JP6059417B2 - Method for producing polyester resin composition - Google Patents

Description

  The present invention relates to a method for producing a polyester resin composition having improved strength, hue and hydrolysis resistance, and having no odor due to a free isocyanate compound, and a resin composition produced by the production method.

  In general, thermoplastic polyesters such as polyethylene terephthalate have excellent mechanical and chemical properties and are widely used as molded articles such as fibers and films. In order to use these in a wide range of applications, it is essential to have advanced physical properties in various mechanical properties represented by strength and impact resistance. To that end, the molecular weight of the polyester is improved. It is necessary to let Usually, the polyester is produced by a melt polycondensation method, but as the molecular weight increases, the melt viscosity becomes higher and it becomes difficult to stir uniformly, and the coloration of the polyester becomes noticeable due to the heat history in the molten state. There were problems such as. Therefore, the high molecular weight polyester is produced by a method of solid phase heating in a temperature range from a temperature lower than the melting point to a temperature higher than the glass transition point (solid phase polymerization). However, polyesters are susceptible to hydrolysis due to the catalytic action of the acidic groups at their ends, and as a result, deterioration of physical properties under superheating conditions such as a fiberizing process and deterioration over time during long-term use have been problems.

  In addition, since petroleum-based general-purpose polymer fibers such as aromatic polyester are made from limited fossil resources such as petroleum, in recent years, not only are there concerns about the remaining reserves of these fossil resources, but they also occur during incineration and disposal. Carbon dioxide is also a big social problem as a cause of global warming. Accordingly, it is a fact that exploration and development of new resources and reduction of the content ratio of petroleum-derived general-purpose polymers in products are urgently required.

  Under such circumstances, polylactic acid synthesized from raw materials derived from plant-derived components has attracted attention. Polylactic acid is a polymer made from lactic acid obtained by fermenting starch or cellulose extracted from plants. Among plant-derived polymers, the balance of mechanical properties, heat resistance, and cost is excellent. Development of resin products, fibers, films, sheets, and the like using this has been performed. However, since the polylactic acid fiber is susceptible to hydrolysis like the above-mentioned polyethylene terephthalate, there is a problem that the product life is short and there is a restriction in application development.

  In order to solve this problem, Patent Document 1 proposes polylactic acid in which hydrolysis resistance is improved by adding a carbodiimide compound or the like. However, when the carbodiimide compound used is used as an end-capping agent for a polymer compound, the compound having an isocyanate group is liberated as the carbodiimide compound binds to the end of polylactic acid, generating a unique odor of the isocyanate compound. However, deteriorating the working environment has been a problem.

  Also, polylactic acid is required to have a high molecular weight in order to improve mechanical properties. However, as in the case of the above-described polyethylene terephthalate, the heat polymerization with time and the resulting coloration are remarkable in melt polymerization. Then, before obtaining the final product using the tin catalyst, the first stage melt polymerization is performed at a temperature lower than the melting point, the polylactic acid is formed into pellets, and the final polymerization is performed by the second stage solid phase polymerization. It proposes a method to make things. However, this method has a problem of productivity because the solid-state polymerization time is as long as 50 hours.

  Patent Document 3 proposes a method of obtaining high molecular weight polylactic acid by adding a carbodiimide compound and then performing melt kneading. However, since this method requires high-temperature heat treatment after the carbodiimide compound is added, there is a problem that the hue of the resulting polylactic acid is deteriorated.

  Patent Documents 4 and 5 propose a method in which a carbodiimide compound is used as a cross-linking agent and only melt kneading is performed after the addition, but this method has a desired high molecular weight due to a short heat treatment time. There was a problem that it was difficult to obtain polylactic acid.

  Furthermore, in the methods of Patent Documents 3 to 5, as in Patent Document 1, the compound having an isocyanate group is liberated with the reaction of the carbodiimide compound and polylactic acid, and a unique odor of the isocyanate compound is generated, thereby reducing the working environment. It was a problem to make it worse.

JP 2009-191411 A Japanese Patent No. 2850776 JP 2006-63111 A JP 2006-77126 A JP 2009-286999 A

  An object of the present invention is to provide a method for producing a polyester resin composition having improved strength, hue, and hydrolysis resistance and free from odor by a free isocyanate compound, and a resin composition produced by the production method. It is in.

  The present inventors have prepared a carbodiimide compound having a structure that does not liberate an isocyanate compound even if it reacts with the terminal of the polyester, and a polyester resin composition containing the carbodiimide compound and having improved strength, hue, and hydrolysis resistance. The method and the resin composition produced by the production method were studied earnestly.

  As a result, the compound having a carbodiimide group in the cyclic structure does not liberate an isocyanate compound even when it reacts with the terminal of the polyester, and the resin composition containing the carbodiimide compound is heated at a temperature below the melting point of the resin composition. It has been found that a polyester resin composition having improved strength, hue, and hydrolysis resistance can be obtained by heating to improve the degree of polymerization of the polyester, thereby completing the present invention.

（式中、Ｑ_ａは、下記式（２−１）、（２−２）または（２−３）で表される２価の結合基である。）

（式中、Ａｒ_ａ ^１およびＡｒ_ａ ^２は各々独立に、２〜４価の炭素数５〜１５の芳香族基である。Ｒ_ａ ^１およびＲ_ａ ^２は各々独立に、２〜４価の炭素数１〜２０の脂肪族基、２〜４価の炭素数３〜２０の脂環族基またはこれらの組み合わせ、またはこれら脂肪族基、脂環族基と２〜４価の炭素数５〜１５の芳香族基の組み合わせである。Ｘ_ａ ^１およびＸ_ａ ^２は各々独立に、２〜４価の炭素数１〜２０の脂肪族基、２〜４価の炭素数３〜２０の脂環族基、２〜４価の炭素数５〜１５の芳香族基、またはこれらの組み合わせである。ｓは０〜１０の整数である。ｋは０〜１０の整数である。なお、ｓまたはｋが２以上であるとき、繰り返し単位としてのＸ_ａ ^１、あるいはＸ_ａ ^２が、他のＸ_ａ ^１、あるいはＸ_ａ ^２と異なっていてもよい。Ｘ_ａ ^３は、２〜４価の炭素数１〜２０の脂肪族基、２〜４価の炭素数３〜２０の脂環族基、２〜４価の炭素数５〜１５の芳香族基、またはこれらの組み合わせである。但し、Ａｒ_ａ ^１、Ａｒ_ａ ^２、Ｒ_ａ ^１、Ｒ_ａ ^２、Ｘ_ａ ^１、Ｘ_ａ ^２およびＸ_ａ ^３は、Ｏ原子、Ｎ原子、Ｓ原子およびＰ原子から選ばれるヘテロ原子を含有していてもよい（但し、ヘテロ原子としてＮ原子を含有する場合には、化合物（Ｂ成分）がポリエステル（Ａ成分）の末端に反応した際にイソシアネート化合物を遊離するものを除く）。

（式中、Ｑ_ｂは、下記式（３−１）、（３−２）または（３−３）で表される３価の結合基である。Ｙは、原子または原子団である（但しポリエステル（Ａ成分）の末端に反応した際にイソシアネート化合物を遊離するものを除く）。

（式中、Ａｒ_ｂ ^１、Ａｒ_ｂ ^２、Ｒ_ｂ ^１、Ｒ_ｂ ^２、Ｘ_ｂ ^１、Ｘ_ｂ ^２、Ｘ_ｂ ^３、ｓおよびｋは、上記に記載の式中のＡｒ_ａ ^１、Ａｒ_ａ ^２、Ｒ_ａ ^１、Ｒ_ａ ^２、Ｘ_ａ ^１、Ｘ_ａ ^２、Ｘ_ａ ^３、ｓおよびｋと同じである。但しこれらの内の一つは３価の基である。）

上記式（４）におけるＱ_ｃは、下記式（４−１）、（４−２）または（４−３）で表される４価の結合基であり、Ｚ^１およびＺ^２は各々独立に、原子または原子団である（但しポリエステル（Ａ成分）の末端に反応した際にイソシアネート化合物を遊離するものを除く）。

（式中、Ａｒ_ｃ ^１、Ａｒ_ｃ ^２、Ｒ_ｃ ^１、Ｒ_ｃ ^２、Ｘ_ｃ ^１、Ｘ_ｃ ^２、Ｘ_ｃ ^３、ｓおよびｋは、上記に記載の式中の、Ａｒ_ａ ^１、Ａｒ_ａ ^２、Ｒ_ａ ^１、Ｒ_ａ ^２、Ｘ_ａ ^１、Ｘ_ａ ^２、Ｘ_ａ ^３、ｓおよびｋと同じである。但し、これらの内の一つが４価の基であるか、二つが３価の基である。） That is, the object of the present invention is to
A resin composition comprising a polyester (component A) and a compound (component B) having a cyclic structure in which one carbodiimide group has a first nitrogen and a second nitrogen bonded by a bonding group A method for producing a polyester resin composition which is heated at a temperature lower than the melting point of the product to improve the degree of polymerization of the polyester (component A), wherein the number of atoms forming the cyclic structure of the component B is 8 to 50 The above compound (component B) is achieved by a method for producing a polyester resin composition represented by the following formula (2), (3) or (4) .

(In the formula, Q _a is a divalent linking group represented by the following formula (2-1), (2-2) or (2-3).)

(In the formula, Ar _a ¹ and Ar _a ² are each independently _a ² to 4 valent aromatic group having 5 to 15 carbon atoms. R _a ¹ and R _a ² are each independently _a ² to 4 valent aromatic group. An aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 2 to 4 carbon atoms and a combination thereof, or an aliphatic group, an alicyclic group and 5 to 4 carbon atoms having 2 to 4 carbon atoms X _a ¹ and X _a ² are each independently _a ² to 4 valent aliphatic group having 1 to 20 carbon atoms and a 2 to 4 valent alicyclic ring having 3 to 20 carbon atoms. Group, a divalent to tetravalent 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, and s or k When X is 2 or more, X _a ¹ or X _a ² as a repeating unit may be different from other X _a ¹ or X _a ² X _a ³ is a 2-4 valent aliphatic group having 1 to 20 carbon atoms, a 2-4 valent alicyclic group having 3-20 carbon atoms, or a 2-4 valent aromatic group having 5-15 carbon atoms. Or a combination thereof, provided that Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² and X _a ³ are an O atom, an N atom, an S atom and a P It may contain a heteroatom selected from atoms (however, when it contains an N atom as a heteroatom, the isocyanate compound is liberated when the compound (component B) reacts with the terminal of the polyester (component A)). Except those that do) .

(Wherein Q _b is a trivalent linking group represented by the following formula (3-1), (3-2) or (3-3). Y is an atom or an atomic group (provided that Excluding those which liberate isocyanate compounds when reacted with the end of the polyester (component A)).

(In the formula, Ar _b ¹ , Ar _b ² , R _b ¹ , R _b ² , X _b ¹ , X _b ² , X _b ³ , s and k are Ar _a ¹ , Ar _{a in} the formula described above, respectively. ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k are the same, provided that one of them is a trivalent group.)

Q _c in the above formula (4) is a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3), and Z ¹ and Z ² are each independently , An atom or an atomic group (excluding those that liberate an isocyanate compound when reacted with the terminal of the polyester (component A)).

(Wherein Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s and k are Ar _a ¹ , Ar in the formulas described above, _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k, provided that one of these is a tetravalent group or two are 3 Valent group.)

  According to the present invention, the end of the polyester can be sealed with the 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, the resin composition containing the carbodiimide compound is heated at a temperature lower than the melting point of the resin composition to improve the degree of polymerization of the polyester, thereby improving the strength, hue, and hydrolysis resistance of the polyester resin composition. You can get things.

  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 B)>
In the present invention, the cyclic carbodiimide compound (component B) 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. For example, when there are a plurality of cyclic structures in the molecule, such as a spiro ring, one cyclic structure bonded to a spiro atom is included in each cyclic structure. Needless to say, the compound may have a plurality of carbodiimide groups as long as it has a carbodiimide group. The number of atoms in the cyclic structure is 8 to 50, more preferably 10 to 30, and still more 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 selected in the range of 10-30, more preferably 10-20.

Cyclic structure, Ru structure der 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 hetero atom and a substituent. In this case, the heteroatom refers to O, N, S, P (however, when an N atom is contained as a heteroatom, the isocyanate is formed when the compound (component B) reacts with the terminal of the polyester (component A)). Except those that liberate compounds). 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.
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. When s and k exceed 10, the cyclic carbodiimide compound is 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.

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

<Cyclic carbodiimide (2)>

In the formula, Q _a 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 (however, an N atom as a hetero atom) In the case where the compound (component B) reacts with the terminal of the polyester (component A), excluding those which liberate an isocyanate compound). 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. Q _a is represented by the following formula (2-1), Ru divalent linking group Der represented by (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.
Preferred examples of the cyclic carbodiimide compound (2) include the following compounds.

<Cyclic carbodiimide (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, Ar _b ¹ , Ar _b ² , R _b ¹ , R _b ² , X _b ¹ , X _b ² , X _b ³ , s and k are respectively represented by the formulas (1-1) to (1-3). The same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k. However, one of these is a trivalent group.
Y is an atom or an atomic group (excluding those that liberate an isocyanate compound when reacted with the terminal of the polyester (component A)). Y is a bonding portion, and a plurality of cyclic structures are bonded via Y to form a structure represented by the formula (3). Preferred examples of the cyclic carbodiimide compound (3) include the following compounds.

<Cyclic carbodiimide (4)>

In the formula, Q _c 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 (however, an N atom as a hetero atom) In the case where the compound (component B) reacts with the terminal of the polyester (component A), excluding those which liberate an isocyanate compound). 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), Q _c is tetravalent. Accordingly, one of these groups is a tetravalent group or two are trivalent groups. Q _c is represented by the following formula (4-1), Ru tetravalent linking group Der represented by (4-2) or (4-3).

Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s and k are each Ar ^{1 in} formulas (1-1) to (1-3). , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k are the same. Provided that Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² and X _c ³ are one of which is a tetravalent group or two of which are trivalent It is a group.
Z ¹ and Z ² are each independently an atom or an atomic group (except for those that liberate an isocyanate compound when reacted with the terminal of the polyester (component A)). 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).
Preferred 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 combining conventionally known methods. 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 the present invention can be produced by modifying and combining the methods described in the following documents.
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。
（上記式中、Ａｒ^１およびＡｒ^２は各々独立に、炭素数１〜６のアルキル基またはフェニル基で置換されていてもよい芳香族基である。Ｅ^１およびＥ^２は各々独立に、ハロゲン原子、トルエンスルホニル基およびメタンスルホニル基、ベンゼンスルホニル基、ｐ−ブロモベンゼンスルホニル基からなる群から選ばれる基である。Ａｒ^ａは、フェニル基である。Ｘは、下記式（ｉ−１）から（ｉ−４）の結合基である。） 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 toluenesulfonyl group, a methanesulfonyl group, a benzenesulfonyl group, and a p-bromobenzenesulfonyl group, Ar ^a is a phenyl group, and X is a group represented by the following formula (i-1): (It is a linking group of (i-4).)

<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 the B 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.

The polyester (component A) is preferably a polyester whose main chain is composed mainly of repeating units 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 B, those obtained by any conventionally known production method can be applied to the present invention.
Among these, from the viewpoint of environmental protection and the like, a polymer containing hydroxycarboxylic acid as a main constituent is preferable, and polylactic acid is particularly preferably used.

  Here, polylactic acid has a main chain mainly composed of lactic acid units represented by the following formula (I), and at least a part of the ends are sealed with a B component. In this specification, “mainly” is preferably a ratio of 90 to 100 mol%, more preferably 95 to 100 mol%, and still more preferably 98 to 100 mol%.

  The lactic acid unit represented by the formula (I) includes an L-lactic acid unit and a D-lactic acid unit which are optical isomers. The main chain of the polylactic acid is preferably mainly an L-lactic acid unit, a D-lactic acid unit or a combination thereof.

The polylactic acid is preferably poly D-lactic acid whose main chain is mainly composed of D-lactic acid units, and poly L-lactic acid whose main chain is mainly composed of L-lactic acid units. The proportion of other units constituting the main chain is preferably in the range of 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 2 mol%.
Examples of other units constituting the main chain include units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples of the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. Or aromatic polyhydric alcohol etc., such as what added ethylene oxide to bisphenol, etc. are mentioned. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid. Examples of the lactone include glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

  The weight average molecular weight of polylactic acid is preferably in the range of 100,000 to 500,000, more preferably 110,000 to 350,000, and still more preferably 120,000 to 250,000 in order to achieve both the mechanical properties and the moldability of the molded product. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

When the polylactic acid (component A) is poly D-lactic acid or poly L-lactic acid and is a homophase polylactic acid, a crystal melting peak (Tmh) between 150 and 190 ° C. is measured by differential scanning calorimetry (DSC) measurement. ) And the crystal melting heat (ΔHmsc) is preferably 10 J / g or more. Heat resistance can be improved by satisfying the range of the crystal melting point and the crystal melting heat.
The main chain of polylactic acid is preferably stereocomplex polylactic acid including a stereocomplex phase formed by poly L-lactic acid units and poly D-lactic acid units. Stereocomplex polylactic acid preferably exhibits a crystal melting peak of 190 ° C. or higher by differential scanning calorimetry (DSC) measurement.

The stereocomplex polylactic acid preferably has a stereocomplex crystallinity (S) defined by the following formula (i) of 90 to 100%.
S = [ΔHms / (ΔHmh + ΔHms)] × 100 (i)
(However, ΔHms represents the crystal melting enthalpy of stereocomplex phase polylactic acid, and ΔHmh represents the melting enthalpy of polylactic acid homophase crystal.)

The stereocomplex polylactic acid preferably has crystallinity, and the stereocomplex crystallization rate (Sc) defined by the following formula (ii) is determined according to the intensity ratio of diffraction peaks by wide-angle X-ray diffraction (XRD) measurement. Is more preferably 50% or more.
Sc (%) = [ΣI _SCi / (ΣI _SCi + I _HM )] × 100 (ii)
(Where ΣI _SCi = I _SC1 + I _SC2 + I _SC3 and I _SCi (i = 1 to 3) are the integrated intensities of diffraction peaks around 2θ = 12.0 °, 20.7 °, and 24.0 °, respectively. I _HM represents the integrated intensity IHM of a diffraction peak derived from a homophase crystal appearing in the vicinity of 2θ = 16.5 °.

  The stereocomplex crystallization ratio (Sc) is preferably selected in the range of 50 to 100%, more preferably 60 to 95%, and particularly preferably 65 to 90%. That is, when the polylactic acid has Sc in the above range, the heat resistance and moisture heat resistance of the molded product can be more suitably satisfied.

  The crystallinity of stereocomplex polylactic acid, particularly the crystallinity by XRD measurement, is preferably at least 5%, more preferably 5 to 60%, even more preferably 7 to 50%, particularly preferably 10 to 45%. is there.

  The crystalline melting point of stereocomplex polylactic acid is preferably 190 to 250 ° C, more preferably 200 to 230 ° C. The crystal melting enthalpy by DSC measurement of stereocomplex polylactic acid is preferably 20 J / g or more, more preferably 20 to 80 J / g, still more preferably 30 to 80 J / g. When the crystalline melting point of stereocomplex polylactic acid is less than 190 ° C., the heat resistance is deteriorated. Moreover, when it exceeds 250 degreeC, it will be necessary to shape | mold at the high temperature of 250 degreeC or more, and it may become difficult to suppress thermal decomposition of resin.

  In the stereocomplex polylactic acid, the weight ratio of poly D-lactic acid to poly L-lactic acid is preferably 90/10 to 10/90. More preferably, it is in the range of 80/20 to 20/80, more preferably 30/70 to 70/30, particularly preferably 40/60 to 60/40, and theoretically preferably as close to 1/1 as possible. .

  The weight average molecular weight of the stereocomplex polylactic acid is preferably in the range of 100,000 to 500,000, more preferably 110,000 to 350,000, and even more preferably 120,000 to 250,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

  Poly L-lactic acid and poly D-lactic acid can be produced by a conventionally known method. For example, it can be produced by ring-opening polymerization of L- or D-lactide in the presence of a metal-containing catalyst. In addition, low molecular weight polylactic acid containing a metal-containing catalyst is crystallized as desired or without crystallization, under reduced pressure or from normal pressure, in the presence of an inert gas stream, or absent It can also be produced by solid phase polymerization. Furthermore, it can be produced by a direct polymerization method in which lactic acid is subjected to dehydration condensation in the presence or absence of an organic solvent.

The polymerization reaction can be carried out in a conventionally known reaction vessel. For example, in a ring-opening polymerization or direct polymerization method, a vertical reactor or a horizontal reactor equipped with a stirring blade for high viscosity, such as a helical ribbon blade, is used alone, or Can be used in parallel. Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.

  Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid, such as decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, ethylene glycol, trimethylolpropane, pentaerythritol, etc. Can be suitably used. It can be said that the polylactic acid prepolymer used in the solid-phase polymerization method is preferably crystallized in advance from the viewpoint of preventing resin pellet fusion. The prepolymer is in a solid state in a fixed vertical or horizontal reaction vessel, or in a reaction vessel (such as a rotary kiln) in which the vessel itself rotates, such as a tumbler or kiln, in the temperature range from the glass transition temperature of the prepolymer to less than the melting point. Polymerized.

  Metal-containing catalysts include alkali metals, alkaline earth metals, rare earths, transition metals, fatty acid salts such as aluminum, germanium, tin, antimony, titanium, carbonates, sulfates, phosphates, oxides, hydroxides , Halides, alcoholates and the like. Among them, fatty acid salts, carbonates, sulfates, phosphates, oxides, hydroxides containing at least one metal selected from tin, aluminum, zinc, calcium, titanium, germanium, manganese, magnesium and rare earth elements Products, halides, and alcoholates are preferred.

  Tin compounds due to low catalytic activity and side reactions, specifically stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, tin myristate, tin octylate Tin-containing compounds such as tin stearate and tetraphenyltin are exemplified as preferred catalysts. Among these, tin (II) compounds, specifically, diethoxytin, dinonyloxytin, tin (II) myristate, tin (II) octylate, tin (II) stearate, tin (II) chloride and the like are suitable. Illustrated.

The amount of the catalyst used is 0.42 × 10 ^{−4 to} 100 × 10 ⁻⁴ (mole) per 1 kg of lactide, and 1.68 × 10 ^{−4 in} consideration of reactivity, color tone and stability of the resulting polylactides. To 42.1 × 10 ⁻⁴ (mol), particularly preferably 2.53 × 10 ^{−4 to} 16.8 × 10 ⁻⁴ (mol).

The metal-containing catalyst used for the polymerization of polylactic acid is preferably deactivated with a conventionally known deactivator prior to using polylactic acid. Examples of such a deactivator include an organic ligand having a group of chelate ligands having an imino group and capable of coordinating with a polymerized metal catalyst. Also, dihydridooxoline (I) acid, dihydridotetraoxodiphosphorus (II, II) acid, hydridotrioxoline (III) acid, dihydridopentaoxodiphosphoric acid (III), hydridopentaoxodi (II, IV) Acid, dodecaoxohexaphosphoric acid (III), hydridooctaoxotriphosphoric acid (III, IV, IV) acid, octaoxotriphosphoric acid (IV, III, IV) acid, hydridohexaoxodiphosphoric acid (III, V) acid, hexaoxodiacid Examples thereof include low oxidation number phosphoric acids having an acid number of 5 or less, such as phosphorus (IV) acid, decaoxotetraphosphoric (IV) acid, hendecaoxotetraphosphoric (IV) acid, and eneoxooxophosphorus (V, IV, IV) acid. Further, orthophosphoric acid represented by the formula xH ₂ O · yP ₂ O ₅ and x / y = 3 may be mentioned. Moreover, polyphosphoric acid which is 2> x / y> 1, and is called diphosphoric acid, triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid or the like based on the degree of condensation, and a mixture thereof can be mentioned. Moreover, the metaphosphoric acid represented by x / y = 1, especially trimetaphosphoric acid and tetrametaphosphoric acid are mentioned. Further, ultraphosphoric acid represented by 1> x / y> 0 and having a network structure in which a part of the phosphorus pentoxide structure is partially removed (these may be collectively referred to as a metaphosphoric acid compound) may be mentioned. . Moreover, the acid salt of these acids is mentioned. Moreover, the monovalent | monohydric and polyhydric alcohol of these acids, the partial ester of polyalkylene glycol, and complete ester are mentioned. Examples thereof include phosphono-substituted lower aliphatic carboxylic acid derivatives of these acids.

In view of the catalyst deactivation ability, orthophosphoric acid represented by the formula xH ₂ O · yP ₂ O ₅ and x / y = 3 is preferred. Moreover, 2> x / y> 1, and polyphosphoric acid referred to as diphosphoric acid, triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid and the like, and a mixture thereof are preferable from the degree of condensation. Further, metaphosphoric acid represented by x / y = 1, particularly trimetaphosphoric acid and tetrametaphosphoric acid are preferable. Ultraphosphoric acid represented by 1> x / y> 0 and having a network structure in which a part of the phosphorus pentoxide structure is left (these may be collectively referred to as a metaphosphoric acid compound) is preferable. Moreover, the acidic salt of these acids is preferable. Further, monovalent or polyhydric alcohols of these acids or partial esters of polyalkylene glycols are preferred.

  The metaphosphoric acid compound used in the present invention is a cyclic metaphosphoric acid in which about 3 to 200 phosphoric acid units are condensed, an ultra-region metaphosphoric acid having a three-dimensional network structure, or an alkali metal salt or an alkaline earth metal salt thereof. Onium salts). Among them, cyclic sodium metaphosphate, ultra-region sodium metaphosphate, phosphono-substituted lower aliphatic carboxylic acid derivative dihexylphosphonoethyl acetate (hereinafter sometimes abbreviated as DHPA) and the like are preferably used.

  The polylactic acid preferably has a lactide content of 1 to 5000 ppm by weight. The lactide contained in the polylactic acid deteriorates the resin and deteriorates the color tone at the time of melt processing, and in some cases, it may be disabled as a product.

  Poly L-lactic acid and / or poly D-lactic acid immediately after melt ring-opening polymerization usually contains 1 to 5% by weight of lactide, but poly L-lactic acid and / or poly D-lactic acid is At any stage up to lactic acid molding, a conventionally known lactide weight loss method, that is, vacuum devolatilization with a single-screw or multi-screw extruder, or high vacuum treatment in a polymerization apparatus is carried out alone or in combination. In addition, lactide can be reduced to a suitable range.

  The smaller the lactide content, the better the melt stability and heat-and-moisture resistance of the resin, but there is also the advantage of lowering the resin melt viscosity, making it reasonable and economical to meet the desired purpose. is there. In other words, it is reasonable to set it to 1 to 1000 ppm by weight where practical melt stability is achieved. More preferably, a range of 1 to 700 ppm by weight, more preferably 2 to 500 ppm by weight, particularly preferably 5 to 100 ppm by weight is selected. By having a lactide content in such a range, the polylactic acid component improves the stability of the resin during the melt molding of the molded product of the present invention, and the advantage that the molded product can be efficiently manufactured and the heat-and-moisture stability of the molded product. , Low gas can be improved.

  The stereocomplex polylactic acid is prepared by bringing poly L-lactic acid and poly D-lactic acid into contact in a weight ratio of 10/90 to 90/10, preferably by melt contact, and more preferably melt kneading. Can be obtained. The contact temperature is preferably in the range of 220 to 290 ° C, more preferably 220 to 280 ° C, and even more preferably 225 to 275 ° C, from the viewpoint of improving the stability of polylactic acid when melted and the stereocomplex crystallinity.

  The method of melt kneading is not particularly limited, but a conventionally known batch type or continuous type melt mixing apparatus is preferably used. For example, melt-stirred tanks, single- and twin-screw extruders, kneaders, non-shaft vertical stirrers (finishers), Vivolac manufactured by Sumitomo Heavy Industries, Ltd., N-SCR manufactured by Mitsubishi Heavy Industries, Ltd., Hitachi, Ltd. Glass-made blades, lattice blades or Kenix type stirrers manufactured by Seisakusho, or Sulzer-type SMLX type static mixer equipped pipe type polymerization equipment can be used, but it is a self-cleaning type polymerization equipment in terms of productivity, quality of polylactic acid, especially color tone. A certain non-shaft vertical stirring tank, N-SCR, twin-screw extruder, etc. are preferably used.

The resin composition of the present invention contains an end-capped polyester (component A) having a structure in which a cyclic carbodiimide compound of component B 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 resin composition of the present invention can be produced by mixing polyester and a cyclic carbodiimide compound (component B). The cyclic carbodiimide compound reacts with the terminal of the polyester to seal the terminal. Excess cyclic carbodiimide compound remains in the resin composition unreacted.

  Therefore, the resin composition of the present invention contains polyester (A component) whose end is sealed and a cyclic carbodiimide compound (B component). Further, depending on the degree of reaction of terminal modification, a polyester whose terminal is not sealed may be contained.

  The content of the cyclic carbodiimide compound (component B) remaining unreacted in the resin composition is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight per 100 parts by weight of the polyester (component A). More preferably, it is 0.1 to 1 part by weight.

<Method for producing resin composition>
In the present invention, the resin composition obtained by mixing the polyester (component A) and the cyclic carbodiimide compound (component B) is heated at a temperature below the melting point of the resin composition, and the degree of polymerization of the polyester (component A) is increased. A polyester resin composition is manufactured by improving. A preferable temperature is higher than the glass transition point of the polyester (A) component and lower than the melting point. If it is above the glass transition point, the degree of polymerization is improved satisfactorily. When the melting point is exceeded, the polyester resin composition is in a molten state, so that the melt viscosity becomes too high as the molecular weight increases, and a composition having a high degree of polymerization cannot be obtained.

  When polylactic acid is employed as the polyester (component A), after mixing poly-L-lactic acid, poly-D-lactic acid as the component A and cyclic carbodiimide compound as the component B to form stereocomplex polylactic acid. The degree of polymerization of polylactic acid can be improved by heating at a temperature below the melting point. Further, after mixing poly L-lactic acid and poly D-lactic acid to form stereocomplex polylactic acid (component A), after mixing with cyclic carbodiimide compound (component B), heating at a temperature below the melting point, polymerization The degree can also be improved.

  The method of adding and mixing the cyclic carbodiimide compound to the polyester is not particularly limited, and a method of adding as a solution, a melt or a master batch of the polyester to be applied, or a cyclic carbodiimide is dissolved, dispersed or melted by a conventionally known method. For example, a polyester solid may be brought into contact with the liquid and the cyclic carbodiimide may be infiltrated.

  When taking the method of adding as a solution, a melt, or a master batch of the polyester to be applied, 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 mixing time with the polymer compound is not particularly specified, and depends on the mixing apparatus and the mixing temperature, but is selected from 0.1 minute 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 the solvent, for example, hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, halogen solvents, amide solvents 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 the polyester and the 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 taking a method in which a solid of a polyester is brought into contact with a liquid in which the cyclic carbodiimide is dissolved, dispersed or melted and the cyclic carbodiimide is infiltrated, a method of bringing the solid polyester into contact with a carbodiimide dissolved in a solvent as described above, or carbodiimide A method of bringing solid polylactic acid into contact with the emulsion liquid can be employed. As a method of contacting, a method of immersing polyester, a method of applying to polyester, a method of spraying, etc. can be suitably employed.

  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. . Although the polyester is more likely to react at a melting temperature, it is preferably reacted 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, more preferably 0.01 to 0.1 part by weight with respect to 100 parts by weight of the total of polylactic acid and cyclic carbodiimide. 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 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.

  In the present invention, the heat treatment method in the solid phase of the resin composition containing the polyester (A component) and the cyclic carbodiimide compound (B component) obtained by the above method is not particularly limited, and a conventionally known method can be used.

  When carrying out the heat treatment in the solid phase, the shape of the polyester resin composition containing the cyclic carbodiimide compound is not particularly limited, and any shape such as a lump, film, pellet, and powder may be used. From the viewpoint of efficiently improving the degree of polymerization in the heat treatment in, it is preferable to use pellets or powder. Examples of a method for forming pellets include a method in which a polyester resin composition containing a cyclic carbodiimide compound is melted, extruded into a strand, and pelletized with a strand cutter. Moreover, as a method of making into powder, the method of grind | pulverizing using grinders, such as a mixer, a blender, a ball mill, and a hammer mill, is mentioned.

  The method for performing the heat treatment step in the solid phase is not particularly limited, and may be a batch method or a continuous method. The reaction vessel is a stirred tank reactor, a mixer reactor, or a column reactor. These reactors can be used in combination of two or more.

  When carrying out this heat treatment step, it is preferable that the polyester resin composition containing the cyclic carbodiimide compound is crystallized. The method for crystallization is not particularly limited, and a known method can be used. For example, a method of holding at a crystallization temperature in a gas phase or a liquid phase, a method of volatilizing a solvent from a polyester resin composition containing a cyclic carbodiimide compound, and a polyester resin composition containing a cyclic carbodiimide compound are melted and stretched Alternatively, a method of cooling and solidifying while performing a shearing operation is exemplified, and from the viewpoint that the operation is simple, a method of holding at a crystallization temperature in a gas phase or a liquid phase is preferable.

  The crystallization temperature here is not particularly limited as long as it is higher than the glass transition temperature and lower than the melting point, but it is a temperature rising crystallization temperature measured in advance by a differential scanning calorimeter (DSC). It is more preferable that the temperature falls within the range of the cooling crystallization temperature. When crystallizing, any of reduced pressure, normal pressure, and increased pressure may be used. Further, the time for crystallization is not particularly limited.

  The temperature condition for carrying out this heat treatment step is not particularly limited as long as the degree of polymerization is improved as long as it is less than the melting point of the polyester resin composition containing the cyclic carbodiimide compound. If the glass transition temperature or higher, the degree of polymerization is improved without any problem. Moreover, in order to shorten heat processing time, you may raise temperature in steps with progress of reaction.

  Moreover, when implementing this heat processing process, it is preferable to carry out in inert gas stream, such as a vacuum or dry nitrogen. In particular, when the polyester (component A) is polylactic acid, heat treatment is preferably performed under vacuum for the purpose of removing residual monomers contained in the polylactic acid.

  The steps of adding and mixing the above-described cyclic carbodiimide compound to the polyester, and the step of heating the polyester resin composition containing the cyclic carbodiimide compound at a temperature below its melting point to improve the polymerization degree are carried out continuously. In addition, each step may be performed batchwise.

  About the various physical properties of the resin composition obtained by the manufacturing method of this invention, the preferable range is as follows. In particular, when the polyester (component A) is any of poly D-lactic acid, poly L-lactic acid, and stereocomplex polylactic acid, the reduced viscosity is preferably in the range of 1.5 to 3.0. Similarly, the weight average molecular weight is preferably 150,000 to 350,000.

  The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene. If the reduced viscosity and the weight average molecular weight are smaller than this, it is not preferable because desired physical properties may not be exhibited in various applications. The color (YI value) of the 1.5 wt% solution of each sample (solvent: chloroform in the case of poly D-lactic acid and poly L-lactic acid, and chloroform containing 5 vol% hexafluoroisopropanol in the case of stereocomplex polylactic acid) is It is preferable that it is 7 or less. When the color (YI value) is larger than this, the appearance of the molded product, particularly the hue, is deteriorated in various applications, and the application development is limited. Further, the carboxyl terminal concentration is preferably 15 eq / ton or less. When the carboxyl terminal concentration is higher than this, deterioration with time due to hydrolysis becomes remarkable, and the life and reliability of the product are lowered, which is not preferable.

<Stabilizer>
The resin composition obtained by the production method 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, 2-ethylhexyl-cyano-3,3'-diphenyl acrylate, and the like.

  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 polylactic acid (component A).

<Crystallization accelerator>
The resin composition obtained by the production method 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 organic carboxylic acid metal 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 resin composition obtained by the production method 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 obtained by the production method 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, with respect to 100 parts by weight of the polyester (component A). Preferably it is 1-30 weight part, Most preferably, it is 1-20 weight part.

<Release agent>
The resin composition obtained by the production method of the present invention can contain a release agent. As the mold release agent used in the present invention, those used for ordinary thermoplastic resins can be used.

  Specific examples of release agents include fatty acids, fatty acid metal salts, oxy fatty acids, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid partial saponified esters, fatty acid lower alcohol esters, fatty acid polyvalents. Examples include alcohol esters, fatty acid polyglycol esters, and modified silicones. By blending these, a polylactic acid molded product excellent in mechanical properties, moldability, and heat resistance can be obtained.

  Fatty acids having 6 to 40 carbon atoms are preferred. Specifically, oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montan Examples thereof include acids and mixtures thereof. The fatty acid metal salt is preferably an alkali metal salt or alkaline earth metal salt of a fatty acid having 6 to 40 carbon atoms, and specific examples include calcium stearate, sodium montanate, calcium montanate, and the like.

  Examples of the oxy fatty acid include 1,2-oxysteric acid. Paraffin having 18 or more carbon atoms is preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like.

  As the low molecular weight polyolefin, for example, those having a molecular weight of 5000 or less are preferable, and specific examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidized type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Fatty acid amides having 6 or more carbon atoms are preferred, and specific examples include oleic acid amide, erucic acid amide, and behenic acid amide.

  The alkylene bis fatty acid amide is preferably one having 6 or more carbon atoms, and specifically includes methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2-hydroxyethyl) stearic acid amide and the like. As the aliphatic ketone, those having 6 or more carbon atoms are preferable, and examples thereof include higher aliphatic ketones.

  Examples of the fatty acid partial saponified ester include a montanic acid partial saponified ester. Examples of the fatty acid lower alcohol ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidonic acid ester, montanic acid ester, isostearic acid ester and the like.

  Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol Examples include tall monostearate, pentaerythritol adipate stearate, sorbitan monobehenate and the like. Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters and polypropylene glycol fatty acid esters.

  Examples of the modified silicone include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.

  Of these, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferred. Of these, montanic acid ester, montanic acid partial saponified ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferred, and particularly, montanic acid partial saponified ester and ethylene bisstearic acid amide are preferred. preferable.

  A mold release agent may be used by 1 type and may be used in combination of 2 or more type. The content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, with respect to 100 parts by weight of the polyester.

<Antistatic agent>
The resin composition obtained by the production method of the present invention can contain an antistatic agent. Examples of the antistatic agent include (β-lauramidopropionyl) trimethylammonium sulfate, quaternary ammonium salts such as 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 resin composition obtained by the production method 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, and bis (2-ethylhexyl) azelate 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.

<Impact resistance improver>
The resin composition obtained by the production method of the present invention can contain an impact resistance improver. The impact resistance improver is one that can be used to improve the impact resistance of a thermoplastic resin, and is not particularly limited. For example, at least one selected from the following impact resistance improvers can be used.

  Specific examples of impact modifiers include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers and their Alkali metal salts (so-called ionomers), ethylene-glycidyl (meth) acrylate copolymers, ethylene-acrylate copolymers (for example, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers), modified ethylene -Propylene copolymer, diene rubber (eg polybutadiene, polyisoprene, polychloroprene), diene and vinyl copolymer (eg styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer) Coalescence, styrene Soprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene graft copolymerized with styrene, butadiene-acrylonitrile copolymer), polyisobutylene, isobutylene and butadiene Or a copolymer with isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber and the like can be mentioned.

In addition, those having various cross-linking degrees, various micro structures such as those having a cis structure, a trans structure, etc., a core layer and one or more shell layers covering the core layer, and adjacent layers are composed of heterogeneous polymers. A so-called core-shell type multi-layered polymer can also be used.
Furthermore, the various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers, block copolymers and the like, and can be used as the impact resistance improver of the present invention.
The impact resistance improver is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, and still more preferably 10 to 20 parts by weight with respect to 100 parts by weight of the polyester (component A).

<Others>
Further, the resin composition obtained by the production method of the present invention contains a thermosetting resin such as a phenol resin, a melamine resin, a thermosetting polyester resin, a silicone resin, and an epoxy resin within a range not departing from the spirit of the present invention. May be. Further, the resin composition of the present invention may contain a flame retardant such as bromine, phosphorus, silicone, antimony compound and the like within a range not departing from the spirit of the present invention. Colorants containing organic and inorganic dyes and pigments, for example, oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as bitumen, and chromium such as zinc chromate Contains acid salts, sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine, phosphates such as manganese violet, carbon such as carbon black, metal colorants such as bronze powder and aluminum powder, etc. You may let them. Also, nitroso type such as naphthol green B, nitro type such as naphthol yellow S, azo type such as naphthol red and chromophthal yellow, phthalocyanine type such as phthalocyanine blue and fast sky blue, and condensed polycyclic coloring such as indanthrone blue An additive such as a slidability improver such as a graphite or fluorine resin may be added. These additives can be used alone or in combination of two or more.

<Molded product>
The resin composition obtained by the production method of the present invention can be molded by injection molding, extrusion molding, vacuum, pressure molding, blow molding or the like. Examples of the molded article include pellets, fibers, fabrics, fiber structures, films, sheets, and sheet nonwoven fabrics.

  The pellet made of the resin composition obtained by the production method of the present invention is not limited in its melt molding method, and those produced by a known pellet production method can be suitably used. That is, the resin composition placed in the form of a strand or plate is cut in the air or in water after the resin is completely solidified or not completely solidified and still in a molten state. These methods are conventionally known, but any of them can be suitably applied in the present invention.

  Examples of the molded product include various housings, electric / electronic parts such as gears and gears, building members, civil engineering members, agricultural materials, automobile parts (interior parts, exterior parts, etc.), and daily parts.

For the fiber and fiber structure comprising the resin composition obtained by the production method of the present invention, materials obtained by ordinary melt spinning and subsequent post-processing can be preferably used.
That is, the resin composition obtained by the production method of the present invention was melted by an extruder type or pressure melter type melt extruder, then weighed by a gear pump, filtered in a pack, and then provided on the die. It is discharged from the nozzle as monofilament, multifilament, etc.

  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 winding speed is not particularly limited, but when the polyester (A) component is stereocomplex polylactic acid, a range of 300 m / min to 5,000 m / min is preferable because a stereocomplex crystal is easily formed.

  From the viewpoint of stretchability, a winding speed at which the stereocomplex crystallization ratio (Sc) of the undrawn yarn is 0% is preferable. The undrawn yarn that has been wound is then subjected to a drawing step, but the spinning step and the drawing step do not necessarily need to be separated, and even if a direct spinning drawing method is used in which the drawing is continued without being wound once after spinning. I do not care.

  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. For example, if the polyester (component A) is polylactic acid, the stretching temperature is selected from the glass transition temperature (Tg) to 170 ° C., preferably 70 ° C. to 140 ° C., particularly preferably 80 to 130 ° C.

  Further, when the polyester (component A) is stereocomplex polylactic acid, it has a high stereocomplex crystallization rate (Sc) and low heat shrinkability by being heat-set at 170 ° C. to 220 ° C. under tension after stretching. In addition, a polylactic acid fiber having a strength of 3.5 cN / dTex or more can be obtained.

  The fiber obtained from the resin composition obtained by the production method of 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, knitted fabric, nonwoven fabric, felt, outer clothing 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 fiber and fiber structure comprising the resin composition obtained by the production method of the present invention may be used alone or in combination 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.

  The resin composition obtained by the production method of the present invention can be formed into a film or sheet by a conventionally known method. For example, in a film or sheet, a molding technique such as extrusion molding or cast molding can be used. That is, an unstretched film is extruded using an extruder or the like equipped with a T die, a circular die or the like, and further stretched and heat-treated to form. At this time, the unstretched film can be used as it is as a sheet. In forming the film, a material obtained by melt-kneading the resin composition and the above-described various components in advance can be used, or it can be formed through melt-kneading during extrusion molding. When extruding an unstretched film, an unstretched film with few surface defects can be obtained by blending an electrostatic adhesive such as a sulfonic acid quaternary phosphonium salt into the molten resin.

  Moreover, an unstretched film can also be cast-molded by melt | dissolving, casting, and drying and solidifying a resin composition and an additive component using solvents, such as chloroform and a methylene dichloride, for example.

  Unstretched film can be uniaxially stretched longitudinally in the direction of mechanical flow and transversely uniaxially stretched in the direction perpendicular to the direction of mechanical flow. A biaxially stretched film can be produced by stretching by a biaxial stretching method using a method such as tubular stretching. Further, the film is usually subjected to a heat setting treatment after stretching in order to suppress heat shrinkability and the like. The stretched film thus obtained can be subjected to surface activation treatment such as plasma treatment, amine treatment, and corona treatment by a conventionally known method if desired.

  The film and sheet obtained by the production method of the present invention can be used in combination with other types of films and sheets other than a single form. Examples of mixed use include various combinations with films and sheets made of other types of materials, such as lamination and lamination, and combinations with other types of forms such as injection molded articles and fiber structures.

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

(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer:
The weight average molecular weight and number average molecular weight of the polymer were measured by gel permeation chromatography (GPC) and converted to standard polystyrene. GPC measuring instrument is detector; differential refractometer (manufactured by Shimadzu Corporation) RID-6A column; Toso-Co., Ltd. TSKgel G3000HXL, TSKgel G4000HXL, TSKgel G5000HXL and TSKguardcocumHXL-L TSKgel G2000HXL, TSKgelG3000HXL, and TSKguardcocumHXL-L connected in series were used.
Chloroform was used as an eluent, 10 μl of a sample having a concentration of 1 mg / ml (chloroform containing 1% hexafluoroisopropanol) was injected at a temperature of 40 ° C. and a flow rate of 1.0 ml / min.

(2) Carboxyl group concentration:
The sample was dissolved in purified o-cresol under a nitrogen stream, and titrated with an ethanol solution of 0.05 N potassium hydroxide using bromocresol blue as an indicator.

(3) DSC measurement of stereocomplex crystallinity [S (%)], crystal melting temperature, etc .:
Using DSC (TA Instrument, TA-2920), the sample was heated to 250 ° C. at 10 ° C./min under a nitrogen stream in the first cycle, and the glass transition temperature (Tg), stereocomplex phase poly Lactic acid crystal melting temperature (Tm *), stereocomplex phase polylactic acid crystal melting enthalpy (ΔHms) and homophase polylactic acid crystal melting enthalpy (ΔHmh) were measured.
In addition, the crystallization start temperature (Tc *) and the crystallization temperature (Tc) were measured by rapidly cooling the measurement sample and then performing a second cycle measurement under the same conditions. The stereocomplex crystallinity is a value obtained by the following formula (ii) from the stereocomplex phase and homophase polylactic acid crystal melting enthalpy obtained by the above measurement.
S = [ΔHms / (ΔHmh + ΔHms)] × 100 (ii)
(However, ΔHms is the melting enthalpy of complex phase crystals, ΔHmh is the melting enthalpy of homophase polylactic acid crystals)

(4) Identification of cyclic carbodiimide structure by NMR and determination of cyclic carbodiimide in polyester composition:
The synthesized cyclic carbodiimide compound was confirmed by ¹ H-NMR and ¹³ C-NMR. For NMR, JNR-EX270 manufactured by JEOL Ltd. was used. Deuterated chloroform was used as the solvent.

(5) Identification of carbodiimide skeleton of cyclic carbodiimide by IR:
The presence or absence of the carbodiimide skeleton of the synthesized cyclic carbodiimide compound was confirmed by FT-IR at 2100-2200 cm ⁻¹ characteristic of carbodiimide. For FT-IR, Magna-750 manufactured by Thermo Nicolay Co., Ltd. was used.

(6) Measurement of reduced viscosity:
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. Viscosity retention was determined as the reduced viscosity after sample treatment for the molecule and the reduced viscosity before sample treatment for the denominator.

(7) Existence of isocyanate odor:
In aromatic polyester composition, when the sample is melted at 300 ° C. for 5 minutes, in aliphatic polyester, when the sample is melted at 260 ° C. for 5 minutes, whether or not the measurer feels an isocyanate odor by sensory evaluation Judged by. When the isocyanate odor was not felt, it was judged to be acceptable.

(8) Good working environment:
Judgment was made based on whether the working environment was deteriorated by the isocyanate odor during the production of the resin composition. When it did not deteriorate, it was evaluated as good.

(9) 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.
(10) Color (YI value):
The PLLA sample is chloroform, and the stereocomplex polylactic acid sample composed of PLLA and PDLA is dissolved in chloroform containing 5 vol% hexafluoroisopropanol so that the concentration of each material is 1.5 wt%. The YI value was determined by measurement.

The following agents were produced and used as the cyclic carbodiimide compound.
<Production Example 1> Cyclic carbodiimide CC2 (MW = 516):
o- nitrophenol (0.11 mol) and pentaerythrityl tetra bromide (0.025 mol), potassium carbonate (0.33mol), _N, N ₂ N- dimethylformamide 200ml in reactor installed with a stirrer and a heating device After charging in an atmosphere and reacting at 130 ° C. for 12 hours, 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 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 of the following structure was obtained by refine | purifying the solid substance obtained by removing dichloromethane. The structure of CC2 was confirmed by NMR and IR.

[Production Example 2] (Production of poly-D-lactic acid)
To 100 parts by weight of D-lactide (manufactured by Musashino Chemical Laboratory, Inc., 100% optical purity), 0.005 part by weight of tin octylate was added, and the reactor was stirred at 180 ° C. with a stirring blade in a nitrogen atmosphere. After reacting for 2 hours, phosphoric acid equivalent to 1.2 times the amount of tin octylate was added, and then the remaining lactide was removed at 13.3 kPa to obtain chips to obtain poly-D-lactic acid.
The resulting poly-D-lactic acid had a weight average molecular weight of 170,000, a glass transition point (Tg) of 63 ° C., and a melting point of 180 ° C.

[Example 1]
50 parts by weight of each of poly D-lactic acid and poly L-lactic acid (reduced viscosity = 1.52, Mw = 130,000, manufactured by Nature Works) obtained in Production Example 2, and a phosphate ester metal salt (phosphoric acid 2,2-phosphate) Methylene bis (4,6-di-tert-butylphenol) sodium salt, average particle size 5 μm, 0.1 part by weight of “ADEKA STAB” NA-11) manufactured by ADEKA Corporation was melt-kneaded at 230 ° C., and the strand was taken in a water bath. A stereocomplex polylactic acid chip was obtained by chipping with a chip cutter. The obtained stereocomplex polylactic acid resin had an Mw of 125,000, a melting point (Tm) of 217 ° C., and a stereocomplex crystallinity of 100%.

The stereocomplex polylactic acid resin obtained here and the cyclic carbodiimide compound (CC2) were each dried, then mixed so as to have a weight ratio of 98.8: 1.2, melt-kneaded at a cylinder temperature of 230 ° C., The strand was extruded into a water tank and chipped with a chip cutter to obtain a CC2-added stereocomplex polylactic acid resin composition. The obtained stereocomplex polylactic acid resin composition had an Mw of 140,000, a melting point (Tm) of 217 ° C., and a stereocomplex crystallinity of 100%.
The chip thus obtained was further held for 5 hours under the conditions of 180 ° C. and 33.3 Pa (0.25 Torr). During the production of the composition, the working environment was well maintained without feeling an isocyanate odor. Moreover, when it melted at 260 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable. The physical properties of this composition are shown in Table 1. About this composition, when isocyanate gas generation amount was confirmed by GC / MS, isocyanate gas was not detected.

[Example 2]
The poly D-lactic acid chip obtained in Production Example 2 and the cyclic carbodiimide compound (CC2) were each dried, then mixed to a weight ratio of 99: 1, melt-kneaded at a cylinder temperature of 230 ° C., and then in a water bath. A strand was extruded into a chip using a chip cutter to obtain a CC2-added poly D-lactic acid resin composition.
The chip thus obtained was further held for 5 hours under conditions of 150 ° C. and 33.3 Pa (0.25 Torr). During the production of the composition, the working environment was well maintained without feeling an isocyanate odor. Moreover, when it melted at 260 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable. The physical properties of this composition are shown in Table 1. About this composition, when isocyanate gas generation amount was confirmed by GC / MS, isocyanate gas was not detected.

[Example 3]
Poly L-lactic acid (reduced viscosity = 1.52, Mw = 130,000, manufactured by Nature Works) and the cyclic carbodiimide compound (CC2) were each dried and then mixed so that the weight ratio was 98.8: 1.2. Then, the mixture was melt-kneaded at a cylinder temperature of 230 ° C., extruded into a water tank, and chipped with a chip cutter to obtain a CC2-added poly L-lactic acid resin composition.
The chip thus obtained was further held for 5 hours under conditions of 150 ° C. and 33.3 Pa (0.25 Torr). During the production of the composition, the working environment was well maintained without feeling an isocyanate odor. Moreover, when it melted at 260 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable. The physical properties of this composition are shown in Table 1. About this composition, when isocyanate gas generation amount was confirmed by GC / MS, isocyanate gas was not detected.

[Comparative Example 1]
50 parts by weight of each of poly D-lactic acid and poly L-lactic acid (manufactured by Nature Works) obtained in Production Example 2, and a phosphoric acid ester metal salt (2,2-methylenebis (4,6-di-tert-butylphenol phosphate) ) Sodium salt, average particle size 5 μm, “ADEKA STAB” NA-11 manufactured by ADEKA Corporation) 0.1 part by weight was melt-kneaded at 230 ° C., strands were taken in a water tank, and chip-converted into a stereo complex polylactic acid. I got a chip. The obtained stereocomplex polylactic acid resin had an Mw of 125,000, a melting point (Tm) of 217 ° C., and a stereocomplex crystallinity of 100%.
The chip thus obtained was further held for 5 hours under the conditions of 180 ° C. and 33.3 Pa (0.25 Torr). During the production of the composition, the working environment was well maintained without feeling an isocyanate odor. Moreover, when it melted at 260 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable. The physical properties of the obtained composition are shown in Table 1. About this composition, when isocyanate gas generation amount was confirmed by GC / MS, isocyanate gas was not detected.

[Comparative Example 2]
50 parts by weight of each of poly D-lactic acid and poly L-lactic acid (manufactured by Nature Works) obtained in Production Example 2, and a phosphoric acid ester metal salt (2,2-methylenebis (4,6-di-tert-butylphenol phosphate) ) Sodium salt, average particle size 5 μm, “ADEKA STAB” NA-11 manufactured by ADEKA Corporation) 0.1 part by weight was melt-kneaded at 230 ° C., strands were taken in a water tank, and chip-converted into a stereo complex polylactic acid. I got a chip. The obtained stereocomplex polylactic acid resin had an Mw of 125,000, a melting point (Tm) of 217 ° C., and a stereocomplex crystallinity of 100%.
The stereocomplex polylactic acid resin and the cyclic carbodiimide compound (CC2) obtained here were each dried and then mixed so as to have a weight ratio of 98.8: 1.2, and a segment mixer (laboratory manufactured by Toyo Seiki Co., Ltd.). CC2 addition stereocomplex polylactic acid resin composition was obtained by kneading in a molten state at 230 ° C. for 1 hour using Plastomyl KF-15V). Mw of the obtained stereocomplex polylactic acid resin composition was 13,000, and the stereocomplex crystallinity was 100%.
During the production of the composition, the working environment was well maintained without feeling an isocyanate odor. Moreover, when it melted at 260 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable. The physical properties of this composition are shown in Table 1. About this composition, when isocyanate gas generation amount was confirmed by GC / MS, isocyanate gas was not detected.

[Comparative Example 3]
A Sb-I-added stereocomplex polylactic acid resin composition was obtained in the same manner as in Example 1, except that the carbodiimide compound was changed to linear carbodiimide Sb-I ("STABAXOL" I manufactured by Rhein Chemie Japan Co., Ltd.). It was. The resulting composition had a strong isocyanate odor during production and required installation of an exhaust device. Moreover, when it melted at 260 ° C. for 5 minutes, the isocyanate odor evaluation was unacceptable. The physical properties of this composition are shown in Table 1.

[Comparative Example 4]
A poly-L-lactic acid (manufactured by Nature Works reduced viscosity = 1.52, Mw = 130,000) chip was further maintained at 150 ° C. and 33.3 Pa (0.25 Torr) for 5 hours. During the production of the composition, the working environment was well maintained without feeling an isocyanate odor. Moreover, when it melted at 260 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable. The physical properties of the obtained composition are shown in Table 1. About this composition, when isocyanate gas generation amount was confirmed by GC / MS, isocyanate gas was not detected.

  According to the present invention, there are provided a method for producing a polyester resin composition having improved strength, hue, and hydrolysis resistance and free from odor by a free isocyanate compound, and a resin composition produced by the production method. Can do.

Claims (8)

A resin composition comprising a polyester (component A) and a compound (component B) having a cyclic structure in which one carbodiimide group has a first nitrogen and a second nitrogen bonded by a bonding group A method for producing a polyester resin composition which is heated at a temperature lower than the melting point of the product to improve the degree of polymerization of the polyester (component A), wherein the number of atoms forming the cyclic structure of the component B is 8 to 50 The compound (component B) is a method for producing a polyester resin composition represented by the following formula (2), (3) or (4).

(In the formula, Q _a is a divalent linking group represented by the following formula (2-1), (2-2) or (2-3).)

(In the formula, Ar _a ¹ and Ar _a ² are each independently _a ² to 4 valent aromatic group having 5 to 15 carbon atoms. R _a ¹ and R _a ² are each independently _a ² to 4 valent aromatic group. An aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 2 to 4 carbon atoms and a combination thereof, or an aliphatic group, an alicyclic group and 5 to 4 carbon atoms having 2 to 4 carbon atoms X _a ¹ and X _a ² are each independently _a ² to 4 valent aliphatic group having 1 to 20 carbon atoms and a 2 to 4 valent alicyclic ring having 3 to 20 carbon atoms. Group, a divalent to tetravalent 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, and s or k When X is 2 or more, X _a ¹ or X _a ² as a repeating unit may be different from other X _a ¹ or X _a ² X _a ³ is a 2-4 valent aliphatic group having 1 to 20 carbon atoms, a 2-4 valent alicyclic group having 3-20 carbon atoms, or a 2-4 valent aromatic group having 5-15 carbon atoms. Or a combination thereof, provided that Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² and X _a ³ are an O atom, an N atom, an S atom and a P It may contain a heteroatom selected from atoms (however, when it contains an N atom as a heteroatom, the isocyanate compound is liberated when the compound (component B) reacts with the terminal of the polyester (component A)). Except what you do ).

(Wherein Q _b is a trivalent linking group represented by the following formula (3-1), (3-2) or (3-3). Y is an atom or an atomic group (provided that Excluding those which liberate isocyanate compounds when reacted with the end of the polyester (component A)).

(In the formula, Ar _b ¹ , Ar _b ² , R _b ¹ , R _b ² , X _b ¹ , X _b ² , X _b ³ , s and k are Ar _a ¹ , Ar _{a in} the formula described above, respectively. ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k are the same, provided that one of them is a trivalent group.)

Q _c in the above formula (4) is a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3), and Z ¹ and Z ² are each independently , An atom or an atomic group (excluding those that liberate an isocyanate compound when reacted with the terminal of the polyester (component A)).

(Wherein Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s and k are Ar _a ¹ , Ar in the formulas described above, _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k, provided that one of these is a tetravalent group or two are 3 Valent group.) 2. The polyester resin composition according to claim 1, wherein the polyester (component A) has a main chain mainly composed of lactic acid units represented by the following formula (I), and at least part of the ends are sealed with the component B. Method.

  The method for producing a polyester resin composition according to claim 2, wherein the main chain of the polyester (component A) is mainly L-lactic acid units, D-lactic acid units, or a combination thereof.   The method for producing a polyester resin composition according to claim 2, wherein the polyester (component A) includes a stereocomplex phase formed by poly L-lactic acid and poly D-lactic acid. 2. The polyester resin composition according to claim 1, wherein 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 the component B. Method.

(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 method for producing a polyester resin composition according to claim 1, wherein the content of component B is 0.001 to 10 parts by weight per 100 parts by weight of polyester (component A).   The manufacturing method of the polyester resin composition of Claim 2 which shows the crystal melting peak of 190 degreeC or more by a differential scanning calorimeter (DSC) measurement. The method for producing a polyester resin composition according to claim 4 , wherein the stereocomplex crystallinity (S) defined by the following formula (i) is 90 to 100%.
S = [ΔHms / (ΔHmh + ΔHms)] × 100 (i)
(However, ΔHms represents the crystal melting enthalpy of stereocomplex phase polylactic acid, and ΔHmh represents the melting enthalpy of polylactic acid homophase crystal.)