of unreacted monocarbodiimide compound (1) About 200 mg of sample is weighed into 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 disk filter having an aperture of 0.45 μm and quantitatively analyzed by HPLC. The 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 volume: 20 μl Detector: UV (280 nm).

4). Monofilament tensile test It was performed according to JIS L1013-1992.
(1) Sample grip interval 25cm
(2) Tensile speed 30 cm / min.
(3) Test temperature 20 ° C.

5. Hydrolysis resistance of monofilament The monofilament was placed in a 100 liter autoclave and treated for 12 days, 14 days, 16 days, and 18 days in 121 ° C saturated steam, and then the strength of the monofilament after treatment was determined by the tensile test of the monofilament described above. The strength retention compared with the strength of the monofilament before treatment was determined as a measure of hydrolysis resistance (hereinafter referred to as strength retention after steaming). The higher the strength retention after steaming, the better the hydrolysis resistance.

6). Resistance to dry pyrolysis of monofilament The monofilament is put into a hot air circulation type heat resistance tester and treated for 10 days, 20 days, 26 days, and 30 days in 180 ° C. heated air. The strength retention obtained by a tensile test and compared with the strength of the monofilament before the treatment was used as a measure of dry pyrolysis resistance (hereinafter referred to as the strength retention after the dry heat treatment). The higher the strength retention after dry heat treatment, the better the dry pyrolysis resistance.

[Example 1]
As raw materials, [η] 0.94 produced by known melt polycondensation and solid phase polycondensation, COOH end group concentration 13 equivalent / 10 ⁶ g PET dry chip (hereinafter referred to as PET chip) 90% by weight, Weighed in a quantity ratio of 10% by weight of PEN dry chip (hereinafter referred to as PEN chip) of [η] 0.72, COOH end group concentration of 20 equivalents / 10 ⁶ g produced by known melt polycondensation and solid phase polycondensation However, the uniaxial extruder was continuously supplied to the uniaxial extruder via the respective hoppers and polymer pipes below the hopper. At the same time, “Stabilizer” (registered trademark) 7000 (product of Raschig AG), which was heated and melted at 80 ° C. as a monocarbodiimide compound (hereinafter referred to as TIC) with respect to 100 parts by weight of the above-mentioned two types of chips in the polymer pipe at the bottom of the hopper, It was continuously fed while weighing at an amount ratio of 1.3 parts by weight. The molten polymer melt-kneaded for 3 minutes at about 288 ° C. in a single-screw extruder was passed through a filter layer in a spinning pack through a gear pump and spun from a spinneret for circular cross-sectional yarn. The spun monofilament was cooled in a hot water bath at 70 ° C. and then stretched and heat-set by a total of 5.0 times in accordance with a conventional method to obtain a monofilament having a diameter of 0.400 mm and a circular cross section. The composition of the polyester and the properties of the resulting polyester monofilament are shown in Tables 1 and 2.

The amount of unreacted monocarbodiimide compound (hereinafter referred to as unreacted MCD) (B) in the obtained monofilament is 0.27 parts by weight, the COOH end group concentration is 1.9 equivalents / 10 ⁶ g, and strength 4 It was .81 cN / dtex. In addition, the strength retention after steaming heat treatment is higher than that of Comparative Example 1 in which PEN is not added, and the strength retention after dry heat treatment is not reduced even if PEN is added, It was suitable for textiles such as a dryer canvas for papermaking of the present invention.

[Reference Example 1]
The polyester monofilament obtained in the same manner as in Example 1 without adding anything other than the PET chip of Example 1 had a COOH end group concentration of 20.3 equivalent / 10 ⁶ g and a strength of 4.86 cN / dtex. On the other hand, the strength retention after steaming was impaired in the short-term treatment, which was unsuitable for textiles such as the paper-making dryer canvas of the present invention. The composition of the polyester, the properties of the polyester monofilament, and the results are shown in Tables 1 and 2 as Reference Example 1.

[Comparative Example 1]
As a result of carrying out in the same manner as in Example 1 except that the PEN chip of Example 1 was not added, the obtained monofilament was inferior in hydrolysis resistance. The results are shown in Table 2.

[Examples 2 to 8, Comparative Examples 2 to 4]
In Examples 2 to 5 and Comparative Example 2, the formulation of the PEN chip in Example 1 was changed as shown in Table 1, and Examples 6 to 8 and Comparative Examples 3 and 4 were the same as those in Comparative Example 1. In this example, the amount of TIC added was changed as shown in Table 1. Otherwise, the contents and results of the polyester monofilament obtained in the same manner as in Example 1 are shown in Tables 1 and 2.
From the results shown in Table 2, the polyester monofilaments of the present invention of Examples 2 to 8 had sufficient strength, hydrolysis resistance, and dry heat resistance, and were suitable for fabrics such as paper making dryer canvas.

[Examples 9 to 27, Comparative Examples 5 to 8]
In Examples 9 to 13 and Comparative Example 6, Comparative Example 5 is in Comparative Example 1, and in Comparative Example 1, 99% by weight or more of the monomer is styrene and 99% by weight of the polymer as the polymer (C). The above is an example in which SPS having a syndiotactic structure and having a weight average molecular weight of about 300,000 is contained. Otherwise, the contents and results of the polyester monofilament obtained in the same manner as in Example 1 are shown in Tables 3 and 4.

  From the results shown in Table 4, the polyester monofilaments of the present invention of Examples 9 to 13 had sufficient strength, hydrolysis resistance and dry heat resistance, and were suitable for textiles such as a dryer canvas for papermaking.

In addition, Examples 14 to 19 and Comparative Example 7 are polymers (C) in Example 1 that are “Apel” (registered trademark) 6015 (manufactured by Mitsui Chemicals, Inc.), which is an ethylene / cyclic olefin copolymer ( Hereinafter, it is an example of containing APEL). Otherwise, the contents and results of the polyester monofilament obtained in the same manner as in Example 1 are shown in Tables 3 and 4.
From the results of Table 4, the polyester monofilaments of Examples 14 to 19 of the present invention had sufficient strength, hydrolysis resistance, and dry heat resistance, and were suitable for fabrics such as paper making dryer canvas.

  As polymer (C), Example 20 has a melting point of 180 ° C. polypropylene (hereinafter referred to as PP), Example 21 has a melting point of 132 ° C. high density polyethylene (hereinafter referred to as HDPE), and Example 22 has a melting point of 235 ° C. This is an example using polymethylpentene (hereinafter referred to as PMPT). Otherwise, the contents and results of the polyester monofilament obtained in the same manner as in Example 1 are shown in Tables 3 and 4.

  From the results shown in Table 4, the polyester monofilaments of the present invention of Examples 20 to 22 had sufficient strength, hydrolysis resistance, and dry heat resistance, and were suitable for fabrics such as paper making dryer canvas.

Examples 23 to 27 and Comparative Example 8 are polymers (C) in Example 1 having a Picat softening point of 116 ° C. and a methacrylic resin “SUMIPEX” (registered trademark) MH (Sumitomo Chemical Co., Ltd. product, hereinafter referred to as PMMA). Is included). Otherwise, the contents and results of the polyester monofilament obtained in the same manner as in Example 1 are shown in Tables 3 and 4.
From the results of Table 4, the polyester monofilaments of the invention of Examples 23 to 27 had sufficient strength, hydrolysis resistance and dry heat resistance and were suitable for fabrics such as paper making dryer canvas.

[Examples 28 to 38, Comparative Examples 9 and 10]
Examples 28 to 34 and Comparative Examples 9 and 10 are the TIC addition amount change of Example 10 and “Stabaxol” (registered trademark) P100 (Rhein-Chemie product) having an average molecular weight of 10,000 which is PCD (D). PET masterbatch (hereinafter referred to as PCD-MD) “Stabaxol” (registered trademark) KE7646 (Rhein-Chemie) containing 15% by weight (PCD having an average molecular weight of 10,000 having 29 carbodiimide groups in one molecule) Product), (hereinafter referred to as KE7646). Further, Example 33 is the same as Example 31 except that tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane (Ciba Specialty), which is the antioxidant (E). This is an example in which a product manufactured by Chemicals, IRGANOX (registered trademark) 1010 (hereinafter referred to as IR1010) was added, and the contents and results of polyester monofilaments obtained in the same manner as in Example 10 are shown in Tables 5 and 6. Show together.

  From the results shown in Table 6, the polyester monofilaments of the present invention of Examples 28 to 34 had sufficient strength, hydrolysis resistance and dry heat resistance, and were suitable for fabrics such as paper making dryer canvas.

  Examples 35 and 36 are the same as Example 15, and Examples 37 and 38 are the same as Example 24, except that PCD (D) and IR1010 were added. The contents and results of the obtained polyester monofilament are shown in Tables 5 and 6.

  From the results shown in Table 6, the polyester monofilaments of the present invention of Examples 35 to 38 had sufficient strength, hydrolysis resistance, and dry heat resistance, and were suitable for fabrics such as paper making dryer canvas.

  As described above, the polyester composition of the present invention comprises a polyester composed of a polyethylene terephthalate component and a polyethylene naphthalate component, an unreacted monocarbodiimide compound and / or a polyester composed of a polyethylene terephthalate component and a polyethylene naphthalate component, and a heat. It contains a plastic resin polymer, an unreacted monocarbodiimide compound and a polycarbodiimide compound, and has hydrolysis resistance and oxidative degradation resistance superior to conventional ones. Also used for at least one selected from the polyester monofilament adapted from the polyester composition of the present invention, a paper-making dryer canvas using this polyester monofilament, a belt fabric for heat bonding process of nonwoven fabric, and a fabric for transport belt in heat treatment furnace The various industrial fabrics are useful and have high industrial utility value due to the properties described above.

Claims (13)

Polyethylene Te terephthalate component is 70 to 99 wt%, with respect to polyester (A) 100 parts by weight of polyethylene naphthalate component consists 30 to 1 wt%, monocarbodiimide compounds of unreacted state (B) 0.01 to 1 .5 a polyester composition ing by parts is contained, polyester composition, wherein the carboxyl terminal group concentration is not more than 10 eq / 10 6 ^g. 70 to 99.8 parts by weight of a polyester (A) comprising 70 to 99% by weight of a polyethylene terephthalate component and 30 to 1% by weight of a polyethylene naphthalate component, and polystyrenes, polyolefins and polymethacrylates other than the polyester (A) A composition comprising 0.2 to 30 parts by weight of at least one thermoplastic resin polymer (C) selected from a polymer, wherein the total of (A) and (C) is 100 parts by weight , a mono-carbodiimide compound (B) polyester compositions ing contain a 0.01 to 1.5 parts by weight of an unreacted state, a carboxyl end group concentration of 10 eq / 10 ⁶ g or less der Rukoto A characteristic polyester composition. The polycarbodiimide compound (D) is further contained in an amount of 0.02 to 1.5 parts by weight with respect to a total of 100 parts by weight of the polyester (A) and the thermoplastic resin polymer (C). Item 3. The polyester composition according to Item 2 . [However, polycarbodiimide compound (D), and unreacted carbodiimide group (D1), the sum of carbodiimide group (D2) which have reacted with the carboxyl end groups and human Dorokishiru end groups of the polyester [(D1) + ( D2)] is an alkyl-substituted aromatic polycarbodiimide compound containing 5 to 50 per molecule. ]. The polyester composition according to claim 2 or 3 , wherein the thermoplastic resin polymer (C) is a polystyrene, and the polystyrene is a polystyrene-based polymer having a syndiotactic structure. A thermoplastic resin polymer (C) polyolefins, the polyolefins, cyclic olefin polymer, polypropylene, claim 2, characterized in that at least one selected from polyethylene and polymethyl pentene or 3. The polyester composition according to 3 . The polyester composition according to any one of claims 1 to 5 , wherein the monocarbodiimide compound (B) is N, N'-di-2,6-diisopropylphenylcarbodiimide. The polycarbodiimide compound (D) having at least the characteristics of claim 3 is an aromatic polycarbodiimide compound in which the ortho position of the phenyl group is substituted with an isopropyl group with respect to the carbodiimide group. The polyester composition according to any one of claims 3 to 6 . At least claims claim 2, wherein, 0.02 to 1.0 weight per 100 parts by weight of the total of the polyester (A) and the thermoplastic resin polymer (C), further antioxidant (E) The polyester composition according to claim 2 , wherein the polyester composition is contained. The polyester according to claim 8, wherein the antioxidant (E) is tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane. Composition. Polyester monofilaments, characterized by comprising a polyester composition according to any one of claims 1-9. The polyester monofilament according to claim 10, wherein the cross-sectional shape perpendicular to the fiber axis direction is a circle or a flat shape. An industrial fabric comprising the polyester monofilament according to claim 10 or 11 as at least a part of a weft or a warp. The industrial woven fabric according to claim 12 , wherein the industrial woven fabric is used in at least one selected from a paper-making dryer canvas, a belt woven fabric for thermal bonding process of a nonwoven fabric, and a woven fabric for a conveyor belt in a heat treatment furnace.