JP5437753B2 - Resin composition containing stereocomplex polylactic acid and method for producing the same - Google Patents

Description

  The present invention relates to a resin composition having improved heat and heat resistance and a molded article comprising the resin composition. More specifically, the present invention relates to a resin composition containing stereocomplex polylactic acid having improved heat and heat resistance and a method for producing the same.

  In recent years, for the purpose of protecting the global environment, biodegradable polymers that are decomposed in a natural environment have attracted attention and are being studied all over the world. As biodegradable polymers, aliphatic polyesters such as polylactic acid, polyhydroxybutyrate and polycaprolactone are known. Since polylactic acid uses lactic acid obtained from a raw material derived from a living body or a derivative thereof as a raw material, it is a high-safety and environmentally friendly polymer material. Therefore, the use as a general-purpose polymer is examined, and the use as a stretched film, a fiber, an injection molded product, etc. is examined.

  However, polylactic acid has a melting point of about 170 ° C. and is not sufficient for use as a general-purpose resin. Furthermore, since it is easily decomposed by moisture at a high temperature, there is a problem that the melt viscosity is greatly reduced in the molten state, and so-called wet heat resistance is poor in the solid state.

  On the other hand, poly L-lactic acid (hereinafter sometimes abbreviated as PLLA) composed of L-lactic acid units and poly D-lactic acid (hereinafter sometimes abbreviated as PDLA) composed of D-lactic acid units are in solution or in a molten state. It is known that stereocomplex polylactic acid is formed by mixing in (see, for example, Patent Document 1, Non-Patent Document 1, etc.). This stereocomplex polylactic acid has a crystal melting temperature of 200 to 230 ° C., a higher melting point than PLLA and PDLA, and an interesting phenomenon showing high crystallinity has been discovered. Further, a polylactic acid unit having an L-lactic acid unit of 90 mol% or more and 100 mol% or less and a polylactic acid unit having a D-lactic acid unit of 90 mol% or more and 100 mol% or less are mixed and subjected to heat treatment at 250 ° C. or more. A simple production method for obtaining stereocomplex polylactic acid has been proposed (see, for example, Patent Documents 2 and 3).

  However, stereocomplex polylactic acid, like polylactic acid homopolymer, is a characteristic of aliphatic polyester, and is easily hydrolyzed by moisture. To improve the wet heat stability of polylactic acid, carboxyl end groups are blocked with carbodiimide compounds. Improvement of moisture and heat resistance stability has been proposed (see, for example, Patent Documents 4 and 5), and some results have been observed. The carbodiimide compound used in this proposal is a linear carbodiimide compound. When a linear carbodiimide compound is used as a terminal group blocking agent for a polymer compound, a compound having an isocyanate group is released along with a reaction in which the linear carbodiimide compound is bonded to the terminal group of polylactic acid, generating a unique odor of the isocyanate compound. However, deteriorating the working environment has become a problem, and this problem remains unsolved.

JP 63-24014 A Japanese Patent Laid-Open No. 2006-036808 JP 2006-265486 A Japanese Patent No. 3440915 Japanese Patent No. 3776578

Macromolecules, 24, 5651 (1991).

An object of the present invention is to provide a resin composition containing a high-melting point stereocomplex polylactic acid, which has excellent wet heat stability and does not generate a free isocyanate compound odor.
Another object of the present invention is to provide a method for producing the resin composition.
Still another object of the present invention is to provide a molded article comprising the resin composition.

The present inventors diligently studied a carbodiimide compound having a structure that does not liberate an isocyanate compound even when it reacts with an end group of polylactic acid.
As a result, it was found that a compound having a carbodiimide group in the cyclic structure (hereinafter sometimes abbreviated as a cyclic carbodiimide compound) does not liberate an isocyanate compound even when reacted with a terminal group of polylactic acid. Was completed.

式中、Ｑは、下記式（１−１）、（１−２）または（１−３）で表される２〜４価の結
合基である。

（式中、Ａｒ^１およびＡｒ^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^１およびＲ^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^１およびＸ^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^１、あるいはＸ^２が、他のＸ^１、あるいはＸ^２と異なっていてもよい。Ｘ^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^１、Ａｒ
^２、Ｒ^１、Ｒ^２、Ｘ^１、Ｘ^２およびＸ^３はヘテロ原子を含有していてもよい、また、Ｑが
２価の結合基であるときは、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、Ｘ^１、Ｘ^２およびＸ^３は全て
２価の基である。Ｑが３価の結合基であるときは、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、Ｘ^１、
Ｘ^２およびＸ^３の内の一つが３価の基である。Ｑが４価の結合基であるときは、Ａｒ^１、
Ａｒ^２、Ｒ^１、Ｒ^２、Ｘ^１、Ｘ^２およびＸ^３の内の一つが４価の基であるか、二つが３価
の基である。）
また本発明の他の目的は、該組成物よりなる成形品により達成される。 That is, the object of the present invention is to
(A) Polylactic acid units A and L (B) in which L-lactic acid units are 90 mol% or more and 99 mol% or less
D-lactic acid unit is composed of polylactic acid unit B having 90 mol% or more and 99 mol% or less,
The weight ratio of (A) to (B) is in the range of 10:90 to 90:10, the weight average molecular weight is 50,000 to 500,000, and in the differential scanning calorimeter (DSC) measurement, Among the melting peaks, the stereocomplex polylactic acid having a melting peak ratio of 200% or more at 80 ° C. or more, and (C) one carbodiimide group, and the first nitrogen and the second nitrogen are bonded by a bonding group. Containing a cyclic carbodiimide compound (C component) having a cyclic structure and represented by the following formula (1) and having 8 to 30 atoms to form the cyclic structure ,
This is achieved by a resin composition that is 0.001 to 10 parts by weight of a cyclic carbodiimide compound (component C) per 100 parts by weight of stereocomplex polylactic acid.

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

(In the formula, Ar ¹ and Ar ² are each independently an aromatic group having 2 to 4 carbon atoms and 5 to 15 carbon atoms. R ¹ and R ² are each independently 1 to 2 carbon atoms having 1 to 4 carbon atoms. 20 aliphatic groups, 2 to 4 valent alicyclic groups having 3 to 20 carbon atoms, or combinations thereof, or these aliphatic groups, alicyclic groups and 2
A combination of a tetravalent aromatic group having 5 to 15 carbon atoms. X ¹ and X ² are each independently
2 to 4 valent aliphatic group having 1 to 20 carbon atoms, 2 to 4 valent aliphatic group having 3 to 20 carbon atoms, 2 to 4 valent aromatic group having 5 to 15 carbon atoms, or a combination thereof It is. s is an integer of 0-10. k is an integer of 0-10. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ² . X ³ is a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, a divalent to tetravalent alicyclic group having 3 to 20 carbon atoms, or 2 to 4
A C5-C15 aromatic group, or a combination thereof. However, 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, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ ,
One of X ² and X ³ is a trivalent group. When Q is a tetravalent linking group, Ar ¹ ,
One of Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ is a tetravalent group, or two are trivalent groups. )
Another object of the present invention is achieved by a molded article comprising the composition.

Furthermore, a further object of the present invention is to
(A) The L-lactic acid unit is 90 mol% or more and 99 mol% or less, the D-lactic acid unit and / or the copolymer component unit other than lactic acid is 1 mol% or more and 10 mol% or less, and the melting point is 140 to 180. Crystalline polymer A,
(B) The D-lactic acid unit is 90 mol% or more and 99 mol% or less, the L-lactic acid unit and / or the copolymer component unit other than lactic acid is 1 mol% or more and 10 mol% or less, and the melting point is 140 to 180. Composed of crystalline polymer B at
Stereocomplex polylactic acid obtained by heat treatment at 245 to 300 ° C. in a weight ratio of (A) to (B) in the range of 10:90 to 90:10;
(C) a carbodiimide group one having its first nitrogen and second nitrogen and is including a cyclic structure linked by linking group, cyclic carbodiimide compound described above and (C component),
Is achieved by a method for producing a resin composition in which an amount of C component corresponding to 0.5 to 100 equivalents of a carbodiimide group is mixed per equivalent of carboxyl end groups of stereocomplex polylactic acid .

  According to the present invention, end groups of polylactic acid can be sealed with a carbodiimide compound without liberating an isocyanate compound. As a result, the generation of malodor due to the isocyanate compound can be suppressed and the working environment can be improved.

  In addition, when the end group of polylactic acid is sealed with a cyclic carbodiimide compound, an isocyanate group is formed at the end of polylactic acid, and the reaction of the isocyanate group makes it possible to increase the molecular weight of polylactic acid. The cyclic carbodiimide compound also has an action of capturing a free monomer in polylactic acid and other compounds having an acidic group. Furthermore, according to the present invention, the cyclic carbodiimide compound has an advantage that the end group can be sealed 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 reaction mechanism of terminal group blocking is as described below.
When a linear carbodiimide compound (general formula: R ₁ —N═C═N—R ₂ ) is used as a terminal blocker for polylactic acid having a carboxyl end group, the reaction is represented by the following formula. .
In the formula, X is a main chain of polylactic acid. When the linear carbodiimide compound reacts with a carboxyl end group, an amide group is formed at the end of polylactic acid, and an isocyanate compound (R ₁ NCO) is released.

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

  According to the production method of the present invention, the resin composition can be obtained. The molded product of the present invention is excellent in heat distortion resistance, and can be used for applications related to high heat resistance products.

Hereinafter, the present invention will be described in detail.
<Resin composition>
(Stereo complex polylactic acid)
The resin composition of the present invention contains stereocomplex polylactic acid composed of polylactic acid unit A and polylactic acid unit B. The polylactic acid unit A and the polylactic acid unit B are mainly composed of an L-lactic acid unit or a D-lactic acid unit represented by the following formula.

  The polylactic acid unit A is mainly composed of L-lactic acid units. A D-lactic acid unit and / or a copolymer component unit other than lactic acid may be included. The L-lactic acid unit is 90 mol% or more and 99 mol% or less. Preferably they are 91 mol% or more and 98 mol% or less, More preferably, they are 94 mol% or more and 98 mol% or less. The D-lactic acid unit and / or the copolymer component unit other than lactic acid is 1 mol% or more and 10 mol% or less. Preferably they are 2 mol% or more and 9 mol% or less, More preferably, they are 2 mol% or more and 6 mol% or less.

  The polylactic acid unit B is composed of a D-lactic acid unit, an L-lactic acid unit and / or a copolymer component unit other than lactic acid. The D-lactic acid unit is 90 mol% or more and 99 mol% or less. Preferably they are 91 mol% or more and 98 mol% or less, More preferably, they are 94 mol% or more and 98 mol% or less. The L-lactic acid unit and / or the copolymer component unit other than lactic acid is 1 mol% or more and 10 mol% or less. Preferably they are 2 mol% or more and 9 mol% or less, More preferably, they are 2 mol% or more and 6 mol% or less.

  The copolymer component unit in the polylactic acid unit (A) and the polylactic acid unit (B) is a unit derived from a dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid, lactone or the like having a functional group capable of forming two or more ester bonds. Units derived from various polyesters, various polyethers, various polycarbonates and the like comprising these various components can be used alone or in combination.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples of polyhydric alcohols 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 hydroxybutylcarboxylic acid. Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

  As the stereocomplex polylactic acid, those having various end group cappings on the end groups may be used. Examples of such end group blocking groups include acetyl groups, ester groups, ether groups, amide groups, urethane groups, and the like.

  Stereocomplex polylactic acid may contain a catalyst involved in the polymerization within a range that does not impair the thermal stability of the resin composition. As such a catalyst, various tin compounds, titanium compounds, calcium compounds, organic acids, inorganic acids, and the like can be raised, and at the same time, a stabilizer that inactivates them may coexist.

  The weight ratio of the polylactic acid unit A to the polylactic acid unit B is 10:90 to 90:10. It is preferable that it is 25: 75-75: 25, More preferably, it is 40: 60-60: 40. Particularly preferred is 50:50.

  The molar ratio of the L-lactic acid unit and the D-lactic acid unit in the stereocomplex polylactic acid can be arbitrarily set in the range of 20:80 to 80:20, preferably 25:75 to 75:25. More preferably, it is 40:60 to 60:40. If the ratio is within this range, a high-melting-point stereocomplex polylactic acid can be produced, but the crystallinity of the stereocomplex polylactic acid is impaired as the ratio deviates from 50:50.

  The molecular weight and molecular weight distribution of the stereocomplex polylactic acid are not particularly limited as long as they can be substantially molded, but the weight average molecular weight is 50,000 to 500,000. More preferably, it is 70,000 to 300,000. The weight average molecular weight is a weight average molecular weight value in terms of standard polystyrene as measured by gel permeation chromatography (GPC) using chloroform as an eluent.

  In the resin composition of the present invention, only two melting peaks at a low temperature (140 to 180 ° C.) and a high temperature (200 ° C. or higher) or only a melting peak at a high temperature in the temperature rising process of the differential scanning calorimeter (DSC) measurement. Is observed. In the resin composition of the present invention, the ratio of the melting peak at 200 ° C. or higher in the temperature rising process of DSC measurement is 80% or higher, preferably 90% or higher, more preferably 95% or higher, and most preferably 100%. This melting peak is derived from stereocomplex polylactic acid.

  The melting point of the high temperature melting peak is in the range of 200 to 250 ° C, more preferably in the range of 200 to 230 ° C. The melting enthalpy per weight of the stereocomplex polylactic acid having a melting peak of 200 ° C. or higher is preferably 25 J or higher, more preferably 30 J or higher. It is especially preferable that it is 40J or more.

(Cyclic carbodiimide compound (component C))
In the present invention, the cyclic carbodiimide compound (C component) has a cyclic structure. The cyclic carbodiimide compound may have a plurality of cyclic structures.
The cyclic structure has one carbodiimide group (—N═C═N—), and the first nitrogen and the second nitrogen are bonded by a bonding group. One cyclic structure has only one carbodiimide group. Atoms in the cyclic structure is 8-3 0, preferably from 10 to 30, more preferably 10 to 20, particularly preferably 10 to 15.

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

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

Wherein binding Gomoto (Q) is represented by the following formula (1-1), Ru divalent to tetravalent linking group Der represented by (1-2) or (1-3).

式中、Ａｒ^１およびＡｒ^２は各々独立に、それぞれヘテロ原子ならびに置換基を含んでいてもよい、２〜４価の炭素数５〜１５の芳香族基である。

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.

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

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

<Cyclic carbodiimide (3)>

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

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

<Cyclic carbodiimide (4)>

In the formula, Qc is a tetravalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may have a hetero atom. Z ¹ and Z ² are carriers that support a cyclic structure. Z ¹ and Z ² may be bonded to each other to form a cyclic structure.

  The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (4), Qc is tetravalent. Accordingly, one of these groups is a tetravalent group or two are trivalent groups. Qc is preferably a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3).

Arc ¹ , Arc ² , Rc ¹ , Rc ² , Xc ¹ , Xc ² , Xc ³ , s and k are respectively Ar ¹ , Ar ² , R ¹ , Same as R ² , X ¹ , X ² , X ³ , s and k. However, Arc ¹ , Arc ² , Rc ¹ , Rc ² , Xc ¹ , Xc ² and Xc ³ are either a tetravalent group or two are trivalent groups.

Z ¹ and Z ² are preferably each independently a single bond, a double bond, an atom, an atomic group or a polymer. Z ¹ and Z ² are bonding portions, and a plurality of cyclic structures are bonded via Z ¹ and Z ² to form a structure represented by the formula (4).
Examples of the cyclic carbodiimide compound (4) include the following compounds.

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

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

  Depending on the compound to be produced, an appropriate production method may be employed. For example, (1) nitrophenol represented by the following formula (a-1), nitrophenol represented by the following formula (a-2), and A step of reacting a compound represented by the following formula (b) to obtain a nitro compound represented by the following formula (c);

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

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

(4) After the obtained triphenylphosphine body is isocyanated in the reaction system and then directly decarboxylated, it can be suitably used as the cyclic carbodiimide compound used in the present invention.
(In the above formula, Ar ¹ and Ar ² are each independently an aromatic group optionally substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group. E ¹ and E ² are each independently a halogen atom. A group selected from the group consisting of an atom, a toluenesulfonyloxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy group, Ar ^a is a phenyl group, X is represented by the following formula (i -1) to (i-3).

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

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

  The resin composition of the present invention is an ordinary additive other than the cyclic carbodiimide compound of the present invention, for example, a plasticizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a heat, and the like, within a range not impairing the object of the present invention. Contains one or more stabilizers, lubricants, mold release agents, antistatic agents, flame retardants, foaming agents, fillers, antibacterial and antifungal agents, nucleating agents, dyes, and coloring agents including pigments. be able to.

  In addition, at least one or more of other thermoplastic resins, thermosetting resins, soft thermoplastic resins, and the like can be further added to the resin composition as long as the object of the present invention is not impaired.

<Method for producing resin composition>
The resin composition of the present invention is obtained by mixing stereocomplex polylactic acid and cyclic carbodiimide compound obtained by coexisting crystalline polymer A and crystalline polymer B in a predetermined weight ratio and heat-treating at 245 to 300 ° C. Can be manufactured.

(Crystalline polymer A)
Crystalline polymer A is mainly composed of L-lactic acid units. A D-lactic acid unit and / or a copolymer component unit other than lactic acid may be included. The L-lactic acid unit is 90 mol% or more and 99 mol% or less. Preferably they are 91 mol% or more and 98 mol% or less, More preferably, they are 94 mol% or more and 98 mol% or less. The D-lactic acid unit and / or the copolymer component unit other than lactic acid is 1 mol% or more and 10 mol% or less. Preferably they are 2 mol% or more and 9 mol% or less, More preferably, they are 2 mol% or more and 6 mol% or less.

  Copolymerization component units other than lactic acid are the above-mentioned units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, etc. having two or more functional groups capable of forming an ester bond, and various polyesters composed of these various components. Units derived from various polyethers, various polycarbonates and the like can be used alone or in combination.

  The melting point of the crystalline polymer A is 140 to 180 ° C, preferably 150 to 176 ° C. The weight average molecular weight of the crystalline polymer A is preferably 50,000 to 500,000, more preferably 70,000 to 300,000, and still more preferably 100,000 to 250,000.

(Crystalline polymer B)
Crystalline polymer B is mainly composed of D-lactic acid units. L-lactic acid units and / or copolymerization component units other than lactic acid may be included. The D-lactic acid unit is 90 mol% or more and 99 mol% or less. Preferably they are 91 mol% or more and 98 mol% or less, More preferably, they are 94 mol% or more and 98 mol% or less. The L-lactic acid unit and / or the copolymer component unit other than lactic acid is 1 mol% or more and 10 mol% or less. Preferably they are 2 mol% or more and 9 mol% or less, More preferably, they are 2 mol% or more and 6 mol% or less.

  Copolymerization component units other than lactic acid are the above-mentioned units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, etc. having two or more functional groups capable of forming an ester bond, and various polyesters composed of these various components. Units derived from various polyethers, various polycarbonates and the like can be used alone or in combination.

  The melting point of the crystalline polymer B is 140 to 180 ° C, preferably 150 to 176 ° C. The weight average molecular weight of the crystalline polymer B is 50,000 to 500,000. Preferably it is 70,000-300,000, More preferably, it is 100,000-250,000. If it is this range, when it becomes a resin composition, since a high melting point crystal | crystallization is formed and also the crystallinity degree becomes high, it is preferable.

  The crystalline polymer A and the crystalline polymer B may contain a catalyst involved in polymerization as long as the thermal stability of the resin is not impaired. As such a catalyst, various tin compounds, titanium compounds, calcium compounds, organic acids, inorganic acids, and the like can be raised, and at the same time, a stabilizer that inactivates them may coexist.

  Crystalline polymer A and crystalline polymer B can be produced by any known polylactic acid polymerization method, such as ring-opening polymerization of lactide, dehydration condensation of lactic acid, and a method combining these with solid phase polymerization. Can be manufactured.

(Stereo complex polylactic acid)
The stereocomplex polylactic acid in the present invention can be obtained by heat-treating the above-mentioned crystalline polymer A and the above-mentioned crystalline polymer B in the range of the above ratio at 245 to 300 ° C. The ratio of the crystalline polymer A and the crystalline polymer B is 10:90 to 90:10 by weight ratio, preferably 25:75 to 75:25, more preferably 40:60 to 60: 40. On the other hand, if the weight ratio is less than 10 or more than 90, homocrystallization is prioritized and it is difficult to form a stereocomplex crystal.

  In the heat treatment, it is preferable to mix the crystalline polymer A and the crystalline polymer B. The mixing can be any method as long as they are uniformly mixed when heat-treated. Examples of such a method include a method in which crystalline polymer A and crystalline polymer B are mixed in the presence of a solvent and then reprecipitated to obtain a mixture, and a method in which the solvent is removed by heating to obtain a mixture. it can. In this case, a solution in which crystalline polymer A and crystalline polymer B are separately dissolved in a solvent is prepared and mixed, or both crystalline polymer A and crystalline polymer B are dissolved in a solvent and mixed together. It is preferable to do so.

  The solvent is not particularly limited as long as the crystalline polymer A and the crystalline polymer B are soluble. For example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol or the like alone or in combination of two or more are preferred.

  Even if a solvent is present, the solvent evaporates by heating, and heat treatment can be performed in a solvent-free state. The rate of temperature increase after evaporation of the solvent (heat treatment) is preferably, but not limited to, a short time since there is a possibility of decomposition when heat treatment is performed for a long time.

  Moreover, in this invention, it can carry out by mixing the crystalline polymer A and the crystalline polymer B in absence of a solvent. That is, a method in which a predetermined amount of crystalline polymer A and crystalline polymer B previously powdered or chipped are mixed and then melted, or after melting, kneaded and mixed, either crystalline polymer A or B It is possible to employ a method in which one remaining after melting is added and kneaded and mixed.

Here, in the above, the size of the powder or chip is not particularly limited as long as the powder or chip of the crystalline polymer A and the crystalline polymer B are uniformly mixed, but is preferably 3 mm or less. Is preferably 1 to 0.25 mm in size. When melting and mixing, a stereocomplex crystal is formed regardless of the size, but when the powder or chip is simply melted after being uniformly mixed, if the size of the powder or chip exceeds 3 mm, A homocrystal is also precipitated, which is not preferable.
In the present invention, the size of the powder or chip refers to the dimension of the portion giving the largest dimension among the dimensions of the powder or chip.

  In the production method of the present invention, as a mixing apparatus used for mixing the crystalline polymer A and the crystalline polymer B, a reactor equipped with a batch type stirring blade when mixed by melting, a continuous reactor In addition, in the case of mixing with a biaxial or uniaxial extruder or powder, a tumbler type powder mixer, a continuous type powder mixer, various milling devices, and the like can be suitably used.

  The heat treatment in the production method of the present invention means that the crystalline polymer A and the crystalline polymer B coexist in the above weight ratio and are maintained in a temperature range of 245 ° C to 300 ° C. The temperature of the heat treatment is preferably 250 to 280 ° C. If it exceeds 300 ° C., it is difficult to suppress the decomposition reaction, which is not preferable. The heat treatment time is not particularly limited, but is 0.2 to 60 minutes, preferably 1 to 20 minutes. As the atmosphere during the heat treatment, any of an atmospheric pressure (atmospheric pressure) air atmosphere, an inert atmosphere, or a reduced pressure can be applied.

  In the production method of the present invention, the apparatus and method used for the heat treatment can be any apparatus and method that can be heated while adjusting the atmosphere. For example, a batch reactor, a continuous reactor, two A method of processing while molding using a shaft or a single-screw extruder, a press machine, or a flow tube type extruder can be employed.

<Method for producing composition>
(Cyclic carbodiimide compound)
The application amount of the cyclic carbodiimide compound to be mixed with the stereocomplex polylactic acid is selected such that the carbodiimide group contained in the cyclic carbodiimide compound is 0.5 to 100 equivalents per equivalent of the acidic group of the stereocomplex polylactic acid. 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. Although that Ru is preferably in the range of 0.5 to 5 equivalents.

  The timing for adding and mixing the cyclic carbodiimide compound to the polylactic acid is not particularly limited, and may be separately mixed with the crystalline polymer A and the crystalline polymer B before the heat treatment, or the crystalline polymer A and the crystalline polymer B may be mixed. They may be mixed at the time of mixing or may be mixed with the stereocomplex polylactic acid obtained after the heat treatment, but are preferably mixed at the same time when the crystalline polymer A and the crystalline polymer B are mixed. The method for adding and mixing the cyclic carbodiimide compound to polylactic acid is not particularly limited, and a method of adding as a master batch of solution, melt or polylactic acid, or cyclic carbodiimide is dissolved, dispersed or melted by a conventionally known method. For example, a method may be used in which a solid of a stereocomplex polylactic acid is brought into contact with a liquid so that cyclic carbodiimide is permeated.

  When taking the method of adding as a master batch of solution, melt, or stereocomplex polylactic acid, it can add using a conventionally well-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 it is 0.1 to 2 hours, preferably 0.2 to 60 minutes, more preferably 1 to 30 minutes. Selected.

  As a solvent, what is inactive with respect to stereocomplex polylactic acid and a cyclic carbodiimide compound can be used. In particular, a solvent having affinity for both and dissolving both or at least partially dissolving both is preferable.

  As the solvent, for example, a hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, a halogen solvent, an amide solvent or the like can be used alone or as a mixed solvent if desired. From the viewpoint, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol, or a mixture of two or more of them is preferable.

  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 stereocomplex polylactic acid 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 adopting a method in which a solid of a stereocomplex polylactic acid is brought into contact with a liquid in which a cyclic carbodiimide compound is dissolved, dispersed or melted and the cyclic carbodiimide compound is infiltrated, solid stereo is added to the cyclic carbodiimide compound dissolved in a solvent as described above. A method of contacting the complex polylactic acid, a method of contacting a solid stereocomplex polylactic acid with an emulsion solution of a cyclic carbodiimide compound, or the like can be employed. As the contact method, a method of immersing stereocomplex polylactic acid, a method of applying to stereocomplex polylactic acid, a method of spraying, and the like 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. . Stereocomplex polylactic acid is more likely to react at a melting temperature, but 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 stereocomplex polylactic acid and increase the stirring efficiency.

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

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

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

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

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

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

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

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

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

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

  Examples of the aromatic benzoate compounds include alkylphenyl salicylates such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate.

  Examples of oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, and 2-ethoxy-3′-. Examples include dodecyl oxalic acid bisanilide.

  Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3'-diphenyl acrylate, 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 Condensation product of 6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethanol Etc. Stable Ingredient Te present invention smell may be used in combination of two or more kinds may be used by one kind. As the stabilizer component, a hindered phenol compound and / or a benzotriazole compound are preferable. The content of the stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of the stereocomplex polylactic acid.

<Crystallization accelerator>
The resin composition of the present invention can contain an organic or inorganic crystallization accelerator. By containing the crystallization accelerator, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.

  That is, by applying the crystallization accelerator, moldability and crystallinity are improved, and a molded product that is sufficiently crystallized even in normal injection molding and excellent in heat resistance and moist heat resistance can be obtained. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.

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

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

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

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

Among these, at least one selected from talc and 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 stereocomplex polylactic acid.

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

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

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

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

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

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

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

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

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

  Such a filler may be coated or converged with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane. May be.

  The 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, particularly preferably 100 parts by weight of the stereocomplex polylactic acid. Is 1-30 parts by weight, most preferably 1-20 parts by weight.

<Release agent>
The resin composition 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 stereocomplex polylactic acid.

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

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

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

  As a polyester plasticizer, acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, Examples thereof include polyesters composed of diol components such as 1,6-hexanediol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-group-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 a terminal group sealing compound such as a terminal group epoxy-modified compound, a terminal group ester-modified compound, and a terminal group 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 stereocomplex polylactic acid. 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 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 stereocomplex polylactic acid.

<Others>
In addition, the resin composition of the present invention may contain 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. 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>
A molded article made of the resin composition 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 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.

  In the injection molding of the present invention, the molding conditions may be set as appropriate. From the viewpoint of increasing the crystallization of the molded product and the molding cycle during injection molding, the mold temperature is preferably 30 ° C. or higher, more preferably 60 ° C. or higher. More preferably, it is 70 ° C. or higher. However, in order to prevent deformation of the molded product, the mold temperature is preferably 140 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.

  Examples of these molded products 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 of the present invention, materials obtained by ordinary melt spinning and subsequent post-processing can be suitably used.
That is, the resin composition of the present invention is melted by an extruder type or pressure melter type melt extruder, weighed by a gear pump, filtered in a pack, and then monofilament through a nozzle provided on the base, It is discharged as a multifilament or the like.

  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 a range of 300 m / min to 5,000 m / min is preferable because a stereo complex crystal is easily formed.

  From the viewpoint of stretchability, a winding speed at which the stereocomplex 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 of the glass transition temperature (Tg) of the stereocomplex polylactic acid 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, 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.

  In addition, after stretching, by heat-setting at 170 ° C. to 220 ° C. under tension, a stereocomplex polylactic acid fiber having a high stereocomplexity ratio (Sc) and low heat shrinkability and a strength of 3.5 cN / dTex or more is obtained. It can also be obtained.

  The fiber obtained from the resin composition of the present invention can take various fiber structure forms. 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 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. When mixed, in order to exhibit the characteristics of stereocomplex polylactic acid, the mixed ratio is selected from the range of 1% by weight or more, more preferably 10% by weight or more, and further preferably 30% by weight or more.

  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 film and sheet of the present invention are formed 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. Also, the biaxial stretching method of roll stretching and tenter stretching, and simultaneous biaxial stretching by tenter stretching 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 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.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Moreover, each value in an Example was calculated | required with the following method.

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

(3) DSC measurement such as degree of stereocomplexation [S (%)] and crystal melting temperature:
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 degree of stereocomplexation 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 the 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) Stability against hydrolysis:
The reduced viscosity retention rate was evaluated when the sample was treated for 100 hours at 80 ° C. and 95% RH with a thermo-hygrostat. When the reduced viscosity retention is from 80 to less than 90%, it is judged as “pass”, when it is from 90% to less than 95%, “excellent pass”, and when it is from 95% to 100%, “excellent pass”. 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 using an Ubbelohde viscosity tube at 35 ° C. The reduced 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:
When the sample was melted and held at 260 ° C. for 5 minutes, it was judged by sensory evaluation whether or not the measurer felt an isocyanate odor. When the isocyanate odor was not felt, it was judged to be acceptable.

(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.
The following agents were produced and used as the cyclic carbodiimide compound.

[Production Example 1] Production of cyclic carbodiimide compound (CC1):
o- nitrophenol (0.11 mol) and pentaerythrityl tetra bromide (0.025 mol), potassium carbonate _{(0.33mol), N, N- N} 2 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 stirring device, 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, the solid substance obtained by removing dichloromethane was purified to obtain a cyclic carbodiimide compound (CC1: MW = 516) represented by the following structural formula. The structure of CC1 was confirmed by NMR and IR.

[Production Example 2] Production of crystalline polymer A1:
48.75 g of L-lactide (made by Musashino Chemical Laboratory Co., Ltd.) and 1.25 g of D-lactide (made by Musashino Chemical Laboratory Co., Ltd.) were added to the flask and the system was purged with nitrogen, and then 0.05 g of stearyl alcohol, As a catalyst, 25 mg of tin octylate was added and polymerized at 190 ° C. for 2 hours to obtain a polymer. This polymer was washed with an acetone solution of 7% 5N hydrochloric acid to remove the catalyst, thereby producing a crystalline polymer A1. The obtained crystalline polymer A1 had a reduced viscosity of 1.45 (mL / g) and a weight average molecular weight of 110,000. The melting point (Tm) was 158 ° C. The crystallization point (Tc) was 121 ° C.
Further, the ratio of L lactic acid to D lactic acid in the obtained crystalline polymer A1 was 97.5 / 2.5 in terms of mole.

[Production Example 3] Production of crystalline polymer B1:
A polymer B1 was produced in the same manner as in Production Example 1 except that 1.25 g of L-lactide (Musashino Chemical Laboratory) and 48.75 g of D-lactide (Musashino Chemical Laboratory) were used. The reduced viscosity of the polymer B1 was 1.65, and the weight average molecular weight was 130,000. The melting point (Tm) was 157 ° C. The crystallization point (Tc) was 122 ° C.
Further, the ratio of L lactic acid to D lactic acid in the obtained crystalline polymer B1 was 2.5 / 97.5 in terms of mole.

[Example 1]
50 parts by weight of each of crystalline polymer A1 and crystalline polymer B1 were added to the flask, and after nitrogen substitution, the temperature was raised to 280 ° C., and melt blending was performed at 280 ° C. for 3 minutes. Further, 1 part by weight of a cyclic carbodiimide compound (CC1) was added to the flask and melt blended at 230 ° C. for 5 minutes. The obtained resin had a weight average molecular weight of 100,000, a reduced viscosity of 1.43 mL / g, a composition having a stereocomplexity (S) of 100% and a crystal melting temperature of 205 ° C. 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. About this composition, when isocyanate gas generation amount was confirmed by GC / MS, isocyanate gas was not detected.

[Comparative Example 1]
In Example 1, it replaced with the cyclic carbodiimide compound (CC1), and it implemented similarly except having changed to linear carbodiimide LA-1 (Nisshinbo Co., Ltd. product, "carbodilite" LA-1), and crystal | crystallization by DSC A composition having a melting temperature of 203 ° C. was obtained. At the time of manufacturing the composition, an isocyanate odor was strongly felt and the working environment was judged to be poor. The isocyanate odor evaluation at 260 ° C. for 5 minutes was also unacceptable.

  The resin composition of the present invention is useful as a raw material for various molded articles.

Claims (15)

(A) a polylactic acid unit A in which L-lactic acid units are 90 mol% or more and 99 mol% or less, and D-lactic acid units and / or copolymerization component units other than lactic acid are 1 mol% or more and 10 mol% or less, and
(B) It comprises a polylactic acid unit B in which D-lactic acid units are 90 mol% or more and 99 mol% or less, and L-lactic acid units and / or copolymerization component units other than lactic acid are 1 mol% or more and 10 mol% or less. ,
The weight ratio of (A) to (B) is in the range of 10:90 to 90:10, the weight average molecular weight is 50,000 to 500,000, and in the differential scanning calorimeter (DSC) measurement, Among the melting peaks, stereocomplex polylactic acid having a melting peak ratio of 200 ° C. or higher of 80% or more,
(C) It includes a cyclic structure in which one carbodiimide group and the first nitrogen and the second nitrogen are bonded by a bonding group, and is represented by the following formula (1), and the number of atoms forming the cyclic structure is 8 to 8 30 cyclic carbodiimide compound (C component), the content ratio is
The resin composition which is a 0.001-10 weight part cyclic carbodiimide compound (C component) per 100 weight part stereocomplex polylactic acid.

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

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

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

(In the formula, Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k are represented by the formulas (1-1) to (1-3), respectively. The same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k in the inside.) The resin composition according to claim 1, wherein the compound containing a cyclic structure of component C is represented by the following formula (3).

(In the formula, Qb is a trivalent linking group which is an aliphatic group, an alicyclic group, an aromatic group or a combination thereof, and may contain a hetero atom. Y carries a cyclic structure. Carrier.) Qb is the following formula (3-1), (3-2) or (3-3) a trivalent linking group is 4. Symbol placement of the resin composition represented by.

(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 represented by the formulas (1-1) to (1-3), respectively. Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s, and k, with one of these being a trivalent group.) Y represents a single bond, double bond, atom, according to claim 4 Symbol placing the resin composition is an atomic group or a polymer. The resin composition according to claim 1, wherein the compound containing a cyclic structure of component C is represented by the following formula (4).

(In the formula, Qc is a tetravalent linking group which is an aliphatic group, an aromatic group, an alicyclic group, or a combination thereof, and may have a hetero atom. Z ¹ and Z ² are It is a carrier carrying a ring structure.) Qc is the following formula (4-1), (4-2) or (4-3) according to claim 7 Symbol placing the resin composition is a tetravalent linking group represented by.

(In the formula, 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 respectively represented by formulas (1-1) to (1-3) Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k, provided that one of them is a tetravalent group or two are 3 Valent group.) Z ¹ and Z ² are each independently a single bond, double bond, atom, group of atoms or claim 7 Symbol placing the resin composition is a polymer. A molded article comprising the resin composition according to any one of claims 1 to 9 . Mold temperature from 30 to 145 10. Symbol placing items injection molded at ° C.. 10. Symbol mounting of moldings thermal deformation temperature of 160 ° C. or higher. In differential scanning calorimetry (DSC) measurement, the crystallization peak in the temperature elevation process (A) and (B) crystallization enthalpy per weight of less than or equal 20J claim 10 Symbol mounting of the molded article. (A) The L-lactic acid unit is 90 mol% or more and 99 mol% or less, the D-lactic acid unit and / or the copolymer component unit other than lactic acid is 1 mol% or more and 10 mol% or less, and the melting point is 140 to 180. Crystalline polymer A,
(B) The D-lactic acid unit is 90 mol% or more and 99 mol% or less, the L-lactic acid unit and / or the copolymer component unit other than lactic acid is 1 mol% or more and 10 mol% or less, and the melting point is 140 to 180. Composed of crystalline polymer B at
Stereocomplex polylactic acid obtained by heat treatment at 245 to 300 ° C. in a weight ratio of (A) to (B) in the range of 10:90 to 90:10;
(C) The cyclic carbodiimide compound (C component) according to claim 1, comprising a cyclic structure in which one carbodiimide group is included and the first nitrogen and the second nitrogen are bonded by a bonding group;
A method for producing a resin composition, comprising mixing C component in an amount corresponding to 0.5 to 100 equivalents of a carbodiimide group per equivalent of carboxyl end groups of stereocomplex polylactic acid. Stereocomplex polylactic carboxyl end groups per equivalent of lactic acid, 0.5 to 5 claim 14 Symbol mounting method of manufacturing a mixing component C in an amount corresponding to equivalent weight of carbodiimide groups.