JP2011084596A - Polyester composition and polyester-based fiber comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester-based fiber which is improved in abrasion resistance and hydrolysis resistance and further has no smell caused by a free isocyanate compound in operation, melting, or the like; and to provide a polyester composition which can achieve the fiber. <P>SOLUTION: The polyester composition contains a polyester (component A); a thermoplastic elastomer (component B); and a compound (component C) having one carbodiimide group and containing a cyclic structure in which its first nitrogen and second nitrogen are coupled through a linking group, and a fiber comprises the polyester composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyester composition and a polyester fiber comprising the same. More specifically, the present invention relates to a polyester fiber having improved abrasion resistance and hydrolysis resistance, and a polyester composition capable of providing the same.

  In general, polyesters such as thermoplastic polyesters such as polyethylene terephthalate have excellent mechanical and chemical properties and have been widely used as molded articles such as polyester fibers and polyester films. However, if the polyester fiber is used in industrial applications where it comes into contact with other materials such as metal, ceramic, and plastic particles or structures, it is susceptible to scratching damage by these particles and structures. Nets and woven fabrics using polyester fibers have the disadvantage of short product life. In addition, polyester polymers are susceptible to hydrolysis due to the catalytic action of acidic groups at the end of the polymer chain, which causes problems such as deterioration of physical properties under overheating conditions such as fiberization process and deterioration over time during long-term use. It was.

  Conventionally, various proposals have been made to improve the abrasion resistance of polyester fibers. For example, polyester monofilaments containing abrasive particles such as alumina powder, silicon carbide, and zirconia-based abrasives have a slight improvement in abrasion resistance, but the yarn quality is poor because of the poor dispersion of the abrasive particles in the polyester. Scratch damage on the surface of various rollers and guides that come into contact with the fibers and various fabrics using the fibers, such as the fiber manufacturing process, the weaving process of various fabrics using the fibers, and the paper machine And other disadvantages.

  In order to eliminate this drawback, a method of applying a hard film such as a polysiloxane coating agent and a cross-linked acrylic coating agent to the surface of the monofilament has been proposed (for example, Patent Document 1). It was easy to drop off and had a problem in terms of durability.

  In addition, although a paper fabric having improved abrasion resistance using a monofilament containing a specific amount of thermoplastic polyurethane in polyethylene terephthalate has been proposed (for example, Patent Document 2), the thermoplastic polyurethane resin to be used is used. However, since it is decomposed at the melt spinning temperature of polyethylene terephthalate, spinning becomes difficult, and there is a big industrial problem, which is not practical.

  Further, although it has been proposed to improve the abrasion resistance of polyester monofilament by containing a thermoplastic elastomer (for example, Patent Document 3), there is no mention of improvement of hydrolysis resistance.

  By the way, in order to suppress hydrolysis, it has already been proposed to use a carbodiimide compound as an end-capping agent for a polymer compound having an acidic group such as a carboxyl group at its terminal to suppress hydrolysis of the polymer compound ( For example, Patent Documents 4 and 5).

  The carbodiimide compound used in this proposal is a linear carbodiimide compound. However, when a linear carbodiimide compound is used as an end-capping agent for a polymer compound, a compound having an isocyanate group is liberated with the reaction of the linear carbodiimide compound binding to the terminal of the polyester, generating a unique odor of the isocyanate compound. However, there is a new problem of deteriorating the working environment.

JP-A-63-42976 Japanese Patent Laid-Open No. 2-80688 JP-A-5-86507 Japanese Patent No. 3440915 Japanese Patent No. 3776578

  The object of the present invention is to solve the above-mentioned problems of the prior art, improve the abrasion resistance and hydrolysis resistance, and further, a polyester system free from odor due to a free isocyanate compound at the time of working or melting. It is to provide a fiber and to provide a polyester composition that can achieve this.

  As a result of intensive studies on the improvement of the abrasion resistance and hydrolysis resistance of polyester fibers and the improvement of the working environment, the present inventors have found that (1) a thermoplastic elastomer is contained in the polyester, and (2 ) The present invention has been completed by finding that the above object can be achieved if the composition contains a carbodiimide compound having a specific structure that does not liberate an isocyanate compound even if it reacts with the polymer chain end of the polyester polymer. .

That is, the object of the present invention is to
Contains polyester (component A), thermoplastic elastomer (component B), and a compound (component C) having a cyclic structure in which one carbodiimide group has its first nitrogen and second nitrogen bonded by a linking group It is achieved by a polyester composition characterized in that
Moreover, the other objective of this invention can be achieved by the polyester fiber which consists of the said composition.

ADVANTAGE OF THE INVENTION According to this invention, the polyester-type fiber with which abrasion resistance and hydrolysis resistance were improved, and the polyester composition which can achieve this can be provided.
Furthermore, the terminal of the polyester can be sealed with a carbodiimide compound without releasing the isocyanate compound. As a result, the generation of malodor due to the isocyanate compound can be suppressed and the working environment can be improved.

  Further, when the end of the polyester is sealed with a cyclic carbodiimide compound, an isocyanate group is formed at the end of the polyester, and the reaction of the isocyanate group enables the polyester to have a high molecular weight. The cyclic carbodiimide compound also has an action of capturing a free monomer in the polyester and other compounds having an acidic group. Furthermore, according to the present invention, the cyclic carbodiimide compound has the advantage of being capable of end-capping under a milder condition than the linear carbodiimide compound by having a cyclic structure.

The difference between the linear carbodiimide compound and the cyclic carbodiimide compound in the end-capping reaction mechanism is as described below.
When a linear carbodiimide compound (R ₁ —N═C═N—R ₂ ) is used as an end-capping agent for a polyester having a carboxy group terminal, the reaction is represented by the following formula. In the formula, X is a main chain of the polyester. When the linear carbodiimide compound reacts with a carboxy group, an amide group is formed at the terminal of the polyester, and the isocyanate compound (R ₁ NCO) is released.

  On the other hand, when a cyclic carbodiimide compound is used as an end capping agent for a polyester having a carboxy group terminal, the reaction is represented by the following formula. It can be seen that when the cyclic carbodiimide compound reacts with a carboxy group, an isocyanate group (—NCO) is formed at the terminal of the polyester via an amide group, and the isocyanate compound is not liberated.

<Cyclic carbodiimide compound (component C)>
In the present invention, the cyclic carbodiimide compound (C component) has a cyclic structure. The cyclic carbodiimide compound may have a plurality of cyclic structures.
The cyclic structure has one carbodiimide group (—N═C═N—), and the first nitrogen and the second nitrogen are bonded by a bonding group. One cyclic structure has only one carbodiimide group. The number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and particularly preferably 10 to 15.

  Here, the number of atoms in the ring structure means the number of atoms that directly constitute the ring structure, and is, for example, 8 for an 8-membered ring and 50 for a 50-membered ring. This is because if the number of atoms in the cyclic structure is smaller than 8, the stability of the cyclic carbodiimide compound is lowered, and it may be difficult to store and use. From the viewpoint of reactivity, there is no particular restriction on the upper limit of the number of ring members, but cyclic carbodiimide compounds having more than 50 atoms are difficult to synthesize, and the cost may increase significantly. From this viewpoint, the number of atoms in the cyclic structure is preferably 10-30, more preferably 10-20, and particularly preferably 10-15.

The cyclic structure is preferably a structure represented by the following formula (1).

  In the formula, Q is a divalent to tetravalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, each of which may contain a heteroatom and a substituent. A heteroatom in this case refers to O, N, S, P. Two of the valences of this linking group are used to form a cyclic structure. When Q is a trivalent or tetravalent linking group, it is bonded to a polymer or other cyclic structure via a single bond, a double bond, an atom, or an atomic group.

  The linking group may include a heteroatom and a substituent, each having a divalent to tetravalent carbon number of 1 to 20 aliphatic group, a divalent to tetravalent carbon number of 3 to 20 alicyclic group, A linking group which is a tetravalent aromatic group having 5 to 15 carbon atoms or a combination thereof and has a necessary number of carbon atoms to form the cyclic structure defined above is selected. Examples of combinations include structures such as an alkylene-arylene group in which an alkylene group and an arylene group are bonded.

式中、Ａｒ^１およびＡｒ^２は各々独立に、それぞれヘテロ原子ならびに置換基を含んでいてもよい、２〜４価の炭素数５〜１５の芳香族基である。 The linking group (Q) is preferably a divalent to tetravalent linking group represented by the following formula (1-1), (1-2) or (1-3).

In the formula, Ar ¹ and Ar ² are each independently a 2- to 4-valent aromatic group having 5 to 15 carbon atoms which may contain a hetero atom and a substituent.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group (divalent) include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

R ¹ and R ² each independently contain a heteroatom and a substituent, each having 2 to 4 valent aliphatic groups having 1 to 20 carbon atoms and 2 to 4 valent fatty acids having 3 to 20 carbon atoms A cyclic group, and a combination thereof, or a combination of the aliphatic group, the alicyclic group, and a divalent to tetravalent aromatic group having 5 to 15 carbon atoms.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As cycloalkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group Group, cyclododecane triyl group, cyclohexadecane triyl group and the like. As cycloalkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Yl group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

X ¹ and X ² each independently contain a heteroatom and a substituent, each having a 2 to 4 valent aliphatic group having 1 to 20 carbon atoms and a 2 to 4 valent fatty acid having 3 to 20 carbon atoms It is a cyclic group, a divalent to tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

In the formulas (1-1) and (1-2), s and k are integers of 0 to 10, preferably 0 to 3, more preferably 0 to 1. If s and k exceed 10, the cyclic carbodiimide compound becomes difficult to synthesize, and the cost may increase significantly. From this viewpoint, the integer is preferably selected in the range of 0 to 3. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ² .

X ³ is a divalent to tetravalent C 1-20 aliphatic group, a divalent to tetravalent C 3-20 alicyclic group, each of which may contain a heteroatom and a substituent, A tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, or an ester group. , Ether group, aldehyde group and the like.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, and an ester. Group, ether group, aldehyde group and the like.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ may contain a hetero atom, and when Q is a divalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ are all divalent groups. When Q is a trivalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ is a trivalent group. When Q is a tetravalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ is a tetravalent group, or two are trivalent It is a group.

  Examples of the cyclic carbodiimide compound used in the present invention include compounds represented by the following formulas (2) to (4).

<Cyclic carbodiimide compound (2)>

  In the formula, Qa is a divalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a heteroatom. The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (2), the aliphatic group, alicyclic group, and aromatic group are all divalent. Qa is preferably a divalent linking group represented by the following formula (2-1), (2-2) or (2-3).

In the formula, Ara ¹ , Ara ² , Ra ¹ , Ra ² , Xa ¹ , Xa ² , Xa ³ , s and k are respectively Ar ¹ , Ar ² in formulas (1-1) to (1-3), The same as R ¹ , R ² , X ¹ , X ² , X ³ , s and k. However, these are all divalent.
Examples of the cyclic carbodiimide compound (2) include the following compounds.

<Cyclic carbodiimide compound (3)>

  In the formula, Qb is a trivalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom. Y is a carrier supporting a cyclic structure. The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (3), one of the groups constituting Qb is trivalent. Qb is preferably a trivalent linking group represented by the following formula (3-1), (3-2) or (3-3).

In the formula, Arb ¹ , Arb ² , Rb ¹ , Rb ² , Xb ¹ , Xb ² , Xb ³ , s and k are respectively Ar ¹ , Ar ² , R in the formulas (1-1) to (1-3). ¹ , R ² , X ¹ , X ² , X ³ , s and k are the same. However, one of these is a trivalent group.
Y is preferably a single bond, a double bond, an atom, an atomic group or a polymer. Y is a bonding portion, and a plurality of cyclic structures are bonded via Y to form a structure represented by the formula (3). Examples of the cyclic carbodiimide compound (3) include the following compounds.

<Cyclic carbodiimide compound (4)>

In the formula, Qc is a tetravalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may have a hetero atom. Z ¹ and Z ² are carriers that support a cyclic structure. Z ¹ and Z ² may be bonded to each other to form a cyclic structure.
The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (4), Qc is tetravalent. Accordingly, one of these groups is a tetravalent group or two are trivalent groups. Qc is preferably a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3).

Arc ¹ , Arc ² , Rc ¹ , Rc ² , Xc ¹ , Xc ² , Xc ³ , s and k are respectively Ar ¹ , Ar ² , R ¹ , Same as R ² , X ¹ , X ² , X ³ , s and k. However, Arc ¹ , Arc ² , Rc ¹ , Rc ² , Xc ¹ , Xc ² and Xc ³ are either a tetravalent group or two are trivalent groups.
Z ¹ and Z ² are preferably each independently a single bond, a double bond, an atom, an atomic group or a polymer. Z ¹ and Z ² are bonding portions, and a plurality of cyclic structures are bonded via Z ¹ and Z ² to form a structure represented by the formula (4).
Examples of the cyclic carbodiimide compound (4) include the following compounds.

<Method for producing cyclic carbodiimide compound>
The cyclic carbodiimide compound can be produced by a conventionally known method. For example, a method for producing an amine body via an isocyanate body, a method for producing an amine body via an isothiocyanate body, a method for producing an amine body via a triphenylphosphine body, a urea body from an amine body The method of manufacturing via a thiourea body, the method of manufacturing via a thiourea body, the method of manufacturing from a carboxylic acid body via an isocyanate body, the method of manufacturing a lactam body, etc. are mentioned.

Moreover, the cyclic carbodiimide compound of this invention can be manufactured by the method described in the following literature.
Tetrahedron Letters, Vol. 34, no. 32, 515-5158, 1993.
Medium- and Large-Membered Rings from Bis (iminophosphoranes): An Efficient Preparation of Cyclic Carbidiimides, Pedro Molina et al.
Journal of Organic Chemistry, Vol. 61, no. 13, 4289-4299, 1996.
New Models for the Study of the Racemization Mechanism of Carbodiimides. Synthesis and Structure (X-ray Crystallography and 1H NMR) of Cyclic Carbodiimides, Pedro Molina et al.
Journal of Organic Chemistry, Vol. 43, No8, 1944-1946, 1978.
Macrocyclic Ureas As Masked Isocynates, Henri Ulrich et al.
Journal of Organic Chemistry, Vol. 48, no. 10, 1694-1700, 1983.
Synthesis and Reactions of Cyclic Carbodiimides,
R. Richter et al.
Journal of Organic Chemistry, Vol. 59, no. 24, 7306-7315, 1994.
A New and Efficient Preparation of Cyclic Carbodiamids from Bis (iminophosphoranea) and the System Boc ₂ O / DMAP, Pedro Molina et al.

（２）得られたニトロ体を還元して下記式（ｄ）で表わされるアミン体を得る工程、

（３）得られたアミン体とトリフェニルホスフィンジブロミドを反応させ下記式（ｅ）で表されるトリフェニルホスフィン体を得る工程、および

（４）得られたトリフェニルホスフィン体を反応系中でイソシアネート化した後、直接脱炭酸させることによって製造したものは、本願発明に用いる環状カルボジイミド化合物として好適に用いることができる。 Depending on the compound to be produced, an appropriate production method may be employed. For example, (1) nitrophenol represented by the following formula (a-1), nitrophenol represented by the following formula (a-2), and A step of reacting a compound represented by the following formula (b) to obtain a nitro compound represented by the following formula (c);

(2) A step of reducing the obtained nitro body to obtain an amine body represented by the following formula (d);

(3) a step of reacting the obtained amine body with triphenylphosphine dibromide to obtain a triphenylphosphine body represented by the following formula (e); and

(4) After the obtained triphenylphosphine body is isocyanated in the reaction system and then directly decarboxylated, it can be suitably used as the cyclic carbodiimide compound used in the present invention.

(In the above formula, Ar ¹ and Ar ² are each independently an aromatic group optionally substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group. E ¹ and E ² are each independently a halogen atom. A group selected from the group consisting of an atom, a toluenesulfonyloxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy group, Ar ^a is a phenyl group, X is represented by the following formula (i -1) to (i-3).

（式中、ｎは１〜６の整数である。）

（式中、ｍおよびｎは各々独立に０〜３の整数である。）

（式中、Ｒ^１およびＲ^２は各々独立に、炭素数１〜６のアルキル基、フェニル基を表す。）

(In the formula, n is an integer of 1 to 6.)

(In the formula, m and n are each independently an integer of 0 to 3.)

(In the formula, R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

<Polyester (component A)>
In the present invention, the polyester (component A) comprises (a) a dicarboxylic acid or an ester-forming derivative thereof and (b) a diol or an ester-forming derivative thereof, (c) a hydroxycarboxylic acid or an ester-forming derivative thereof, (d) a lactone At least one part of the terminal of the polymer or copolymer obtained by polymerizing one or more selected from the above is sealed with a C component. Examples of (i) dicarboxylic acid or ester-forming derivatives thereof include terephthalic acid, isophthalic acid, phthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, and 4,4′-diphenoxyethane. Dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bis (4-carboxyphenyl) methane, anthracene dicarboxylic acid, Examples include aromatic dicarboxylic acids such as 4,4′-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium sulfoisophthalic acid, and 5-sodium sulfoisophthalic acid, and ester-forming derivatives thereof.

Further, aliphatic dicarboxylic acids such as succinic acid, succinic acid, adipic acid, 1,6-hexanedicarboxylic acid, and dimer acid, or ester-forming derivatives thereof can be used.
In addition, cycloaliphatic-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, decalin-2,6-dicarboxylic acid, alicyclic dicarboxylic acid such as tetralin-2,6-dicarboxylic acid, or ester-forming derivatives thereof. Etc.

  Examples of the (ro) diol or ester-forming derivative thereof include aliphatic glycols having 2 to 20 carbon atoms, such as ethylene glycol, polyethylene glycol, 1,3-trimethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, dimer diol, or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, polytrimethylene Examples thereof include aliphatic diols such as glycol, polypropylene glycol, and polytetramethylene glycol, and ester-forming derivatives thereof.

  Further, alicyclic diols such as cyclohexane 1,2-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethylol, or ether-forming derivatives thereof can be used.

  In addition, aromatic dihydroxy compounds such as xylylene glycol, 4,4′-dihydroxybiphenyl, hydroquinone, tert-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F and the like aromatic diols or ester-forming derivatives thereof. Can be mentioned.

式中、ｎは２から４の整数である。Ａｒは、フェニレン基またはナフタレンジイル基が好ましい。Ａｒは、特に１，４−フェニレン基、２，６−ナフタレンジイル基が好ましい。 The polyester (component A) is preferably a polyester whose main chain is a repeating unit mainly represented by the following formula (II).

In the formula, n is an integer of 2 to 4. Ar is preferably a phenylene group or a naphthalenediyl group. Ar is particularly preferably a 1,4-phenylene group or a 2,6-naphthalenediyl group.

The reduced viscosity of the polyester is preferably 0.2 to 1.5 dl / g, more preferably 0.3 to 1.3 dl / g.
Examples of the above (c) hydroxycarboxylic acid or ester-forming derivatives thereof include glycolic acid, D-lactic acid, L-lactic acid, racemic lactic acid, hydroxypropionic acid, 3-hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, p-hydroxy Examples thereof include benzoic acid, m-hydroxybenzoic acid, p-β-hydroxyethoxybenzoic acid, 6-hydroxy-2-naphthoic acid, oligo or polycaprolactone, and ester-forming derivatives thereof.

  Among the ester-forming derivatives of hydroxycarboxylic acid, lactone is preferably applied to the production of polyester. Examples of such lactone (d) include glycolide, D-lactide, L-lactide, mesolactide, ε-caprolactone, δ. -Valerolactone, β-propiolactone, pivalolactone, β-benzylmalolactonate, γ-butyrolactone, 1,4-dioxan-2-one, undecalactone, 1,4-dioxepan-2-one, (R) -3-methyl-4-oxa-6-hexanolide, (S) -3-methyl-4-oxa-6-hexanolide, and the like. In addition, monofunctional components such as stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, tert-butylbenzoic acid, benzoylbenzoic acid, tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane Trifunctional or polyfunctional components such as trimethylolpropane, glycerol, pentaerythritol and the like may be used.

Specifically, polyglycolic acid, polylactic acid, poly-3-hydroxybutyric acid, poly-4-hydroxybutyric acid, poly-4-hydroxyvaleric acid, poly-3-hydroxyhexanoic acid or polycaprolactone, polyethylene adipate, polyethylene succinate, polybutylene Aliphatic polyesters such as adipate, polybutylene succinate or polycyclohexane dimethanol cyclohexane dicarboxylate, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, poly 1,4-methylol cyclohexane terephthalate, polyethylene 2,6-naphthalate, polybutylene Aromatic polyesters such as 2,6-naphthalate and polytrimethylene 2,6-naphthalate can be mentioned, and these can be used alone or in 2 Or more can be used.
As the polyester sealed with the component C, those obtained by any conventionally known production method can be applied to the present invention.

<Thermoplastic elastomer (component B)>
As the thermoplastic elastomer used in the present invention, any known thermoplastic elastomer can be used, and it is a polymer that has the property of softening when heated to show plasticity and returning to a rubber-like elastic body when cooled.

  For example, styrene-based thermoplastic elastomers consisting mainly of block copolymers with mainly polystyrene as hard segments and polybutadiene or hydrogenated butadiene or polyisoprene as soft segments, and polyolefins such as polypropylene or polyethylene as hard segments, mainly ethylene A polyolefin-based thermoplastic elastomer consisting of a blend of propylene / diene terpolymers as a soft segment, mainly block copolymer containing polybutylene terephthalate as a hard segment and polytetramethylene ether glycol or aliphatic polyester as a soft segment. Polyester thermoplastic elastomer made of polymer, vinylidene fluoride / hexafluoropropylene copolymer Or fluoroplastic elastomers such as tetrafluoroethylene / propylene copolymers, polyamide thermoplastic elastomers such as polyesteramide or polyetheramide, 1,2-polybutadiene thermoplastic elastomer, vinyl chloride thermoplastic elastomer, ethylene・ Vinyl acetate thermoplastic elastomer, chlorinated polyethylene thermoplastic elastomer, copolymer of ethylene and α, β-ethylenically unsaturated carboxylic acid or its alkyl ester with metal ions such as Na, Ca, Zn, Mg Examples include neutralized ionomer-based thermoplastic elastomers, and one or more of these thermoplastic elastomers can be appropriately used. There are various types of these thermoplastic elastomers ranging from soft to fairly hard, but the use of relatively flexible thermoplastic elastomers tends to have a remarkable effect of improving wear resistance, which is the object of the present invention. And preferred.

  The content of the thermoplastic elastomer in the polyester composition is in the range of 1% by weight to 40% by weight. When the content is less than 1% by weight, the abrasion resistance is not sufficient, while when it is more than 40% by weight, the strength and elongation of the monofilament to be obtained are decreased and the filament diameter of the monofilament is also increased. In addition, when the content of the thermoplastic elastomer in the polyester composition is 5% by weight or more and 30% by weight or less, the wear resistance and the strength and elongation characteristics are further improved, and uniform fibers with less fiber diameter unevenness are obtained. Since it is obtained, it is preferable.

  The polyester composition of the present invention contains an end-capped polyester having a structure in which a C-component cyclic carbodiimide compound is bonded to the end of the polyester. The cyclic carbodiimide compound reacts with the carboxyl group of the polyester as follows to form the following structure at the end of the polyester.

（Ｘはポリエステルの主鎖で、Ｑはカルボジイミド基の第一窒素と第二窒素とを結ぶ結合基である。）

(X is the main chain of the polyester, and Q is a linking group that connects the primary nitrogen and secondary nitrogen of the carbodiimide group.)

  As will be described later, the polyester fiber of the present invention can be produced by spinning a polyester composition in which a polyester (component A), a thermoplastic elastomer (component B) and a cyclic carbodiimide compound (component C) are mixed. . The cyclic carbodiimide compound reacts with the terminal of the polyester to seal the terminal. Excess cyclic carbodiimide compound remains in the polyester composition unreacted.

  Therefore, the polyester fiber of the present invention contains polyester whose end is sealed, a thermoplastic elastomer and a cyclic carbodiimide compound. Further, depending on the degree of reaction of terminal modification, a polyester whose terminal is not sealed may be contained.

  In the polyester composition constituting the fiber, the content of the cyclic carbodiimide compound (C component) remaining in the composition in an unreacted state is 0.001 to 10 parts by weight, preferably 100 parts by weight of polyester fiber. Is 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight.

<Method for producing polyester fiber>
The polyester fiber of the present invention can be produced by discharging a composition obtained by mixing polyester, a thermoplastic elastomer and a cyclic carbodiimide compound from a spinneret.

  Mixing of the polyester and the thermoplastic elastomer can be performed at any stage from immediately after the completion of the polycondensation of the polyester until it is discharged from the spinneret. For example, in a polymerization can immediately after the completion of the polycondensation, After adding thermoplastic elastomer to polyester, kneading, making chips by conventional methods, drying at a temperature lower than the softening point of thermoplastic elastomer, then melt spinning and stretching using a melt pressure type or extruder type spinning machine, etc. Or after adding and blending thermoplastic elastomer chips to the dried polyester chips, melt spinning and stretching while melting and kneading with an extruder-type spinning machine, or with a predetermined amount of polyester chips and heat Extruder type while supplying plastic elastomer Kneading, melt spinning, and drawing with a yarn machine, or a polyester and thermoplastic elastomer are melted and kneaded in advance using a uniaxial or biaxial extruder kneader and then chipped and dried at a temperature lower than the softening point of the thermoplastic elastomer. Then, melt spinning / stretching methods and the like can be mentioned, but it is preferable to forcibly knead the polyester and the thermoplastic elastomer at least once before discharging from the spinneret.

  Also, the cyclic carbodiimide compound (component C) can be added at any stage immediately after completion of the polycondensation of the polyester until it is discharged from the spinneret, for example, polyester and thermoplastic elastomer are chip blended. Examples thereof include a method of adding the powder as a powder and a method of adding the polyester and the thermoplastic elastomer at the stage of forced kneading at the stage before melt spinning.

  The method for adding and mixing the cyclic carbodiimide compound (component C) to the polyester or / and thermoplastic elastomer is not particularly limited, and it can be used as a master batch of polyester or / and thermoplastic elastomer to be applied by solution, melt or application by a conventionally known method. A method of adding, or a method in which a solid of a polyester or / and a thermoplastic elastomer is brought into contact with a liquid in which the cyclic carbodiimide compound is dissolved, dispersed or melted and the cyclic carbodiimide compound is permeated can be employed.

  When taking the method of adding as a master batch of solution, melt, or applied polyester or / and thermoplastic elastomer, it can be added using a conventionally known kneading apparatus. In kneading, a kneading method in a solution state or a kneading method in a molten state is preferable from the viewpoint of uniform kneading properties. The kneading apparatus is not particularly limited, and examples thereof include conventionally known vertical reaction vessels, mixing tanks, kneading tanks or uniaxial or multiaxial horizontal kneading apparatuses such as uniaxial or multiaxial ruders and kneaders. The kneading time is not particularly specified, and depends on the kneading apparatus and kneading temperature, but is selected from 0.1 minutes to 2 hours, preferably 0.2 minutes to 60 minutes, more preferably 1 minute to 30 minutes.

As a solvent, what is inactive with respect to polyester and a cyclic carbodiimide compound can be used. In particular, a solvent is preferred to have affinity for both and at least partially dissolve both, or at least partially dissolve in both.
As such a solvent, for example, a hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, a halogen solvent, an amide solvent and the like can be used.

Examples of the hydrocarbon solvent include hexane, cyclohexane, benzene, toluene, xylene, heptane, decane and the like.
Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, and isophorone.

Examples of ester solvents include ethyl acetate, methyl acetate, ethyl succinate, methyl carbonate, ethyl benzoate, and diethylene glycol diacetate.
Examples of the ether solvent include diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, triethylene glycol diethyl ether, diphenyl ether and the like.

Examples of the halogen solvent include dichloromethane, chloroform, tetrachloromethane, dichloroethane, 1,1 ′, 2,2′-tetrachloroethane, chlorobenzene, dichlorobenzene and the like.
Examples of amide solvents include formamide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or as a mixed solvent as desired.

  In the present invention, the solvent is applied in the range of 1 to 1,000 parts by weight per 100 parts by weight of the total of polyester, thermoplastic elastomer and cyclic carbodiimide compound. If the amount is less than 1 part by weight, there is no significance in applying the solvent. The upper limit of the amount of solvent used is not particularly limited, but is about 1,000 parts by weight from the viewpoints of operability and reaction efficiency.

  When a method in which a polyester or / and thermoplastic elastomer solid is brought into contact with a liquid in which the cyclic carbodiimide compound is dissolved, dispersed or melted and the cyclic carbodiimide compound is infiltrated, the solid carbodiimide dissolved in the solvent as described above is used. A method of bringing a polyester or / and a thermoplastic elastomer into contact with each other, a method of bringing a solid polyester or / and a thermoplastic elastomer into contact with a carbodiimide emulsion, or the like can be employed. As a method of contacting, a method of immersing polyester or / and a thermoplastic elastomer, a method of applying to polyester, a method of spraying, or the like can be suitably used.

  The sealing reaction with the cyclic carbodiimide compound is possible at a temperature of room temperature (25 ° C.) to about 300 ° C., but is more accelerated in the range of 50 to 250 ° C., more preferably 80 to 200 ° C. from the viewpoint of reaction efficiency. . The polyester is more likely to react in a molten state, but it is preferable to react at a temperature lower than 300 ° C. in order to suppress volatilization and decomposition of the cyclic carbodiimide compound. It is also effective to apply a solvent to lower the melting temperature of the polyester and increase the stirring efficiency.

  Although the reaction proceeds sufficiently rapidly without a catalyst, a catalyst that accelerates the reaction can also be used. As a catalyst, the catalyst used with the conventional linear carbodiimide compound is applicable. These can be used alone or in combination of two or more. The addition amount of the catalyst is not particularly limited, but is preferably 0.001 to 1 part by weight and more preferably 0.01 to 0.1 part by weight with respect to 100 parts by weight of the total of the polyester and the cyclic carbodiimide compound. More preferably, 0.02 to 0.1 parts by weight is most preferable.

  The application amount of the cyclic carbodiimide compound is selected such that the carbodiimide group contained in the cyclic carbodiimide compound is 0.5 to 100 equivalents per equivalent of the acidic group. If the amount is less than 0.5 equivalent, there may be no significance in applying carbodiimide. On the other hand, if it exceeds 100 equivalents, the characteristics of the substrate may be altered. From this viewpoint, on the above criteria, a range of preferably 0.6 to 100 equivalents, more preferably 0.65 to 70 equivalents, further preferably 0.7 to 50 equivalents, and particularly preferably 0.7 to 30 equivalents is selected. Is done.

  The melt spinning conditions may be normal polyester melt spinning conditions. That is, a polyester composition in which polyester (A component), thermoplastic elastomer (B component) and cyclic carbodiimide compound (C component) are mixed is melted by an extruder type or pressure melter type melt extruder, and then the gear pump. After being measured and filtered in the pack, it is discharged as a monofilament, a multifilament, etc. from a nozzle provided in the base.

  The shape of the base and the number of the bases are not particularly limited, and any of circular, irregular, solid, hollow and the like can be adopted. The discharged yarn is immediately cooled and solidified, then converged, applied with oil, and wound.

  The stretching may be one-stage stretching or multi-stage stretching of two or more stages. From the viewpoint of producing a high-strength fiber, the stretching ratio is preferably 3 times or more, and more preferably 4 times or more. Preferably 3 to 10 times is selected. However, if the draw ratio is too high, the fiber is devitrified and whitened, the strength of the fiber is lowered, the elongation at break is too low, and it is not preferable for fiber use.

As a preheating method for stretching, in addition to the temperature rise of the roll, a flat or pin-like contact heater, a non-contact hot plate, a heat medium bath, and the like can be used, and a commonly used method may be used.
Subsequent to stretching, it is preferable that heat treatment is performed at a temperature not lower than the melting point and not lower than the glass transition temperature (Tg) of the polyester (component A) before winding. In addition to the hot roller, any method such as a contact heater or a non-contact hot plate can be adopted for the heat treatment.

  The polyester fiber obtained in the present invention can take various forms of fiber structures. Specifically, thread form products such as sewing thread, embroidery thread, string, fabric such as woven fabric, knitting, nonwoven fabric, felt, outer clothes such as shirt, blouson, pants, coat, sweater, uniform, underwear, pantyhose, socks, Lining, interlining, sports clothing, high value-added clothing products such as women's clothing and formal wear, clothing products such as cups and pads, curtains, carpets, chair upholstery, mats, furniture, baskets, furniture upholstery, wall materials, etc. Products for daily use such as belts and slings, as well as various textile products such as canvas, belts, nets, ropes, heavy cloth, bags, industrial materials such as felts and filters, vehicle interior products, and artificial leather products.

  The polyester-based fiber of the present invention may be used alone as a fiber comprising the polyester composition of the present invention, or may be mixed with other types of fibers. In addition to various combinations with fiber structures composed of other types of fibers, mixed modes include mixed yarns with other fibers, composite false twisted yarns, mixed spun yarns, long and short composite yarns, fluid processed yarns, covering yarns, and twisted yarns. Examples thereof include union, union, pile, pile, mixed cotton, mixed non-woven fabric of long fibers and short fibers, and felt. In the case of mixing, the mixing ratio is selected to be 1% by weight or more, more preferably 10% by weight or more, and further preferably 30% by weight or more in order to exhibit the characteristics of polyester (component A).

  Examples of other fibers to be mixed include cellulose fibers such as cotton, hemp, rayon, and tencel, wool, silk, acetate, polyester, nylon, acrylic, vinylon, polyolefin, and polyurethane.

<Stabilizer>
The polyester composition of the present invention can contain a stabilizer. As a stabilizer, what is used for the stabilizer of a normal thermoplastic resin can be used. For example, an antioxidant, a light stabilizer, etc. can be mentioned. By blending these agents, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.
Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphite compounds, thioether compounds, and the like.

  Examples of hindered phenol compounds include n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5 ′). -Tert-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -Propionate], 2,2'-methylene-bis (4-methyl-tert-butylphenol), triethylene glycol-bis 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro ( 5,5) Undecane and the like can be mentioned.

  As a hindered amine compound, N, N′-bis-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis [3- (3′-Methyl-5′-tert-butyl-4′-hydroxyphenyl) propionyl] diamine, N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionyl ] Hydrazine, N-salicyloyl-N'-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N'-bis [2- {3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide and the like. Preferably, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate] and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl) -4-hydroxyphenyl) propionate] methane and the like.

  As the phosphite compound, those in which at least one P—O bond is bonded to an aromatic group are preferable. Specifically, tris (2,6-di-tert-butylphenyl) phosphite, tetrakis ( 2,6-di-tert-butylphenyl) 4,4′-biphenylene phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, tris (mixed mono and di-no Butylphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4'-isopropylidene-bis (phenyl - dialkyl phosphite), and the like.

  Among them, tris (2,6-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,6-di-tert-butyl) -4-Methylphenyl) pentaerythritol-diphosphite, tetrakis (2,6-di-tert-butylphenyl) 4,4′-biphenylene phosphite and the like can be preferably used.

  Specific examples of thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio) Propionate) and the like.

  Specific examples of the light stabilizer include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, hindered amine compounds, and the like.

  Examples of the benzophenone compounds include benzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′. -Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy -2 - carboxy benzophenone, 2-hydroxy-4- (2-hydroxy-3-methyl - acryloxy-isopropoxyphenyl) benzophenone.

  Examples of the benzotriazole compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-4′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (Α, α-Dimethylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α Dimethylbenzyl) phenyl] -2H- benzotriazole, 2- (4'-octoxy-2'-hydroxyphenyl) benzotriazole.

Examples of the aromatic benzoate compounds include alkylphenyl salicylates such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate.
Examples of oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, and 2-ethoxy-3′-. Examples include dodecyl oxalic acid bisanilide.
Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3′-diphenyl acrylate and 2-ethylhexyl-cyano-3,3′-diphenyl acrylate.

  Examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2, 6,6-tetramethylpiperidine, 4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarba Yloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethylpi-4-peridyl) adipate, bis (2,2,6,6-tetramethylpi-4-peridyl) terephthalate, 1,2-bis (2,2,6,6-tetramethylpi-4-peridylo) Cis) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) -Tolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl -4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- “2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid And 1,2,2, , 6-Pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethanol And the like. In this invention, E component may be used by 1 type and may be used in combination of 2 or more type. As the stabilizer component, a hindered phenol compound and / or a benzotriazole compound are preferable. The content of the stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of the polyester (component A).

<Crystallization accelerator>
The polyester composition of the present invention can contain an organic or inorganic crystallization accelerator. By containing the crystallization accelerator, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
That is, by applying the crystallization accelerator, moldability and crystallinity are improved, and a molded product that is sufficiently crystallized even in normal injection molding and excellent in heat resistance and moist heat resistance can be obtained. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.

  As the crystallization accelerator used in the present invention, those generally used as crystallization nucleating agents for crystalline resins can be used, and both inorganic crystallization nucleating agents and organic crystallization nucleating agents are used. be able to.

  As inorganic crystallization nucleating agents, talc, kaolin, silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide, boron nitride , Montmorillonite, neodymium oxide, aluminum oxide, phenylphosphonate metal salt and the like. These inorganic crystallization nucleating agents are treated with various dispersing aids in order to enhance the dispersibility in the composition and the effect thereof, and are in a highly dispersed state with a primary particle size of about 0.01 to 0.5 μm. Are preferred.

  Organic crystallization nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate , Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicy Organic carboxylic acid metal salts such as zinc acid, aluminum dibenzoate, β-naphthoic acid sodium, β-naphthoic acid potassium, sodium cyclohexanecarboxylic acid and the like, and organic sulfonic acid metal salts such as sodium p-toluenesulfonate and sodium sulfoisophthalate. Can be mentioned.

  Also, organic carboxylic acid amides such as stearic acid amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (tert-butylamide), low density polyethylene, high density polyethylene, polyiso Propylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid copolymer, sodium of styrene-maleic anhydride copolymer Examples thereof include salts (so-called ionomers), benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.

Among these, at least one selected from talc and metal organic carboxylic acid salts is preferably used. Only one type of crystallization accelerator may be used in the present invention, or two or more types may be used in combination.
The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight per 100 parts by weight of the polyester (component A).

<Filler>
The polyester composition of the present invention can contain an organic or inorganic filler. By containing the filler component, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.

  Organic fillers such as rice husks, wood chips, okara, waste paper ground materials, clothing ground materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute fibers, banana fibers, coconut fibers Plant fibers such as pulp or cellulose fibers processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, angora, cashmere and camel, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers , Paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like. From the viewpoint of moldability, powdery materials such as paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, and starch are preferred. Powder, bamboo powder, cellulose powder and kenaf powder are preferred. Paper powder and wood powder are more preferable. Paper dust is particularly preferable.

These organic fillers may be those directly collected from natural products, but may also be those obtained by recycling waste materials such as waste paper, waste wood and old clothes.
The wood is preferably a softwood material such as pine, cedar, oak or fir, or a hardwood material such as beech, shii or eucalyptus.

  Paper powder is an adhesive from the viewpoint of moldability, especially emulsion adhesives such as vinyl acetate resin emulsions and acrylic resin emulsions that are usually used when processing paper, polyvinyl alcohol adhesives, polyamide adhesives Those containing hot melt adhesives such as are preferably exemplified.

  In the present invention, the blending amount of the organic filler is not particularly limited, but from the viewpoint of moldability and heat resistance, it is preferably 1 to 300 parts by weight, more preferably 5 parts per 100 parts by weight of the polyester (component A). It is -200 weight part, More preferably, it is 10-150 weight part, Most preferably, it is 15-100 weight part. If the blending amount of the organic filler is less than 1 part by weight, the effect of improving the moldability of the composition is small, and if it exceeds 300 parts by weight, uniform dispersion of the filler becomes difficult, or other than moldability and heat resistance In addition, the strength and appearance of the material may decrease, which is not preferable.

  The composition of the present invention preferably contains an inorganic filler. A composition excellent in mechanical properties, heat resistance and moldability can be obtained by the inorganic filler. As the inorganic filler used in the present invention, a fibrous, plate-like, or powder-like material used for reinforcing ordinary thermoplastic resins can be used.

  Specifically, for example, carbon nanotube, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, imogolite, sepiolite, Asbestos, slag fiber, zonolite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, and other fibrous inorganic fillers, layered silicate, and organic onium ions Layered silicate, glass flake, non-swelling mica, graphite, metal foil, ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, powdered silicic acid, feldspar powder, potassium titanate, shirasuba Plates and particles of inorganic fillers such as carbon nanoparticles such as carbon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dosonite and white clay fullerene Agents.

  Specific examples of layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halosite, kanemite, and kenyanite, Li-type fluorine teniolite, Na And swellable mica such as Li-type fluorine teniolite, Li-type tetrasilicon fluorine mica and Na-type tetrasilicon fluorine mica. These may be natural or synthetic. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Li type fluorine teniolite and Na type tetrasilicon fluorine mica are preferable.

  Among these inorganic fillers, fibrous or plate-like inorganic fillers are preferable, and glass fiber, wollastonite, aluminum borate whisker, potassium titanate whisker, mica, and kaolin, a cation-exchanged layered silicate. Is preferred. The aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.

Such a filler may be coated or converged with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane. May be.
The blending amount of the inorganic filler is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 50 parts by weight, based on 100 parts by weight of the polyester (component A). Preferably it is 1-30 weight part, Most preferably, it is 1-20 weight part.

<Antistatic agent>
The polyester composition of the present invention can contain an antistatic agent. Examples of the antistatic agent include quaternary ammonium salt compounds such as (β-lauramidopropionyl) trimethylammonium sulfate and sodium dodecylbenzenesulfonate, sulfonate compounds, and alkyl phosphate compounds.

In the present invention, the antistatic agent may be used alone or in combination of two or more. The content of the antistatic agent is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyester (component A).

<Plasticizer>
The polyester composition of the present invention can contain a plasticizer. As the plasticizer, generally known plasticizers can be used. Examples include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.

  As a polyester plasticizer, acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, Examples thereof include polyesters composed of diol components such as 1,6-hexanediol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or a monofunctional alcohol.

  Examples of the glycerol plasticizer include glycerol monostearate, glycerol distearate, glycerol monoacetomonolaurate, glycerol monoacetomonostearate, glycerol diacetomonooleate, and glycerol monoacetomonomontanate.

  Polyvalent carboxylic acid plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellitic acid tributyl, trimellitic acid trioctyl, Trimellitic acid esters such as trihexyl meritate, isodecyl adipate, adipic acid esters such as adipate-n-decyl-n-octyl, citrate esters such as tributyl acetylcitrate, bis (2-ethylhexyl) azelate, etc. Examples include sebacic acid esters such as azelaic acid ester, dibutyl sebacate, and bis (2-ethylhexyl) sebacate.

  Examples of the phosphate ester plasticizer include tributyl phosphate, tris phosphate (2-ethylhexyl), trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylhexyl phosphate, and the like.

  Polyalkylene glycol plasticizers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide-propylene oxide) block and / or random copolymers, ethylene oxide addition polymers of bisphenols, tetrahydrofuran addition polymers of bisphenols, etc. And end-capping compounds such as a terminal epoxy-modified compound, a terminal ester-modified compound, and a terminal ether-modified compound.

  Examples of the epoxy plasticizer include an epoxy triglyceride composed of alkyl epoxy stearate and soybean oil, and an epoxy resin using bisphenol A and epichlorohydrin as raw materials.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol-bis (2-ethylbutyrate), and fatty acids such as stearamide. Examples thereof include fatty acid esters such as amide and butyl oleate, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.

As the plasticizer, at least one selected from polyester-type plasticizers and polyalkylene-type plasticizers can be preferably used, and only one type may be used, or two or more types may be used in combination.
The content of the plasticizer is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, and still more preferably 0.1 to 10 parts by weight per 100 parts by weight of the polyester (component A). . In the present invention, each of the crystallization nucleating agent and the plasticizer may be used alone, or more preferably used in combination.

Hereinafter, the present invention will be described by way of examples.
Various characteristics were measured by the following methods.

(1) Stability against hydrolysis:
The reduced viscosity retention when the polyester fiber was treated with a pressure cooker at 120 ° C. and 100% RH for 50 hours was evaluated.
The hydrolysis resistance is “pass” when the reduced viscosity retention is 80 to less than 90%, “excellent pass” when it is less than 90% to less than 95%, and “particularly pass” when it is between 95% and 100%. It is judged.
The reduced viscosity (η _sp / c) was measured by dissolving 1.2 mg of a sample in 100 ml of [tetrachloroethane / phenol = (6/4) wt% mixed solvent] and measuring at 35 ° C. using an Ubbelohde viscosity tube. The viscosity retention was determined as the reduced viscosity after sample treatment for the molecule and the reduced viscosity before sample treatment for the denominator.

(2) Wear resistance evaluation method:
When the sample is a monofilament, a calcium carbonate manufactured by Sankyo Seimitsu Co., Ltd. is used as a filler for neutral paper making on a ceramic cylinder surface with a diameter of 60 cm rotating at 1500 rpm with a weight of 100 g on the filament tip. A 0.5% aqueous suspension of the powder “Escalon # 800” was brought into contact while being dropped, and the time until the fiber was cut was measured.
Moreover, when the sample was a multifilament, the above evaluation was performed by taking out one arbitrary short fiber constituting the multifilament. The index for evaluation is the amount of wear (mm) / time (h).

(3) Existence of isocyanate odor:
When the obtained polyester fiber was melted at 300 ° C. for 5 minutes, it was judged by sensory evaluation whether or not the measurer felt an isocyanate odor. When the isocyanate odor was not felt, it was judged to be acceptable.

(4) Quality of work environment:
Judgment was made based on whether the working environment was deteriorated by an isocyanate odor during the production of the polyester composition. When it did not deteriorate, it was evaluated as good.

(5) Qualitative and quantitative evaluation of isocyanate gas generation:
The sample was heated at 260 ° C. for 8 minutes, and qualitatively and quantitatively analyzed by pyrolysis GC / MS analysis. In addition, fixed_quantity | quantitative_assay was performed using the analytical curve created with isocyanate. GC / MS used was GC / MS Jms Q1000GC K9 manufactured by JEOL Ltd.

Hereinafter, the agent used by this invention is described.
The following agents were produced and used as the C component in the present invention.

[Production Example 1] Synthesis of cyclic carbodiimide compound CC1 (MW = 252):
Reaction in which 200 ml of o-nitrophenol (0.11 mol), 1,2-dibromoethane (0.05 mol), potassium carbonate (0.33 mol), and N, N-dimethylformamide (DMF) were installed with a stirrer and a heating device The apparatus was charged in an N ₂ atmosphere and reacted at 130 ° C. for 12 hours. After that, DMF was removed under reduced pressure, and the resulting solid was dissolved in 200 ml of dichloromethane and separated three times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and dichloromethane was removed under reduced pressure to obtain an intermediate product A (nitro form).

  Next, intermediate product A (0.1 mol), 5% palladium carbon (Pd / C) (1 g), and 200 ml of ethanol / dichloromethane (70/30) were charged into a reactor equipped with a stirrer, and 5 hydrogen substitution was performed. The reaction is performed in a state where hydrogen is constantly supplied at 25 ° C., and the reaction is terminated when there is no decrease in hydrogen. When Pd / C was recovered and the mixed solvent was removed, an intermediate product B (amine body) was obtained.

Next, in a reactor equipped with a stirrer, a heating device, and a dropping funnel, triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane are charged and stirred in an N ₂ atmosphere. A solution prepared by dissolving intermediate product B (0.05 mol) and triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane is gradually added dropwise thereto at 25 ° C. After completion of dropping, the reaction is carried out at 70 ° C. for 5 hours. Thereafter, the reaction solution was filtered, and the filtrate was separated 5 times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and 1,2-dichloroethane was removed under reduced pressure to obtain an intermediate product C (triphenylphosphine compound).

Next, in a reactor equipped with a stirrer and a dropping funnel, di-tert-butyl dicarbonate (0.11 mol), N, N-dimethyl-4-aminopyridine (0.055 mol), dichloromethane under N ₂ atmosphere. 150 ml was charged and stirred. Thereto, 100 ml of dichloromethane in which the intermediate product C (0.05 mol) was dissolved was slowly added dropwise at 25 ° C. After dropping, react for 12 hours. Then, CC1 shown by the following structural formula was obtained by refine | purifying the solid substance obtained by removing dichloromethane. The structure of CC1 was confirmed by NMR and IR.

[Production Example 2] Synthesis of cyclic carbodiimide compound CC2 (MW = 516) o-nitrophenol (0.11 mol), pentaerythrityl tetrabromide (0.025 mol), potassium carbonate (0.33 mol), N, N-dimethyl 200 ml of formamide was charged in a reactor equipped with a stirrer and a heating device under N ₂ atmosphere, reacted at 130 ° C. for 12 hours, DMF was removed under reduced pressure, and the resulting solid was dissolved in 200 ml of dichloromethane, and 3 ml with 100 ml of water. Batch dispensing was performed. The organic layer was dehydrated with 5 g of sodium sulfate, and dichloromethane was removed under reduced pressure to obtain an intermediate product D (nitro form).

  Next, intermediate product D (0.1 mol), 5% palladium carbon (Pd / C) (2 g), and 400 ml of ethanol / dichloromethane (70/30) were charged into a reactor equipped with a stirrer, and 5 hydrogen substitution was performed. The reaction was performed in a state where hydrogen was constantly supplied at 25 ° C., and the reaction was terminated when there was no decrease in hydrogen. When Pd / C was recovered and the mixed solvent was removed, an intermediate product E (amine body) was obtained.

Next, triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane were charged and stirred in a reactor equipped with a stirrer, a heating device, and a dropping funnel in an N ₂ atmosphere. A solution prepared by dissolving the intermediate product E (0.025 mol) and triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane was gradually added dropwise thereto at 25 ° C. After completion of dropping, the reaction is carried out at 70 ° C. for 5 hours. Thereafter, the reaction solution was filtered, and the filtrate was separated 5 times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and 1,2-dichloroethane was removed under reduced pressure to obtain an intermediate product F (triphenylphosphine compound).

Next, in a reactor equipped with a stirrer and a dropping funnel, di-tert-butyl dicarbonate (0.11 mol), N, N-dimethyl-4-aminopyridine (0.055 mol), dichloromethane under N ₂ atmosphere. 150 ml is charged and stirred. Thereto, 100 ml of dichloromethane in which the intermediate product F (0.025 mol) was dissolved was slowly added dropwise at 25 ° C. After dropping, react for 12 hours. Then, CC2 shown by the following structural formula was obtained by refine | purifying the solid substance obtained by removing dichloromethane. The structure of CC2 was confirmed by NMR and IR.

In addition, the following was used as A component and B component.
<A component: Aromatic polyester> Polyester: Polyethylene terephthalate (PET)
Polyethylene terephthalate “TR-8580” manufactured by Teijin Fibers Limited was used. The reduced viscosity was 0.35 dl / g. Table 1 shows the carboxyl group concentration and the stability results against hydrolysis.
<B component: polyester-based thermoplastic elastomer>"Hytrel" (registered trademark) 4057 manufactured by Toray DuPont Co., Ltd.
<Component B: Polyolefin Elastomer> “Thermo Run” (registered trademark) 3550 manufactured by Mitsubishi Chemical Corporation
<Component B: Polystyrene Elastomer> “Lavalon” (registered trademark) MJ5301C manufactured by Mitsubishi Chemical Corporation

[Example 1]
In a nitrogen atmosphere, 88 parts by weight of PET chips as the A component and 11 parts by weight of thermoplastic elastomer and polyester thermoplastic elastomer chips (“Hytrel” (registered trademark) 4057 manufactured by Toray DuPont Co., Ltd.) as the B component And blended in a V-type blender to obtain a blend chip.
Next, this blended chip was supplied from the first supply port of an extruder type melt spinning machine equipped with a nozzle having a hole diameter of 1.5 mm, melt-kneaded while evacuating at a cylinder temperature of 270 ° C. and venting pressure at 13.3 Pa, C 1 part by weight of the component (CC2 obtained by the operation of Production Example 2) is supplied from the second supply port, melt-kneaded and spun at a cylinder temperature of 270 ° C., cooled once, and further stretched 5.7 times at 120 ° C. Next, a relaxation heat setting was performed at 0.9 times to obtain a polyester fiber (monofilament) having a diameter of 0.22 mm and a strength of 3.6 cN / dtex.
When the wear resistance of this monofilament was evaluated, it took 90 minutes to cut (wear resistance = 0.15 mm / h). Generation of isocyanate odor was not felt during melt-kneading and spinning. Moreover, when it melted at 300 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable. The stability evaluation against hydrolysis was excellent. The results are shown in Table 1.

[Example 2]
In Example 1, the same operation was performed except that CC1 obtained in the operation of Production Example 1 was used as the C component. The results are shown in Table 1.

[Example 3]
In Example 1, the same operation was performed except that a polyolefin-based elastomer (“Thermo Run” (registered trademark) 3550 manufactured by Mitsubishi Chemical Corporation) was used as the B component. The results are shown in Table 1.

[Example 4]
In Example 1, the same operation was performed except that a styrene-based thermoplastic elastomer ("Lavalon" (registered trademark) MJ5301C manufactured by Mitsubishi Chemical Corporation) was used as the B component. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, the same operation was performed except that neither the B component nor the C component was used. The results are shown in Table 1.

[Comparative Example 2]
In Example 1, the same operation was carried out except that 99 parts by weight of component A (PET) and 1 part by weight of component C (CC2 obtained by the operation of Reference Example 2) were used. The results are shown in Table 1.

[Comparative Example 3]
In Example 1, it replaced with C component and performed the same operation except having used the carbodiimide (Nisshinbo Co., Ltd. product, "Carbodilite" (trademark) LA-1) which has a linear structure. The results are shown in Table 1.

[Comparative Example 4]
In Example 1, the same operation was performed except that the C component was not used. The results are shown in Table 1.

Claims (19)

  Contains polyester (component A), thermoplastic elastomer (component B), and a compound (component C) having a cyclic structure in which one carbodiimide group has its first nitrogen and second nitrogen bonded by a linking group A polyester composition characterized by comprising:   The polyester composition according to claim 1, wherein the number of atoms forming the cyclic structure of the component C is 8 to 50. The polyester composition according to claim 1 or 2, wherein the cyclic structure of component C is represented by the following formula (1).

(In the formula, Q is a divalent to tetravalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom.) The polyester composition according to claim 3, wherein Q is a divalent to tetravalent linking group represented by the following formula (1-1), (1-2), or (1-3).

(In the formula, Ar ¹ and Ar ² are each independently an aromatic group having 2 to 4 carbon atoms and 5 to 15 carbon atoms. R ¹ and R ² are each independently 1 to 2 carbon atoms having 1 to 4 carbon atoms. 20 aliphatic groups, 2 to 4 valent alicyclic groups having 3 to 20 carbon atoms, or combinations thereof, or these aliphatic groups, alicyclic groups and 2 to 4 valent aromatic carbon atoms having 5 to 15 carbon atoms X ¹ and X ² are each independently a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, a divalent to tetravalent carbon atom having 3 to 20 alicyclic groups, 2 to 4 A valent aromatic group having 5 to 15 carbon atoms, or a combination thereof, s is an integer of 0 to 10. k is an integer of 0 to 10. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ^2. X ³ is a divalent to tetravalent carbon number. An aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 2 to 4 carbon atoms having 3 to 20 carbon atoms, an aromatic group having 2 to 4 carbon atoms having 5 to 15 carbon atoms, or a combination thereof, provided that Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ may contain a hetero atom, and when Q is a divalent linking group, Ar ¹ , Ar ² , R 3 ¹ , R ² , X ¹ , X ² and X ³ are all divalent groups, and when Q is a trivalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ^{One of 2} and X ³ is a trivalent group, and when Q is a tetravalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ One of them is a tetravalent group or two are trivalent groups.) The polyester composition according to claim 3, wherein the compound containing a cyclic structure of component C is represented by the following formula (2).

(In the formula, Qa is a divalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom.) The polyester composition according to claim 5, wherein Qa is a divalent linking group represented by the following formula (2-1), (2-2) or (2-3).

(In the formula, Ara ¹ , Ara ² , Ra ¹ , Ra ² , Xa ¹ , Xa ² , Xa ³ , s and k are Ar ¹ and Ar ^{2 in} formulas (1-1) to (1-3), respectively. , R ¹ , R ² , X ¹ , X ² , X ³ , s and k.) The polyester composition according to claim 3, wherein the compound containing a cyclic structure of component C is represented by the following formula (3).

(In the formula, Qb is a trivalent linking group which is an aliphatic group, an alicyclic group, an aromatic group or a combination thereof, and may contain a hetero atom. Y carries a cyclic structure. Carrier.) The polyester composition according to claim 7, wherein Qb is a trivalent linking group represented by the following formula (3-1), (3-2) or (3-3).

(In the formula, Arb ¹ , Arb ² , Rb ¹ , Rb ² , Xb ¹ , Xb ² , Xb ³ , s and k are respectively Ar ¹ , Ar ² , Formula (1-1) to (1-3), R ¹ , R ² , X ¹ , X ² , X ³ , s and k are the same, provided that one of them is a trivalent group.)   The polyester composition according to claim 7 or 8, wherein Y is a single bond, a double bond, an atom, an atomic group or a polymer. The polyester composition according to claim 3, wherein the compound containing a cyclic structure of component C is represented by the following formula (4).

(In the formula, Qc is a tetravalent linking group which is an aliphatic group, an aromatic group, an alicyclic group, or a combination thereof, and may have a hetero atom. Z ¹ and Z ² are It is a carrier carrying a ring structure.) The polyester composition according to claim 10, wherein Qc is a tetravalent linking group represented by the following formula (4-1), (4-2), or (4-3).

(In the formula, Arc ¹ , Arc ² , Rc ¹ , Rc ² , Xc ¹ , Xc ² , Xc ³ , s and k are respectively Ar ¹ , Ar ^{2 in} formulas (1-1) to (1-3). , R ¹ , R ² , X ¹ , X ² , X ³ , s and k, provided that one of them is a tetravalent group or two are trivalent groups.) The polyester composition according to claim 11, wherein Z ¹ and Z ² are each independently a single bond, a double bond, an atom, an atomic group or a polymer. The polyester (component A) has a main chain mainly composed of repeating units represented by the following formula (II), and at least a part of the ends are sealed with a component C. Polyester composition.

(In the formula, n represents an integer of 2 to 4, Ar represents a 1,4-phenylene group or a 2,6-naphthalenediyl group.)   The polyester composition according to any one of claims 1 to 13, wherein the content of component C is 0.001 to 10 parts by weight per 100 parts by weight of polyester (component A).   The polyester composition in any one of Claims 1-14 in which B component contains a polyester-type elastomer.   The polyester composition according to claim 15, wherein the B component includes a polyester block copolymer of a hard segment composed of an aromatic-containing polyester component and a soft segment composed of a polyether glycol component or an aliphatic polyester component.   The polyester composition in any one of Claims 1-14 in which B component contains the polyolefin-type thermoplastic elastomer which mainly has the blend body of an ethylene-propylene-diene terpolymer and polyolefin.   18. The polyester composition according to claim 17, wherein the B component comprises a styrene-based thermoplastic elastomer made of a block copolymer having polystyrene as a hard segment and polybutadiene, hydrogenated butadiene, or polyisoprene as a soft segment.   A polyester fiber comprising the polyester composition according to claim 1.