JP2010174219A - Polylactic acid composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polylactic acid composition which gives off no bad smell and is excellent in hue and wet-heat resistant stability. <P>SOLUTION: The polylactic acid composition contains 100 pts.wt. of a polylactic aid (component A) and 0.001-10 pts.wt. of a silylcarbodiimide compound (component B). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a composition containing a silylcarbodiimide compound and polylactic acid and having excellent hue and moist heat resistance. Furthermore, the present invention relates to a melt-molded product comprising the composition and excellent in hue and heat and humidity resistance.

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. In particular, polylactic acid is a general-purpose polymer because the raw material lactic acid or its derivatives have been produced in large quantities at low cost from biological materials by fermentation, in addition to the excellent properties of transparency and high rigidity. The use as a stretched film, a fiber, an injection molded product, etc. is examined.
However, since polylactic acid is easily hydrolyzed, for example, the melt viscosity is greatly decreased and the moldability is greatly changed in the molten state, and the mechanical properties of the molded product are largely decreased in the solid state. In addition, since the crystallization speed is slow, there is a limit to the moldability even when crystallized and used as a molded product, and there are some problems to be solved for practical use.
In order to improve moldability, a method of adding an agent for promoting crystallization such as a crystallization nucleating agent has been proposed (Patent Document 1). Moreover, the method of adding an organic and inorganic filler is proposed (patent document 2). Although these methods are effective to some extent in improving the crystallization rate itself, the wet heat stability remains low, and it is far from the essential solution of the problem.

On the other hand, a solution of 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. Alternatively, it is known that stereocomplex polylactic acid is formed by mixing in a molten state (Patent Document 3 and Non-Patent Document 1). This stereocomplex polylactic acid has a crystal melting temperature of 200 to 250 ° C., a higher melting point than PLLA and PDLA, and an interesting phenomenon showing high crystallinity has been discovered.
However, formation of stereocomplex polylactic acid is not easy, and the difficulty becomes even more pronounced especially when the weight average molecular weight of PLLA or PDLA exceeds 150,000 (Patent Document 3).
That is, the stereocomplex polylactic acid usually does not show a single phase, but the PLLA and PDLA phases (hereinafter sometimes referred to as homophases) and the stereocomplex polylactic acid phase (hereinafter sometimes referred to as complex phases). This is a mixed phase composition. In this mixed composition, if the ratio of the complex phase is small, it is difficult to exhibit the heat resistance inherent in stereocomplex polylactic acid.

With regard to improving the heat and heat resistance of polylactic acid or stereocomplex polylactic acid, the heat and humidity resistance of carbodiimide compounds, specifically, the carbodiimide group's nitrogen atom bonded to the carbon atom by sealing the carboxyl group with a hydrocarbon carbodiimide Has been proposed (Patent Documents 4 and 5).
However, in these proposals, the hydrocarbon-based carbodiimide compound kneaded in the resin tends to react with the carboxyl group and decompose to generate malodorous substances. There is a problem of deteriorating the environment, and the problem of deteriorating the working environment is waiting for an immediate solution. Furthermore, the malodorous substance produced in the resin deteriorates the color tone of the polylactic acid composition to 4 to 8 or more in the color b value, and there is a problem that the use as a product is restricted.

JP 2003-192894 A Japanese Patent Laid-Open No. 2005-2174 JP 63-24014 A JP 2004-332166 A JP 2005-350829 A

Macromolecules, 24, 5651 (1991).

  An object of the present invention is to provide a polylactic acid composition that does not cause the work environment to deteriorate due to bad odor. Another object of the present invention is to provide a polylactic acid composition having excellent hue and heat-and-heat stability. Another object of the present invention is to provide a melt-formed product comprising the composition.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies, and compositions containing polylactic acid and a silylcarbodiimide compound, particularly a silylcarbodiimide compound having a specific structure, do not generate malodor during melt molding. The present invention was completed by discovering excellent hue and wet heat resistance.

That is, the subject of the present invention is
1. A composition containing 100 parts by weight of polylactic acid (component A) and 0.001 to 10 parts by weight of a silylcarbodiimide compound (component B);
2. The silylcarbodiimide compound (component B) is a compound mainly composed of repeating units represented by the following formula (i), having a polymerization degree of 1 to 20, and having a substituent represented by X or formula (ii) at the terminal. A composition according to the preceding item 1,

(R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. X and Y are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Alkyloxy groups, cycloalkyloxy groups having 5 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, or polyalkylenes whose ends are sealed with ester groups or ether groups It is an oxy group.)
3. In formulas (i) and (ii), the silylcarbodiimide compound (component B) has a total number of carbon atoms of R ¹ and R ² of 10 or more, and a total number of carbon atoms of R ³ and R ⁴ of 10 or more. The composition according to item 1,
4). The composition according to item 2 or 3, wherein the polymerization degree of the silylcarbodiimide compound (component B) is 6 to 12,
5). The composition according to any one of the preceding items 2 to 4, wherein the content of the trimethylsilyl group of the silylcarbodiimide compound (component B) is 0.1 to 200 ppm,
6). The composition according to any one of items 2 to 5 above, wherein the hydrolyzable halogen content of the silylcarbodiimide compound (component B) is 0.01 to 100 ppm,
7). Polylactic acid (component A) is composed of units other than 90 to 100 mol% L-lactic acid units and 0 to 10 mol% L-lactic acid units, and 90 to 100 mol% D-lactic acid units And the composition according to any one of the preceding items 1 to 6, comprising poly D-lactic acid comprising units other than 0 to 10 mol% of D-lactic acid,
8). 8. The composition according to item 7 above, wherein the polylactic acid (component A) is crystalline polylactic acid showing a crystal melting peak of 160 ° C. or higher by differential scanning calorimetry (DSC) measurement.
9. 9. The composition according to item 7 or 8 above, containing 0.001 to 5 parts by weight of a phosphate ester metal salt represented by formula (I) or (II) per 100 parts by weight of polylactic acid (component A);

(In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₁ is an alkali. A metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom, p is 1 or 2, q is 0 when M ₁ is an alkali metal atom, an alkaline earth metal atom or a zinc atom, and when it is an aluminum atom 1 or 2)

Wherein R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₂ is an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. Is 1 or 2, q is 0 when M ₂ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₂ is an aluminum atom.)
10. Polylactic acid (component A) shows a crystal melting peak of 200 ° C. or higher by differential scanning calorimetry (DSC) measurement, and the ratio of the crystal melting peak of 200 ° C. or higher of the crystal melting peak is 80 to 100%. The composition according to any one of 7 to 9,
11. A melt-molded article comprising the composition according to any one of 1 to 10 above,
12 The melt molded product according to 11 above, which is a film, a fiber, a fiber structure, or an injection molded product,
Can be achieved.

  The composition of the present invention does not generate malodor during melt molding, and there is no fear of deterioration of the working environment. In addition, the composition of the present invention is excellent in hue and wet heat resistance. Further, the melt-molded product of the present invention is excellent in hue and wet heat stability.

Based on the knowledge described below, the composition of the present invention is replaced with a conventional hydrocarbon-based carbodiimide compound, and the silylcarbodiimide compound (component B) is added in an amount of 0.001 to 10 weights per 100 parts by weight of polylactic acid (component A). Contains.
The conventional hydrocarbon carbodiimide in which the nitrogen atom of the carbodiimide group is bonded to the carbon atom is
1) It reacts with a carboxyl group in polylactic acid to produce a urea compound and an isocyanate compound via an N-acyl compound.
2) When the isocyanate compound is melted, it is evaporated and becomes the main cause of work environment deterioration.
3) Further, in the polylactic acid, a hydrocarbon carbodiimide compound, an N-acyl compound derived therefrom and an isocyanate compound deteriorate the hue of the resin.
In contrast, a silylcarbodiimide compound in which a nitrogen atom of a carbodiimide group is bonded to a silicon atom,
1) It has the ability to seal the carboxyl group in polylactic acid with at least the same activity as that of hydrocarbon-based carbodiimide, and improve wet heat resistance.
2) However, the generation of isocyanate, which is the main cause of malodor, is greatly suppressed.
3) It has been found that silylcarbodiimide, the compound, and an N-acyl compound derived therefrom significantly suppress the action of deteriorating the hue of the resin.
Thereby, while the hue of a composition and heat-and-moisture resistance stability improve significantly, generation | occurrence | production of a malodorous substance can be reduced significantly and the deterioration of a working environment can be suppressed.

In addition, when the content of the silylcarbodiimide compound (component B) is less than 0.001 part by weight per 100 parts by weight of polylactic acid (component A), the desired effect of improving the humidification heat resistance is effectively exhibited. There are things you can't do. Moreover, even if it contains more than 10 weight part, the effect by it is not only large, but it cannot recommend from a viewpoint of manufacturing cost.
The heat-and-moisture stability is the stability of polylactic acid molecules against hydrolysis by moisture.In the present invention, the stability of the melt in the molten state and the stability of hydrolysis in the solid state described in the item of evaluation items are used. Be evaluated.
(B component: silylcarbodiimide compound)
As the silylcarbodiimide compound (component B), a compound mainly composed of a repeating unit represented by the following formula (i), having a degree of polymerization of 1 to 20, and having a substituent represented by X or formula (ii) at the terminal. preferable.

In the formula, R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. is there.

As the alkyl group having 1 to 20 carbon atoms R ¹ to R ^4, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, t- butyl group, n- hexyl group, t-amyl Examples include a group, a decyl group, a dodecyl group, a hexadecyl group, and an oleyl group. Examples of the cycloalkyl group having 5 to 20 carbon atoms include cyclopentyl group, cyclohexyl group, decalyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group, 2,6-di-t-butylcyclohexyl group and the like. . Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, xylyl group, tolyl group, 4-t-butylphenyl group, 2,6-di-t-butylphenyl group, dodecylphenyl group, 1-naphthyl group and the like. Illustrated. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, 4-t-butylbenzyl group, 2,6-di-t-butylbenzyl group, dodecylbenzyl group and the like.

X and Y are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or 1 to 20 carbon atoms. An alkyloxy group, a cycloalkyloxy group having 5 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or a polyalkylene whose ends are sealed with an ester group or an ether group It is an oxy group.
As X and Y, as an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, The substituents exemplified for R ^{1 to} R ⁴ are preferably exemplified.

As an alkyloxy group having 1 to 20 carbon atoms, methyloxy group, ethyloxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group, t-butyloxy group, n-hexyloxy group, t-amyloxy group Decyloxy group, dodecyloxy group, hexadecyloxy group, oleyloxy group and the like. Examples of the cycloalkyloxy group having 5 to 20 carbon atoms include a cyclopentyloxy group, a cyclohexyloxy group, a decalyloxy group, and a 2,4-dimethylcyclohexyloxy group.
As the aryloxy group having 6 to 20 carbon atoms, phenyloxy group, xylyloxy group, tolyloxy group, 4-t-butylphenyloxy group, dodecylphenyloxy group, 2,6-di-t-butylphenyloxy group, 1- A naphthyloxy group etc. are illustrated.
Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, 4-t-butylbenzyloxy group, 2,6-di-t-butylbenzyloxy group, dodecylbenzyloxy group and the like. As a polyalkyleneoxy group whose terminal is sealed with an ester group or an ether group, the degree of polymerization is 5 to 100, preferably the degree of polymerization is 6 to 70, more preferably 7 to 65, and more preferably the terminal having a degree of polymerization of 10 to 50. Examples include a methoxylated polyethyleneoxy group, a terminal acetoxylated polyethyleneoxy group, a terminal ethoxylated polytetramethyleneoxy group, and a terminal butoxylated polypropyleneoxy group.

The degree of polymerization of the silylcarbodiimide compound (component B) is selected in the range of 1-20. Even if the degree of polymerization exceeds 20, the hydrolysis resistance of polylactic acid can be improved. However, if the degree of polymerization exceeds 20, the compatibility with polylactic acid becomes low, and there is a concern that the resin composition will be dirty. Moreover, from the production efficiency of the prepolymer, the degree of polymerization is preferably in the range of 2 to 20, more preferably 4 to 18, still more preferably 6 to 14, and particularly preferably 6 to 12.
The content of the repeating unit represented by the formula (i) in the silylcarbodiimide compound (component B) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 98 to 100 mol%. is there.
The trimethylsilyl group content in the silylcarbodiimide compound (component B) is preferably 0.1 to 200 ppm. The trimethylsilyl group is a substituent in which R ³ , R ⁴ and Y are each a methyl group in the formula (ii).
The hydrolyzable halogen content in the silylcarbodiimide compound (component B) is preferably 0.01 to 100 ppm.
The 5% weight loss temperature by thermogravimetric analysis (TGA) measurement of the silylcarbodiimide compound (component B) is preferably 300 ° C. or higher. When applied to polylactic acid with a 5% heat loss temperature of 300 ° C. or higher, deterioration of the work environment due to malodor can be suppressed.
The silylcarbodiimide compound (component B) can be suitably used as a hydrolysis-resistant stabilizer for polylactic acid because deterioration of the working environment due to bad odor is suitably suppressed, and the resin hue is less likely to deteriorate. The silylcarbodiimide compound (component B) is composed of polylactic acid, especially poly L- and poly D-lactic acid, and is applied to stereocomplex polylactic acid having a crystal melting temperature of 200 ° C. or higher by a differential scanning calorimeter. The polylactic acid composition having a good hue and good stability is effectively provided.

The polysilylcarbodiimide compound (component B), when applied to polylactic acid, further suppresses the deterioration of the working environment due to bad odor, and further suitably increases the 5% heat loss temperature to 300 ° C. or higher, so that the formulas (i) and ( In ii), the total number of carbon atoms of R ¹ and R ² is preferably 10 or more, and the total number of carbon atoms of R ³ and R ⁴ is preferably 10 or more.
The silylcarbodiimide compound (component B), when applied to polylactic acid, more preferably suppresses the deterioration of the working environment due to malodor or the like, and further increases the 5% heat loss temperature to 310 ° C. or higher, so that the formula (i) and In (ii), the total carbon number of R ¹ , R ² and X is preferably 15 or more, and the total carbon number of R ³ , R ⁴ and Y is preferably 15 or more.

In the silylcarbodiimide compound (component B), the terminal group represented by the formula (ii) is, for example,
A trimethylsilyl group,
(Dimethyl) (hexyl) silyl group,
(Dimethyl) (octyl) silyl group,
(Dimethyl) (decyl) silyl group,
(Dimethyl) (phenyl)) silyl group,
(Dimethyl) (4-tert-butylphenyl)) silyl group,
(Dimethyl) (hexadecyl) silyl group,
(Dimethyl) (icosyl) silyl group,
(Methyl) (ethyl) (heptyl) silyl group,
(Methyl) (ethyl) (tridecyl) silyl group,
(Methyl) (propyl) (tetradecyl) silyl group,
(Methyl) (propyl) (octadecyl) silyl group,
(Methyl) (hexyl) (octyl) silyl group,
(Methyl) (hexyl) (tridecyl) silyl group,
(Methyl) (hexyl) (heptadecyl) silyl group,
(Methyl) (nonyl) (icosyl) silyl group,
(Dipropyl) (butyl) silyl group,
(Hexyl) (octyl) (nanodecyl) silyl group,
(Hexyl) (octyl) (dodecyl) silyl group,
(Dihexyl) (nonadecyl) silyl group,
(Octyl) (decyl) (pentadecyl) silyl group,
(Nonyl) (hexdecyl) (octadecyl) silyl group,
(Dioctyl) (hexadecyl) silyl group,
(Dodecyl) (cyclohexyl) (oleyl) silyl group,
(Hexyl) (nonyl) (icosyl) silyl group,
(Pentyl) (dioleoyl) silyl group,
(Tridecyl) (diheptyl) (oleyl) silyl group,
(Hexyl) (dioleyl) silyl group,
(Heptyl) (dinonyl) (icosyl) silyl group,
(Cyclohexyl) (dimethyl) silyl group,
(Cyclohexyl) (methyl) (tridecyl) silyl group,
(Cyclohexyl) (methyl) (nanodecyl) silyl group,
(Cyclohexyl) (propyl) (nanodecyl) silyl group,
(4-propylcyclohexyl) (dimethyl) silyl group,
(Cyclohexyl) (decyl) (nanodecyl) silyl group (dihexyl) (propyl) silyl group,
(Dihexyl) (tetradecyl) silyl group,
(Dihexyl) (nanodecyl) silyl group,
Tris (2,4,6-trimethylcyclohexyl) silyl group,
Tricyclopentylsilyl group, (dimethyl) (phenyl) silyl group,
(Dimethyl) (4-methylphenyl) silyl group,
(Dimethyl) (2,6-di-butylphenyl) silyl group,
(Dimethyl) (4-methyl-2,6-di-butylphenyl) silyl group,
(Dibutyl) (phenyl) silyl group,
(Dibutyl) (4-methylphenyl) silyl group,
(Dihexyl) (4-ethylphenyl) silyl group,
(Dinonyl) (phenyl) silyl group,
(Dinonyl) (2,6-di-butylphenyl) silyl group,
(Ditridecyl) (4-methyl-2,6-di-butylphenyl) silyl group,
(Dinanodecyl) (phenyl) silyl group,
(Dinanodecyl) (4-ethylphenyl) silyl group,
(Butyl) (octyl) (phenyl) silyl group,
(Octyl) (tridecyl) (phenyl) silyl group,
(Butyl) (nanodecyl) (phenyl) silyl group,
(Methyl) (phenyl) (oleyl) silyl group,
(Methyl) (phenyl) (icosyl) silyl group,
(Dihexyl) (4-methylphenyl) silyl group,
(Dihexyl) (phenyl) silyl group,
(Methyl) (diphenyl) silyl group,
(Methyl) (hexyl) (4-methylphenyl) silyl group,
(Methyl) (dodecyl) (4-ethylphenyl) silyl group,
(Methyl) (tetradecyl) (2,6-di-butylphenyl) silyl group,
(Methyl) (heptadecyl) (4-methyl-2,6-di-butylphenyl) silyl group,
(Butyl) (cyclohexyl) (4-methylphenyl) silyl group,
(Octyl) (nonyl) (4-ethylphenyl) silyl group,
(Dodecyl) (oleyl) (2,6-di-butylphenyl) silyl group,
(Diaicosyl) (4-methyl-2,6-di-butylphenyl) silyl group,
(Methyl) (diphenyl) silyl group,
(Methyl) [bis (4-methylphenyl)] silyl group,
(Methyl) [bis (4-ethylphenyl)] silyl group,
(Methyl) [bis (2,6-di-butylphenyl)] silyl group,
(Methyl) [bis (4-methyl-2,6-di-butylphenyl)] silyl group,
(Methyl) [bis (4-methylphenyl)] silyl group,
(Methyl) [bis (4-ethylphenyl)] silyl group,
(Methyl) [bis (2,6-di-butylphenyl)] silyl group,
(Methyl) [bis (4-methyl-2,6-di-butylphenyl)] silyl group,
(Butyl) [bis (4-methylphenyl)] silyl group,
(Dodecyl) (diphenyl) silyl group,
(Nonyl) [bis (2,6-di-butylphenyl)] silyl group,
(Tridecyl) [bis (4-methyl-2,6-di-butylphenyl)] silyl group,
(Hexadecyl) [bis (4-methylphenyl)] silyl group,
Triphenylsilyl group, tris (4-ethylphenyl) silyl group,
Tris (2,6-di-butylphenyl) silyl group,
Tris (4-methyl-2,6-di-butylphenyl) silyl group,
Tris (4-methylphenyl) silyl group,
Tris (4-ethylphenyl) silyl group,
Tris (2,6-di-butylphenyl) silyl group,
Tris (4-methyl-2,6-di-butylphenyl) silyl group,
(Dimethyl) (benzyl) silyl group,
(Dimethyl) (4-propylbenzyl) silyl group,
(Methyl) (benzyl) (oleyl) silyl group,
(Methyl) (benzyl) (icosyl) silyl group,
(Dihexyl) (4-methylbenzyl) silyl group,
(Dihexyl) (benzyl) silyl group,
(Octyl) (nonyl) (4-ethylbenzyl) silyl group,
(Dodecyl) (oleyl) (2,6-di-butylbenzyl) silyl group,
(Diaicosyl) (4-methyl-2,6-di-butylbenzyl) silyl group,
(Methyl) [bis (4-methylbenzyl)] silyl group,
(Propyl) [bis (4-methyl-2,6-di-butylbenzyl)] silyl group,
(Nonyl) (dibenzyl) silyl group,
(Diphenyl) (dibenzyl) silyl group,
(Butyl) [bis (4-methylbenzyl)] silyl group,
(Tridecyl) [bis (4-ethylbenzyl)] silyl group,
(Nonyl) [bis (2,6-di-butylbenzyl)] silyl group,
(Tridecyl) [bis (4-methyl-2,6-di-butylbenzyl)] silyl group,
(Hexadecyl) [bis (4-methylbenzyl)] silyl group,
(Nanodecyl) [bis (4-ethylbenzyl)] silyl group,
A tribenzylsilyl group,
Tris (4-t-butylbenzyl) silyl group,
Tris (4-methylbenzyl) silyl group,
(Dimethyl) (propyloxy) silyl group,
(Dimethyl) (hexyloxy) silyl group,
(Dimethyl) (cyclohexyloxy) silyl group,
(Dimethyl) (decyloxy) silyl group,
(Dimethyl) (phenyloxy) silyl group,
(Dimethyl) (4-tert-butylphenyloxy) silyl group,
(Dimethyl) (dodecyloxy) silyl group,
(Dimethyl) (hexadecyloxy) silyl group,
(Methyl) (ethyl) (heptyloxy) silyl group,
(Methyl) (propyl) (octadecyloxy) silyl group (methyl) (hexyl) (octyloxy) silyl group,
(Methyl) (cyclohexyl) (tridecyloxy) silyl group,
(Methyl) (hexyl) (heptadecyloxy) silyl group,
(Methyl) (nonyl) (icosyl) silyl group,
(Decyl) (hexadecyl) (octyloxy) silyl group,
(Dipropyl) (butyloxy) silyl group,
(Propyl) (butyl) (pentyloxy) silyl group,
(Butyl) (pentyl) (pentadecyloxy) silyl group,
(Hexyl) (octyl) (nanodecyloxy) silyl group,
(Dihexyl) (nonadecyloxy) silyl group,
(Octyl) (decyl) (pentadecyloxy) silyl group,
(Nonyl) (hexdecyl) (octadecyloxy) silyl group,
(Dioctyl) (hexadecyloxy) silyl group,
(Didodecyl) (nonadecyloxy) silyl group,
(Dodecyl) (cyclohexyl) (oleyloxy) silyl group,
(Hexyl) (nonyl) (icosyloxy) silyl group,
(Pentyl) (dioleoyloxy) silyl group,
(Tridecyl) (diheptyl) (oleyl) silyl group,
(Hexyl) (dioleoyloxy) silyl group,
(Heptyl) (dinonyl) (icosyl) silyl group,
(Cyclohexyloxy) (dimethyl) silyl group,
(Cyclohexyloxy) (methyl) (nanodecyl) silyl group,
(Cyclohexyloxy) (propyl) (nanodecyl) silyl group,
(4-propylcyclohexyloxy) (dimethyl) silyl group,
(Cyclohexyloxy) (decyl) (nanodecyl) silyl group,
(Cyclohexyl) (propyl) (cyclohexyloxy) silyl group,
(Hexyl) (nanodecyl) (cyclohexyloxy) silyl group,
(Dicyclohexyl) (cyclohexyloxy) silyl group,
Bis (4-butylcyclohexyl) (4-butylcyclohexyloxy) silyl group,
Bis (2,4,6-trimethylcyclohexyl) (2,4,6-trimethylcyclohexyloxy) silyl group,
(Dicyclopentyl) (cyclopentyloxy) silyl group,
(Dimethyl) (phenyloxy) silyl group,
(Dimethyl) (4-methylphenyloxy) silyl group,
(Dimethyl) (2,6-di-butylphenyloxy) silyl group,
(Dimethyl) (4-methyl-2,6-di-butylphenyloxy) silyl group,
(Dimethyl) (4-ethylphenyloxy) silyl group,
(Dimethyl) (2,6-di-butylphenyloxy) silyl group,
(Dibutyl) (phenyloxy) silyl group,
(Dibutyl) (4-methylphenyloxy) silyl group,
(Dihexyl) (4-ethylphenyloxy) silyl group,
(Dinonyl) (phenyloxy) silyl group,
(Dinonyl) (2,6-di-butylphenyloxy) silyl group,
(Ditridecyl) (4-methyl-2,6-di-butylphenyloxy) silyl group,
(Dihexadecyl) (phenyloxy) silyl group,
(Dihexadecyl) (4-methylphenyloxy) silyl group,
(Dinanodecyl) (phenyloxy) silyl group,
(Dinanodecyl) (4-ethylphenyloxy) silyl group,
(Butyl) (octyl) (phenyloxy) silyl group,
(Octyl) (tridecyl) (phenyloxy) silyl group,
(Methyl) (oleyl) (phenyloxy) silyl group,
(Methyl) (icosyl) (phenyloxy) silyl group,
(Dihexyl) (phenyloxy) silyl group,
(Methyl) (phenyl) (phenyloxy) silyl group,
(Methyl) (hexyl) (4-methylphenyloxy) silyl group,
(Methyl) (heptadecyl) (4-methyl-2,6-di-butylphenyloxy) silyl group,
(Butyl) (cyclohexyl) (4-methylphenyloxy) silyl group,
(Octyl) (nonyl) (4-ethylphenyloxy) silyl group,
(Dodecyl) (oleyl) (2,6-di-butylphenyloxy) silyl group,
(Diaicosyl) (4-methyl-2,6-di-butylphenyloxy) silyl group,
(Methyl) (phenyl) (phenyloxy) silyl group,
(Methyl) (4-ethylphenyl) (4-ethylphenyloxy) silyl group,
(Methyl) (4-methylphenyl) (4-methylphenyloxy) silyl group,
(Methyl) (4-ethylphenyl) (4-ethylphenyloxy) silyl group,
(Methyl) (2,6-di-butylphenyl) (2,6-di-butylphenyloxy) silyl group,
(Methyl) (4-methyl-2,6-di-butylphenyl) (4-methyl-2,6-di-butylphenyloxy) silyl group,
(Butyl) (4-methylphenyl) (4-methylphenyloxy) silyl group,
(Octyl) (phenyl) (phenyloxy) silyl group,
(Nonyl) (2,6-di-butylphenyl) (2,6-di-butylphenyloxy) silyl group,
(Tridecyl) (4-methyl-2,6-di-butylphenyl) (4-methyl-2,6-di-butylphenyloxy) silyl group,
(Nanodecyl) (4-ethylphenyl) (4-ethylphenyloxy) silyl group,
(Diphenyl) (phenyloxy) silyl group,
Bis [(4-methylphenyl)] (4-methylphenyloxy) silyl group,
Bis [(2,6-di-butylphenyl)] (2,6-di-butylphenyloxy) silyl group,
Bis [(4-methyl-2,6-di-butylphenyl)] (4-methyl-2,6-di-butylphenyloxy) silyl group,
Bis [(4-ethylphenyl)] (4-ethylphenyloxy) silyl group,
Bis [(2,6-di-butylphenyl)] (2,6-di-butylphenyloxy) silyl group,
(Dimethyl) (benzyloxy) silyl group,
(Dimethyl) (4-propylbenzyloxy) silyl group,
(Methyl) (oleyl) (benzyloxy) silyl group,
(Methyl) (icosyl) (benzyloxy) silyl group,
(Dihexyl) (4-methylbenzyloxy) silyl group,
(Dihexyl) (benzyloxy) silyl group,
(Octyl) (nonyl) (4-ethylbenzyloxy) silyl group,
(Dodecyl) (oleyl) (2,6-di-butylbenzyloxy) silyl group,
(Diaicosyl) (4-methyl-2,6-di-butylbenzyloxy) silyl group,
(Methyl) (4-methylbenzyl) (4-methylbenzyloxy) silyl group,
(Propyl) (4-methyl-2,6-di-butylbenzyl) (4-methyl-2,6-di-butylbenzyloxy) silyl group,
(Nonyl) (benzyl) (benzyloxy) silyl group,
(Phenyl) (benzyl) (benzyloxy) silyl group,
(Butyl) (4-methylbenzyl) (4-methylbenzyloxy) silyl group,
(Tridecyl) (4-ethylbenzyl) (4-ethylbenzyloxy) silyl group,
(Tridecyl) (4-methyl-2,6-di-butylbenzyl) (4-methyl-2,6-di-butylbenzyloxy) silyl group,
(Hexadecyl) (4-methylbenzyl) (4-methylbenzyloxy) silyl group,
(Nanodecyl) (4-ethylbenzyl) (4-ethylbenzyloxy) silyl group,
(Dibenzyl) (benzyloxy) silyl group,
Examples include bis (4-methylbenzyl) (4-methylbenzyloxy) silyl group.

  Examples of the silylcarbodiimide (component B) include the following polysilylcarbodiimide compounds having a polymerization degree of 1 to 20, preferably 2 to 18, more preferably 3 to 15, and further preferably 6 to 12.

As a carbodiimide having an alkylsilyl structure,
Poly (dimethylsilanediylcarbodiimide-1,3-diyl),
Poly [(methyl) (ethyl) silanediylcarbodiimide-1,3-diyl],
Poly [(methyl) (heptyl) silanediylcarbodiimide-1,3-diyl],
Poly [(methyl) (nonyl) silanediylcarbodiimide-1,3-diyl],
Poly [(methyl) (dodecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(methyl) (hexadecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(methyl) (heptadecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(diethyl) silanediylcarbodiimide-1,3-diyl],
Poly [(propyl) (hexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(butyl) (octyl) silanediylcarbodiimide-1,3-diyl],
Poly [(ethyl) (undecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(propyl) (tetradecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(butyl) (octadecyl) silanediylcarbodiimide-1,3-diyl],
Poly (dipentylsilanediylcarbodiimide-1,3-diyl),
Poly [(hexyl) (decyl) silanediylcarbodiimide-1,3-diyl],
Poly [(heptyl) (tridecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(pentyl) (tetradecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(hexyl) (heptadecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(octyl) (nonyl) silanediylcarbodiimide-1,3-diyl],
Poly [(nonyl) (dedosyl) silanediylcarbodiimide-1,3-diyl],
Poly [(decyl) (hexadecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(octyl) (eicosyl) silanediylcarbodiimide-1,3-diyl,
Poly [(nonyl) (dedosyl) silanediylcarbodiimide-1,3-diyl],
Poly [(decyl) (hexadecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(octyl) (eicosyl) silanediylcarbodiimide-1,3-diyl],
Poly [(undecyl) (dodecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(dodecyl) (hexadecyl) silanediylcarbodiimide-1,3-diyl]
Poly [(tridecyl) (nonadecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(pentadecyl) (hexadecyl) silanediylcarbodiimide-1,3-diyl],
Poly [(hexadecyl) (hexadecyl) silanediylcarbodiimide-1,3-diyl],
And poly [(tridecyl) (octadecyl) silanediylcarbodiimide-1,3-diyl].

Moreover, as a carbodiimide having a cycloalkylalkylsilyl structure,
Poly [(methyl) (cyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(propyl) (cyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(heptyl) (cyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(undecyl) (cyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(dodecyl) (cyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(hexadecyl) (cyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(eicosyl) (cyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(methyl) (cyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(butyl) (cyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(octyl) (cyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(undecyl) (cyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(tetradecyl) (cyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(nonadecyl) (cyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(decalyl) (cyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(methyl) (3methyl-cyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(propyl) (3-ethylcyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(heptyl) (2,3-dimethylcyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(dodecyl) (3-butylcyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(hexadecyl) (3-hexylcyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(eicosyl) (2,3,4-trimethylcyclopentyl) silanediylcarbodiimide-1,3-diyl],
Poly [(methyl) (4-methylcyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(ethyl) (2.4-dimethylcyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(butyl) (butylcyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(octyl) (cyclohexylcyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(undecyl) (4-ethylcyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(tetradecylsil) (dibutylcyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(nonadecyl) (hexylcyclohexyl) silanediylcarbodiimide-1,3-diyl],
Poly (dicyclopentylsilanediylcarbodiimide-1,3-diyl),
Poly [(cyclohexyl) (pentyl) silanediylcarbodiimide-1,3-diyl],
Poly (dicyclohexylsilanediylcarbodiimide-1,3-diyl),
And poly [(4-methylcyclohexyl) (2,4-dimethylcyclohexyl) silanediylcarbodiimide-1,3-diyl].

As ilcarbodiimide having an arylsilane structure,
Poly [(methyl) (phenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(cyclopentyl) (methylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(octyl) (methylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(tetradecyl) (methylphenyl) silanediylcarbodiimide-1,3-diyl],
(Poly [(hexadecyl) (methylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(methyl) (2-methylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(pentyl) (4-t-butylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(pentyl) (2-methyl-4-t-butylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(octyl) (2,4-dimethylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(tetradecyl) (4-ethyl-2-methylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(hexadecyl) (phenylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(cyclohexyl) (tolyl) silanediylcarbodiimide-1,3-diyl],
Poly [(4-ethylcyclohexyl) (4-ethylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(2,6-dimethylcyclohexyl) (4-t-butylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly (diphenylsilanediylcarbodiimide-1,3-diyl),
Poly (ditolylsilanediylcarbodiimide-1,3-diyl),
Poly (dixylylsilanediylcarbodiimide-1,3-diyl),
Poly [(phenyl) (diphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(phenyl) (tolyl) silanediylcarbodiimide-1,3-diyl],
Poly [(phenyl) (4-ethylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(phenyl) (4-t-butylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(phenyl) (2,4,6-trimethylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly (ditolylsilanediylcarbodiimide-1,3-diyl),
Poly (dixylylsilanediylcarbodiimide-1,3-diyl),
Poly [bis (4-ethylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [bis (4-t-butylphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(bis (2,4,6-trimethylphenyl) silanediylcarbodiimide-1,3-diyl),
Poly [(phenyl) (diphenyl) silanediylcarbodiimide-1,3-diyl],
Poly [(benzyl) (hexyl) silanediylcarbodiimide-1,3-diyl],
Poly [(benzyl) (octyl) silanediylcarbodiimide-1,3-diyl],
Poly [(benzyl) (cyclohexyl) silanediylcarbodiimide-1,3-diyl],
And poly [(dibenzylsilanediylcarbodiimide-1,3-diyl).

<Method for producing silylcarbodiimide compound>
The silylcarbodiimide compound (component B) is a step (I) for producing a halogenated polysilylcarbodiimide (prepolymer) represented by the following formula (v), and the halogen atom of the resulting prepolymer is represented by X or formula (ii) It can manufacture by process (II) substituted by the substituent represented by these.

(Step (I): Production of prepolymer)
The halogenated polysilylcarbodiimide (prepolymer) comprises, as described below, a bistrialkylsilylcarbodiimide (a) represented by the following formula (iii) and a dihalosilyl compound (b) represented by the following formula (iv): Produced by reacting.

R in formula (iii) is each independently an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group and an ethyl group. As the compound of formula (iii), bistrimethylsilylcarbodiimide is preferred.
Q in the formula (iv) is each independently a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. As the compound of formula (iv), a silyl dichloride compound is preferred. R ¹ and R ² are the same as in formula (i), and each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number. 7 to 20 aralkyl groups. Q, R ¹ and R ² in the formula (v) are the same as in the formula (iv).

The polymerization degree of the prepolymer can be set to a desired range by appropriately setting the molar ratio of (a) :( b). In order to make the degree of polymerization about 18-22, (a): (b) is in the range close to 1: 1, and in order to make the degree of polymerization about 8-12, the range is 1: 1.1-1.2. When the degree of polymerization is in the range close to 1, (a) :( b) is preferably selected in the range of 1: 2-5.
The components (a) and (b) mixed in the above-mentioned quantitative ratio are charged into a reaction vessel equipped with a stirrer, a thermometer, a distilling tube, and a vacuum pipe, and at 140 to 170 ° C. under normal pressure conditions. The mixture is stirred for 2 to 3 hours, and the resulting trimethylsilane chloride is distilled off. When 50 to 90% of the theoretical amount of trimethylsilane chloride is distilled off, the degree of vacuum in the reaction vessel is gradually increased, and the reaction is continued for another 3 to 10 hours. The degree of vacuum is usually 0.1 to 10 kPa. The reaction time and reaction temperature are appropriately changed depending on the structure of component (b).

(Step (II): replacement step, first method)
Step (II) comprises the obtained prepolymer and the following formula (vi)

(In formula (vi), X is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.)
The halogen compound at both ends of the prepolymer is reacted with an alkyloxy group having 1 to 20 carbon atoms, a cycloalkyloxy group having 5 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and the number of carbon atoms. This is a step of obtaining the polysilylcarbodiimide compound of the present invention by substituting 7-20 aralkyloxy groups or polyalkyleneoxy groups whose ends are blocked with ester groups or ether groups.
The reaction can be carried out as follows. The prepolymer is dissolved in a solvent, mixed with the hydroxy compound represented by formula (vi), and reacted at a temperature of room temperature to about 200 ° C. At this time, the inside of the system is completely in a liquid phase, and further, the inside of the system is reacted in a two-phase separated state in which the above-described prepolymer and polysilylcarbodiimide-containing layer and the above-mentioned hydroxy compound-containing layer are separated into two phases. As a result, halogen can be effectively converted into the aforementioned functional group, impurities such as halogen in the polysilylcarbodiimide compound can be suitably removed, heat resistance is improved, and 5% weight loss starting temperature is 300 ° C. or higher in thermogravimetric analysis. Can be increased.

In order to realize such a two-phase separation state, the solvent may be a linear or cyclic ether having a boiling point of 30 to 150 ° C., more preferably 50 to 120 ° C., examples of halogenated hydrocarbons, aliphatic ketones, lower Hydrocarbons can be used.
As these solvents, for example, diethyl ether, dibutyl ether, THF, and the like, chloroform, methylene chloride, tetrachloroethane, and the like, for example, acetone, MEK, and the like, cyclohexane, octane, and the like are suitably selected. Of these, THF, acetone, MEK, cyclohexane and the like are preferably selected from the viewpoints of reactivity and product purity.
In order to efficiently replace the halogen element of the prepolymer with the aforementioned hydroxyl compound, the molar ratio of halogen / hydroxyl compound is 1 or more, preferably 2 or more, more preferably 3 to 20, more preferably 5 to 10 in range. Is selected. Further, the reaction time is preferably set by appropriately checking the residual halogen amount in order to completely replace the residual halogen amount to 100 ppm or less.

(Step (II): replacement step, second method)
As a second method of the substitution step, the halogen at both ends of the prepolymer may be reacted with the monohalosilyl compound (c) represented by the formula (vii) in order to convert the halogen to both of the substituents of the formula (ii). That is, the obtained prepolymer and the following formula (vii)

(In formula (vii), R ³ , R ⁴ and Y are the same as in formula (ii). Q is a halogen atom.)
You may react the compound represented by these.

In the second method, the reaction between the prepolymer and the monohalosilyl compound (c) can be carried out according to the prepolymer production conditions. In this case, however, the solvent exemplified in the first method is preferably used as the reaction solvent.
In order to further reduce the trimethylsilyl group content and halogen content of the polysilylcarbodiimide compound produced by the first and / or second methods, a combination of both methods can also be exemplified as a preferred embodiment. At this time, it is preferable to first produce a polysilylcarbodiimide compound by the first method and then apply the second method.
When a silylcarbodiimide compound (component B) is applied to polylactic acid, the halogen content is gradually converted to hydrogen halide, which catalyzes the hydrolysis resistance of polylactic acid, thus reducing the halogen content to 100 ppm or less. This is a key point of the present invention, but in order to reduce it to 0.01 ppm or less, a complicated operation such as repeating the above operation is required.
Furthermore, by applying such a method, in the silylcarbodiimide compound (component B), the content of trimethylsilyl groups in which R ³ , R ⁴ and Y in formula (ii) are each a methyl group is preferably 0.1 to 1000 ppm. Can be reduced. This is because, when the trimethylsilyl group is present in a large amount exceeding such a range, when it is applied to polylactic acid, bad odor generation may become remarkable.

When applied to polylactic acid, the silylcarbodiimide compound (component B) can be suitably used as a hydrolysis-resistant stabilizer because the deterioration of the working environment due to bad odor is suitably suppressed and the hue of the resin is less deteriorated.
The silylcarbodiimide compound (component B) is blended in one or more types of polylactic acid, but is blended in the range of 0.001 to 10 parts by weight per 100 parts by weight of polylactic acid (component A). If it is less than 0.001 part by weight, it is difficult to realize the heat-and-moisture resistance stability of the present invention, and when it exceeds 10 parts by weight, an undesirable phenomenon such as deterioration of the hue of the resin composition occurs. It is to do. From this viewpoint, the range of preferably 0.01 to 8 parts by weight, more preferably 0.05 to 7 parts by weight is selected.

<Polylactic acid (component A)>
Polylactic acid (component A) is obtained by direct polycondensation of L-lactic acid, D-lactic acid, and mesolactic acid, melt ring-opening polymerization of L-lactide, D-lactide, and meso-lactide, or solid phase polymerization of relatively low molecular weight oligomers. It includes poly L-lactic acid, poly D-lactic acid, polylactic acid in which these components are randomly or block copolymerized, and a mixture of these polylactic acids.
In the present invention, the polylactic acid (component A) preferably has a weight average molecular weight of 100,000 to 500,000 from the viewpoint of compatibility between moldability and physical properties of the molded product. When the weight average molecular weight is less than 100,000, the mechanical strength and toughness of the molded product are lowered, which is not preferable for practical use. Further, if the weight average molecular weight exceeds 500,000, the melt viscosity is high, and melt molding may be difficult. From this viewpoint, the weight average molecular weight is more preferably in the range of 110,000 to 350,000, and still more preferably in the range of 1 to 250,000.
In the present invention, poly-D-lactic acid has a D-lactic acid unit represented by the following formula (III) as a main repeating unit, preferably 90 to 100 mol% of D-lactic acid units and 0 to 10 mol% of D- Consists of copolymerized units other than lactic acid.
Further, the poly-L-lactic acid is mainly composed of L-lactic acid units represented by the following formula (III), preferably other than 90 to 100 mol% L-lactic acid units and 0 to 10 mol% L-lactic acid. Consists of copolymerized units. The D-lactic acid unit and the L-lactic acid unit, which are the main repeating units, are more preferably selected in the range of 95 to 100 mol%, more preferably 98 to 100 mol%. The copolymer unit other than the main repeating unit is preferably selected in the range of 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 2 mol%.

  Copolymerized units include units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like having functional groups capable of forming two or more ester bonds, and various polyesters, various polyethers, various types composed of these various components. Examples are units derived from polycarbonate and the like.

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

Poly L-lactic acid and poly D-lactic acid can be produced by a conventionally known reaction process, preferably by a process in which a metal-containing catalyst is applied.
That is, polylactic acid can be produced by a melt ring-opening polymerization method of L- or D-lactide, a solid phase polymerization method of low molecular weight polylactic acid, a dehydration condensation polymerization method of lactic acid, or the like. In the melt ring-opening polymerization or dehydration condensation polymerization method, a vertical reactor or a horizontal reactor equipped with a stirring blade for high viscosity such as a helical ribbon blade can be used alone or in combination in series or in parallel.
In the solid-state polymerization method, a solid in a temperature range between the glass transition temperature and the melting point of the prepolymer in a fixed vertical or horizontal reaction vessel or a reaction vessel (such as a rotary kiln) in which the vessel itself rotates like a tumbler or kiln. Polymerized in the state. These polymerization processes may be batch-wise, continuous, or semi-batch, or may be combined.

In the melt ring-opening polymerization, alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid, such as decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, ethylene glycol, trimethylolpropane, pentaerythritol, etc. Can be suitably used.
Metal-containing catalysts include alkali metals, alkaline earth metals, rare earths, transition metals, fatty acid salts such as aluminum, germanium, tin, antimony, titanium, carbonates, sulfates, phosphates, oxides, hydroxides , Halides, alcoholates and the like.
Among the tin compounds, tin (II) compounds are specifically exemplified by diethoxytin, dinonyloxytin, myristate tin (II), octylate tin (II), and stearate (II). And the like are preferably exemplified.
In the melt ring-opening polymerization of lactide, the amount of the catalyst used is 0.42 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol per 1 kg of lactide. .68 × 10 ^{−4 to} 42.1 × 10 ⁻⁴ mol, particularly preferably 2.53 × 10 ^{−4 to} 16.8 × 10 ⁻⁴ mol.

Prior to the use of polylactic acid, the metal-containing catalyst used in the polymerization is preferably deactivated by a conventionally known method, for example, by application of a deactivator. Examples of the deactivator include an organic ligand having an imino group and a coordination ability to a polymer metal catalyst, and an orthophosphoric acid represented by the formula xH ₂ O · yP ₂ O ₅ , x / y = 3, 2> x / y> 1, polyphosphoric acid referred to as diphosphoric acid, triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid and the like based on the degree of condensation and mixtures thereof, metaphosphoric acid represented by x / y = 1, especially trimetalin Acid, tetrametaphosphoric acid, ultraphosphoric acid represented by 1> x / y> 0 and having a network structure in which a part of the phosphorus pentoxide structure is left (these may be collectively referred to as metaphosphoric acid compounds). ), And acidic salts of these acids, monovalent and polyhydric alcohols, or partial esters of polyalkylene glycols, phosphorooxo acids or acidic esters thereof, phosphono-substituted lower aliphatic carboxylic acid derivatives and the like Metaphosphoric acid-based compounds are preferably used.

The metaphosphoric acid compound used in the present invention is a cyclic metaphosphoric acid in which about 3 to 200 phosphoric acid units are condensed, an ultra-regional metaphosphoric acid having a three-dimensional network structure, or their (alkal metal salt, alkaline earth metal salt, Onium salts). Among them, cyclic sodium metaphosphate, ultra-region sodium metaphosphate, phosphono-substituted lower aliphatic carboxylic acid derivative dihexylphosphonoethyl acetate (hereinafter sometimes abbreviated as DHPA) and the like are preferably used.
In the present invention, the polylactic acid (component A) is preferably crystalline from the viewpoints of moist heat resistance and heat resistance, and shows a crystal melting peak (Tmh) at 160 ° C. or higher by differential scanning calorimetry (DSC) measurement. The crystal melting heat (ΔHmh) is preferably 10 J / g or more. This is because the heat resistance can be suitably increased by satisfying the range of the crystal melting point and the crystal melting heat. In particular, from the viewpoint of heat resistance, the crystal melting heat is selected in the range of 15 to 90 J / g.

In order to improve heat resistance and moist heat resistance, the polylactic acid (component A) is preferably composed of poly L-lactic acid and poly D-lactic acid. Polylactic acid (component A) is composed of 90 to 100 mol% of L-lactic acid units and 0 to 10 mol% of units other than L-lactic acid units, as well as 90 to 100 mol% of D-lactic acid units. And 0 to 10 mol% of poly-D-lactic acid composed of units other than D-lactic acid. Polylactic acid (component A) is composed of poly-L-lactic acid and poly-D-lactic acid, and has a stereocomplex phase of 190 ° C. or higher (hereinafter sometimes abbreviated as complex phase) by DSC measurement. It is preferable to have.
In order to exhibit the heat resistance inherent in the stereocomplex phase polylactic acid, the degree of stereolation (S) defined by the following formula (1) of the polylactic acid (component A) is preferably 80 to 100%, more preferably 90%. It is -100%, More preferably, it is 95-100% of range. Particularly preferred is when the degree of stereoification is 100%.
S (%) = [ΔHms / (ΔHmh + ΔHms)] × 100 (1)
(ΔHms represents the crystal melting enthalpy of complex phase polylactic acid, and ΔHmh represents the crystal melting enthalpy of homophase polylactic acid.)
Furthermore, from the same viewpoint, the crystal melting temperature (Tms) of the complex phase polylactic acid is preferably 190 to 250 ° C, more preferably 200 to 230 ° C. The crystal melting enthalpy (ΔHms) by DSC measurement is preferably 20 J / g or more, more preferably 20 to 80 J / g, and further preferably 30 to 80 J / g. If the complex phase crystal melting temperature is less than 190 ° C., the significance of forming the complex phase becomes small. Further, when the temperature exceeds 250 ° C., it is necessary to mold at a high temperature of 250 ° C. or higher when molding a molded product, which may promote thermal decomposition of the resin. The same argument applies to the value of crystal melting enthalpy. Polylactic acid (component A) shows a crystal melting peak of 200 ° C. or higher by differential scanning calorimetry (DSC) measurement, and the ratio of the crystal melting peak of 200 ° C. or higher of the crystal melting peak is 80 to 100%. Is preferred.

Polylactic acid (component A) containing complex phase polylactic acid can be produced by contacting and mixing poly L-lactic acid and poly D-lactic acid at a predetermined weight ratio. Contact is a method of melt kneading after mixing a predetermined amount of poly L-lactic acid and poly D-lactic acid in the presence or absence of a solvent, and a method of kneading by adding one remaining after melting one of them. Can be adopted.
The solvent is not particularly limited, but for example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol and the like alone Or what mixed 2 or more types is preferable.
In the case of melt kneading, the contact temperature is selected in the range of 220 to 290 ° C., preferably 220 to 280 ° C., more preferably 225 to 275 ° C. from the viewpoint of improving the stability at the time of melting polylactic acid and the stereogenicity. .

Alternatively, as the contact, a block polylactic acid in which a poly L-lactic acid segment and a poly D-lactic acid segment are chemically bonded can also be suitably used. The block polymer can be produced by, for example, a method of sequential ring-opening polymerization, a method of polymerizing poly L-lactic acid and poly D-lactic acid, and then binding them with a chain exchange reaction or a chain extender, poly L-lactic acid. And poly-D-lactic acid are polymerized and blended, followed by solid-phase polymerization and chain extension, or a method of producing from racemic lactide using a stereoselective ring-opening polymerization catalyst. Among these, it is more preferable to use a high melting point block polymer obtained by sequential ring-opening polymerization and a polymer obtained by a solid phase polymerization method from the viewpoint of ease of production.
Although the contact kneading method is not particularly limited, a conventionally known batch type or continuous type melt mixing apparatus is preferably used. For example, melt stirring tank, single-screw or twin-screw extruder, kneader, non-shaft vertical stirring tank (finisher), Violac made by Sumitomo Heavy Industries, N-SCR made by Mitsubishi Heavy Industries, glasses blade made by Hitachi, lattice blade or Kenix type stirrer Alternatively, a Sulzer-type SMLX type static mixer equipped pipe type polymerization apparatus can be used, but a non-axial vertical stirring tank, N-SCR, which is a self-cleaning type polymerization apparatus in terms of productivity, quality of polylactic acid, especially color tone A biaxial extrusion ruder or the like is preferably used.

Polylactic acid (component A) composed of poly L-lactic acid and poly D-lactic acid has a stereoification rate (Sc) defined by the formula (2) according to the intensity ratio of diffraction peaks measured by wide-angle X-ray diffraction (WAXS). Is preferably 10% or more. The stereoization rate (Sc) is more preferably in the range of 20 to 100%, further preferably 30 to 100%, and particularly preferably 45 to 100%. When polylactic acid (component A) has Sc in the above range, the heat resistance and heat-and-moisture resistance of the molded product can be more suitably satisfied.
Sc (%) = [ΣISCi / (ΣISCi + IHM)] × 100 (2)
[However, ΣISCi = ISC1 + ISC2 + ISC3 and ISCi (i = 1 to 3) are the integrated intensities of diffraction peaks of complex phase polylactic acid crystals measured around 2θ = 12.0 °, 20.7 °, and 24.0 °, respectively. The summation, IHM, represents the integrated intensity IHM of diffraction peaks derived from homophase crystals appearing around 2θ = 16.5 °. ]
Furthermore, from the same viewpoint, the crystallinity obtained from the intensity ratio between the amorphous halo and the crystal peak by WAXS measurement is preferably at least 5%, more preferably 5 to 60%, still more preferably 7 to 60%, More preferably, it is 10 to 55% of range.

In order to increase the degree of stereolization and stereogenicity of polylactic acid (component A) and satisfy various crystallinity parameters, the weight ratio of poly D-lactic acid to poly L-lactic acid is 90/10 to 10/90. Preferably there is. More preferably, it is in the range of 80/20 to 20/80, more preferably 30/70 to 70/30, particularly preferably 40/60 to 60/40, and theoretically preferably as close to 1/1 as possible. .
Polylactic acid (component A) preferably has a lactide content of 1 to 5000 ppm by weight. Lactide in polylactic acid (component A) deteriorates the resin and deteriorates the color tone at the time of melt processing, and in some cases, it may be disabled as a product.

  Poly L-lactic acid and poly D-lactic acid immediately after melt ring-opening polymerization usually contain 1 to 5% by weight of lactide, but any time from the end of polymerization to molding of the polylactic acid (component A) composition In this stage, the lactide is obtained in a desired manner by a conventionally known lactide weight loss method, i.e., vacuum devolatilization in a single-screw or multi-screw extruder, or high vacuum treatment in a polymerization apparatus alone or in combination. Can be reduced to a range. The lower the lactide content, the better the melt stability and heat-and-moisture resistance of the resin, but there is also the advantage of lowering the resin melt viscosity, making it reasonable and economical to meet the desired purpose. is there. That is, it is reasonable to set it to 1-1000 wtppm at which practical melt stability and flow characteristics are achieved. More preferably, a range of 1 to 700 wtppm, more preferably 2 to 500 wtppm, and particularly preferably 5 to 100 wtppm is selected. A molded product made of polylactic acid (component A) having a lactide content in such a range can suitably improve so-called low gas properties required for electric and electronic parts.

<Stereoization accelerator>
In order to enhance the crystallinity of the polylactic acid (A component) used in the present invention, in particular, in the case of polylactic acid (A component) composed of poly L-lactic acid and poly D-lactic acid, the formation of a complex phase is stable and highly advanced. It is preferable to contain an additive in order to proceed.
The following are mentioned as an additive.

(1) Stereolization accelerator Polylactic acid (component A) preferably contains a phosphate ester metal salt represented by the following formula (I) or (II) as a stereolation accelerator.

In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₁ is an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. p is 1 or 2, q is 0 when M ₁ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₁ is an aluminum atom.

In the formula, R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. M ₂ is an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. p is 1 or 2, and q is 0 when M ₂ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₂ is an aluminum atom.

In these phosphoric acid ester metal salts, M ₁ and M ₂ are Na, K, Al, Mg, and Ca. In particular, K, Na, and Al can be preferably used. Among them, trade names manufactured by ADEKA Corporation, ADK STAB NA-10, NA-11, NA-21, NA-30, NA-35 and the like are exemplified as suitable agents.
The content of the phosphoric acid ester metal salt is preferably 0.001 to 2 parts by weight, more preferably 0.005 to 1 part by weight, still more preferably 0.01 to 100 parts by weight of polylactic acid (component A). -0.5 part by weight, particularly preferably 0.02-0.3 part by weight. When the amount is too small, the effect of improving the degree of stereoization is small, and when too large, the complex phase crystal melting point is lowered, which is not preferable.
Further, in order to enhance the action of the phosphate metal salt, it is preferable to use a crystallization nucleating agent described below in combination. As such a crystallization nucleating agent, various agents described below in the section of crystallization nucleating agent are used, among which calcium silicate, talc, kaolinite, and montmorillonite are preferably selected. The content of the crystal nucleating agent that strengthens the action of the phosphoric acid ester metal salt is preferably 0.05 to 5 parts by weight, more preferably 0.06 to 2 parts by weight, more preferably 100 parts by weight of polylactic acid (component A). Preferably it is 0.06-1 weight part.

(2) Stereolization aid Polylactic acid (component A) has an epoxy group, an oxazoline group, an oxazine group, an isocyanate group, a ketene group, and a carbodiimide group (hereinafter abbreviated as a specific functional group) as a stereolation aid. It is preferable to contain a compound having at least one group selected from the group consisting of The aforementioned silylcarbodiimide is suitably applied as a stereogenic aid.
In the present invention, the stereogenic assistant means that a specific functional group reacts with a molecular end of polylactic acid (component A) to partially link a poly L-lactic acid unit and a poly D-lactic acid unit, thereby producing a stereocomplex phase. It promotes formation.
As a stereogenic assistant, a known agent can be suitably applied as a carboxyl group blocking agent for conventional polyesters described below. Especially, a carbodiimide compound is suitably selected from the complex phase formation promotion effect.
However, in the present invention, the conventionally known agents described below can be suitably applied to the carbodiimide compound as a stereogenic aid, but the agent bleed-out, transpiration, and further deterioration of the working environment due to transpiration is suppressed. Therefore, it is preferable to apply the aforementioned low-volatile carbodiimide compound.
The content of the stereogenic assistant is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, and still more preferably 0.01 to 1 part by weight per 100 parts by weight of polylactic acid (component A). Part. If it is applied in a large amount beyond this range, there is a great concern that the resin hue will be deteriorated or plasticization will occur.
The above (1) and (2) can be applied alone, but it is preferable to apply them in combination because the formation of the stereocomplex phase can be more effectively promoted.

In the present invention, the carboxyl group concentration of polylactic acid (component A) is preferably 0.01 to 10 equivalents / 10 ⁶ g (hereinafter, equivalents / 10 ⁶ g may be abbreviated as eq / ton). More preferably, it is 0.02-5 eq / ton, More preferably, it is 0.02-3 eq / ton, Most preferably, it is 0.02-1 eq / ton. When the carboxyl group concentration is within this range, it is possible to obtain a resin composition that is excellent in heat-and-moisture resistance stability and excellent in melt stability and hydrolysis resistance. When the carboxyl group concentration is 10 eq / ton or less, a known carboxyl group-capping agent can be suitably applied to the polyester, but the carboxyl group-capping agent is not added, and the ester or amide is added with alcohol or amine. It can also be converted. Such a carboxyl group-capping agent is an agent that can be suitably applied as a stereogenic aid in the present invention.
As the carbodiimide compound that can be applied as a stereogenic aid in the present invention, for example, the above-mentioned silylcarbodiimide compound can be suitably applied. Conventionally known hydrocarbon-based carbodiimide compounds can also be applied as carboxyl group-capping agents and stereogenic aids, but as mentioned above, because of the deterioration of the hue of polylactic acid and the work environment, in its application, Attention is necessary.

  Examples of such hydrocarbon-based carbodiimide compounds include dicyclohexylcarbodiimide, diisopropylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, octyldecylcarbodiimide, di-t-butylcarbodiimide, dibenzylcarbodiimide, diphenylcarbodiimide, N-octadecyl-N′-phenylcarbodiimide. N-benzyl-N′-phenylcarbodiimide, N-benzyl-N′-tolylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, bis (p-aminophenyl) carbodiimide, bis (p-chlorophenyl) Carbodiimide, bis (o-chlorophenyl) carbodiimide, bis (o-ethylphenyl) carbodiimide, bis (p-ethylphenyl) Nyl) carbodiimide bis (o-isopropylphenyl) carbodiimide, bis (p-isopropylphenyl) carbodiimide, bis (o-isobutylphenyl) carbodiimide, bis (p-isobutylphenyl) carbodiimide, bis (2,5-dichlorophenyl) carbodiimide, bis (2,6-dimethylphenyl) carbodiimide, bis (2,6-diethylphenyl) carbodiimide, bis (2-ethyl-6-isopropylphenyl) carbodiimide, bis (2-butyl-6-isopropylphenyl) carbodiimide, bis (2 , 6-Diisopropylphenyl) carbodiimide, bis (2,6-di-t-butylphenyl) carbodiimide, bis (2,4,6-trimethylphenyl) carbodiimide, bis (2,4,6-triisopro Ruphenyl) carbodiimide, bis (2,4,6-tributylphenyl) carbodiimide, diβ-naphthylcarbosiimide, N-tolyl-N′-cyclohexylcarboimide, N-tolyl-N′-phenylcarbosiimide, p- Phenylenebis (o-toluylcarbodiimide), p-phenylenebis (cyclohexylcarbodiimide), p-phenylenenebis (p-chlorophenylcarbodiimide), 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, hexamethylenebis (cyclohexylcarbodiimide) ), Ethylene bis (phenylcarbodiimide), ethylene bis (cyclohexylcarbodiimide), and other mono- or polycarbodiimide compounds.

Of these, bis (2,6-diisopropylphenyl) carbodiimide and 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide are preferred from the viewpoints of reactivity and stability. Of these, industrially available dicyclohexylcarbodiimide and bis (2,6-diisopropylphenyl) carbodiimide can be suitably used.
Furthermore, a commercially available polycarbodiimide compound as the polycarbodiimide compound can be suitably used without the need for synthesis. Examples of such commercially available polycarbodiimide compounds include “Carbodilite” LA-1 sold under the trade name “Carbodilite” marketed by Nisshinbo Co., Ltd., HMV-8CA, and the like.
Epoxy compounds that can be used as stereogenic aids in the present invention and are known as carboxyl group-capping agents include glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, glycidyl imide compounds, glycidyl amide compounds, alicyclic types. Epoxy compounds can be preferably used. By blending such an agent, a polylactic acid resin composition and a molded product excellent in mechanical properties, moldability, heat resistance, and durability can be obtained.

  Examples of glycidyl ether compounds include, for example, stearyl glycidyl ether, phenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylene glycol diglycidyl ether, Bisphenol A obtained by condensation reaction of epichlorohydrin with polytetramethylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and other bisphenols such as bis (4-hydroxyphenyl) methane Diglycidyl ether type epoxy resin Etc. can be mentioned. Of these, bisphenol A diglycidyl ether type epoxy resins are preferred.

  Examples of glycidyl ester compounds include benzoic acid glycidyl ester, stearic acid glycidyl ester, persic acid glycidyl ester, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid Examples include acid diglycidyl ester, dodecanedioic acid diglycidyl ester, and pyromellitic acid tetraglycidyl ester. Of these, glycidyl benzoate and glycidyl versatate are preferred.

Examples of the glycidylamine compound include tetraglycidylamine diphenylmethane, triglycidyl-p-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, and triglycidyl isocyanurate.
As glycidyl imide and glycidyl amide compounds, N-glycidyl phthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3,6-dimethylphthalimide, N-glycidyl succinimide, N-glycidyl-1,2,3 , 4-tetrahydrophthalimide, N-glycidyl maleimide, N-glycidyl benzamide, N-glycidyl stearyl amide and the like. Of these, N-glycidylphthalimide is preferable.

As an alicyclic epoxy compound, 3,4-epoxycyclohexyl-3,4-cyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4,5-epoxycyclohexane- 1,2-dicarboxylic imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide and the like can be mentioned.
As other epoxy compounds, epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, cresol novolac type epoxy resins and the like can be used.

  In the present invention, the oxazoline compound that can be used as a stereogenic auxiliary and is known as a carboxyl group-capping agent includes 2-methoxy-2-oxazoline, 2-butoxy-2-oxazoline, 2-stearyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-benzyloxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-cyclohexyl-2 -Oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-o-ethylphenyl-2-oxazoline, 2-o-propylphenyl-2-oxazoline, 2- p-Phenylphenyl-2-oxazoline 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2′-bis (4-butyl-2-oxazoline), 2,2′-m -Phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4'-methyl-2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylenebis (2-oxazoline), 2,2′-ethylenebis (4 -Methyl-2-oxazoline), 2,2'-tetramethylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-cyclohexylenebis (2-oxazoline), 2,2'-diphenylene Screw (4 Methyl-2-oxazoline) and the like. Furthermore, the polyoxazoline compound etc. which contain the said compound as a monomer unit are mentioned.

In the present invention, oxazine compounds that can be used as a stereogenic auxiliary and are known as carboxyl group-capping agents include 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-hexyloxy-5, 6-dihydro-4H-1,3-oxazine, 2-decyloxy-5,6-dihydro-4H-1,3-oxazine, 2-cyclohexyloxy-5,6-dihydro-4H-1,3-oxazine, 2 -Allyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy-5,6-dihydro-4H-1,3-oxazine and the like.
Further, 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′- Ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylene Bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-P, P′-diphenylenebis (5,6-dihydro-4H-1,3-oxazine) and the like can be mentioned. Furthermore, the polyoxazine compound etc. which contain the above-mentioned compound as a monomer unit are mentioned.
Among the oxazoline compounds and oxazine compounds, 2,2′-m-phenylenebis (2-oxazoline) and 2,2′-p-phenylenebis (2-oxazoline) are preferably selected.

  Examples of the isocyanate compound that can be used as a stereolation aid in the present invention and are known as a carboxyl group-capping agent include aromatic, aliphatic, and alicyclic isocyanate compounds, and mixtures thereof.

Examples of the monoisocyanate compound include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.
As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate , (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate) mixture, cyclohexane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate , Tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl-1,4-diisocyanate, and the like.
Among these isocyanate compounds, aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate and phenyl isocyanate are preferable, but in the present invention, it is more preferable to apply an isocyanate compound which is a raw material for the low-volatility carbodiimide described above.

Examples of ketene compounds that can be used as a stereogenic aid in the present invention and are known as carboxyl group-capping agents include aromatic, aliphatic, and alicyclic ketene compounds, and mixtures thereof.
Specific examples of the compound include diphenyl ketene, bis (2,6-di-t-butylphenyl) ketene, bis (2,6-di-isopropylphenyl) ketene, dicyclohexyl ketene and the like. Among these ketene compounds, aromatic ketenes such as diphenyl ketene, bis (2,6-di-t-butylphenyl) ketene, and bis (2,6-di-isopropylphenyl) ketene are preferable.
One or two or more compounds can be appropriately selected and used as the agent that can be applied as the stereogenic assistant and the carboxyl group blocking agent. Promoting the formation of a block structure as a stereogenic assistant and sealing a carboxyl group terminal and a part of an acidic low molecular weight compound are exemplified as one of preferred embodiments.
The composition of the present invention includes a thermoplastic resin other than polylactic acid, a stabilizer, a crystallization accelerator, a filler, a release agent, an antistatic agent, a carboxyl group-reactive terminal without departing from the gist of the present invention. It can contain at least one selected from the group consisting of a sealant, a plasticizer, an impact stabilizer and the like.

<Thermoplastic resin>
If desired, examples of the thermoplastic resin applicable to the composition of the present invention include polyester resins other than polylactic acid resins, polyamide resins, polyacetal resins, polyolefin resins such as polyethylene resins and polypropylene resins, polystyrene resins, acrylic resins, and polyurethanes. Resin, chlorinated polyethylene resin, chlorinated polypropylene resin, aromatic and aliphatic polyketone resin, fluorine resin, polyphenylene sulfide resin, polyether ketone resin, polyimide resin, thermoplastic starch resin, AS resin, ABS resin, AES resin, ACS resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl ester resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy tree , Can be exemplified polyphenylene oxide resin, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, a thermoplastic resin such as polyvinyl alcohol resins.
In particular, it is preferable to blend at least one selected from polyester resins other than polyacetal resins and polylactic acid resins, for example, polyester resins such as PET, PTT, PBTT, and PEN, and polyamide resins.
By blending these resins, the surface properties, moldability, mechanical properties, durability, toughness and the like of the molded product made of the composition of the present invention can be made excellent.
The content of the thermoplastic resin is preferably 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, still more preferably 3 to 70 parts by weight, and still more preferably 5 to 5 parts by weight per 100 parts by weight of polylactic acid. 50 parts by weight. By blending these resins, a composition and a molded product having excellent characteristics can be obtained.

<Stabilizer>
The composition of the present invention preferably contains 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-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5 ′). -T-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-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-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl- -Hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3- t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane and the like.

  As a hindered amine compound, N, N′-bis-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis [3- (3′-Methyl-5′-t-butyl-4′-hydroxyphenyl) propionyl] diamine, N, N′-bis [3- (3,5-di-t-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) -T-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide and the like. Preferably, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate] and tetrakis [methylene-3- (3 ′, 5′-di-t-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-t-butylphenyl) phosphite, tetrakis ( 2,6-di-t-butylphenyl) 4,4′-biphenylene phosphite, bis (2,6-di-t-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-nonylphenyl) phosphite, tris (no Butylphenyl) phosphite, 4,4'-isopropylidene-bis (phenyl - dialkyl phosphite), and the like.
Among them, tris (2,6-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl) -4-Methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,6-di-t-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 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-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5- Di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-t-butyl-4′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (3,5- Di-t-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-t-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 pt-butylphenyl salicylate and p-octylphenyl salicylate.
Examples of the oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, and 2-ethoxy-3′-. Examples include dodecyl oxalic acid bisanilide.
Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3′-diphenyl acrylate and 2-ethylhexyl-cyano-3,3′-diphenyl acrylate.

  Examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2, 6,6-tetramethylpiperidine, 4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarba Yloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethylpi-4-peridyl) adipate, bis (2,2,6,6-tetramethylpi-4-peridyl) terephthalate, 1,2-bis (2,2,6,6-tetramethylpi-4-peridylo) Cis) -ethane, α, α′-bis (2,2,6,6-tetramethylpi-4-peridyloxy) -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 , 2,2,6,6 Examples include condensates of pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethanol. be able to.

  In this invention, a stabilizer may be used by 1 type and may be used in combination of 2 or more type. As the stabilizer, hindered phenol compounds and / or benzotriazole compounds are preferable. The content of the stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of polylactic acid (component A).

<Crystallization accelerator>
In the composition of the present invention, an organic or inorganic crystallization accelerator can be contained. By containing the crystallization accelerator, the action of the phosphoric acid ester metal salt can be further enhanced, and a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained. That is, by applying a crystallization accelerator, the moldability and crystallinity of polylactic acid (component A) are improved, and a molded product that is sufficiently crystallized in normal injection molding and has excellent heat resistance and moist heat resistance is obtained. be able to. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.

As the crystallization nucleating agent used in the present invention, those generally used as crystal nucleating agents for crystalline resins can be used, and both inorganic crystal nucleating agents and organic crystal nucleating agents can be used. .
As inorganic crystal 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, Examples thereof include montmorillonite, neodymium oxide, aluminum oxide, and phenylphosphonate metal salt. These inorganic crystal nucleating agents are treated with various dispersion 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. Some are preferred.

  Organic nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, lauric acid Sodium phosphate, 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, salicylate Examples include organic carboxylic acid metal salts such as zinc, aluminum dibenzoate, sodium β-naphthoate, potassium β-naphthoate, and sodium cyclohexanecarboxylate, and organic sulfonic acid metal salts such as sodium p-toluenesulfonate and sodium sulfoisophthalate. It is done.

In addition, stearic acid amide, ethylene bislauric acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide) and other organic carboxylic acid amides, 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 crystal nucleating agent 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 polylactic acid (component A).

<Filler>
In the present invention, an organic or inorganic filler can be contained. 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, cellulose fibers processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, Angola, cashmere, camel, etc., 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 collected directly from natural products, but may be recycled recycled waste paper 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-based adhesives such as vinyl acetate resin-based emulsions and acrylic resin-based emulsions when processing paper, polyvinyl alcohol-based adhesives, polyamide-based adhesives, etc. Preferred examples include those containing a hot melt adhesive.

In the present invention, the content of the organic filler is not particularly limited, but from the viewpoint of moldability and heat resistance, it is preferably from 1 to 300 parts by weight, more preferably from 100 parts by weight of polylactic acid (component A). 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, and particularly preferably 15 to 100 parts by weight. When the content of the organic filler is less than 1 part by weight, the effect of improving the moldability of the composition is small, and when 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, 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, Elestite, Gypsum fiber, Silica fiber, Silica / Alumina fiber, Zirconia fiber, Boron nitride fiber, Silicon nitride fiber, Boron fiber and other fibrous inorganic fillers, layered silicate, layered silicic acid exchanged with organic onium ions Salt, 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, shirasu balloon, Calcium, magnesium carbonate, barium sulfate, oxide Karushikumu, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, include plate-like or granular inorganic fillers such as dawsonite and white clay.

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. Also good.
The content of the inorganic filler is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 50 parts by weight with respect to 100 parts by weight of polylactic acid (component A). Especially preferably, it is 1-30 weight part, Most preferably, it is 1-20 weight part.

<Release agent>
The composition of the present invention preferably contains 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. As the fatty acid metal salt, an antari (earth) metal salt of a fatty acid having 6 to 40 carbon atoms is preferable, 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 array acid amides, erucic acid amides, behenic acid amides and the like.
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 stearate, pentaerythritol adipate stearate, and sorbitan monobehenate. 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 polylactic acid (component A).

<Antistatic agent>
Examples of the antistatic agent used in the present invention include (β-lauramidopropionyl) trimethylammonium sulfate, quaternary ammonium salts such as sodium dodecylbenzenesulfonate, sulfonate compounds, and alkyl phosphate compounds. It is done. 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 polylactic acid (component A).

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

As a polyester plasticizer, acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, Examples thereof include polyesters composed of diol components such as 1,6-hexanediol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or a monofunctional alcohol.
Examples of the glycerol plasticizer include glycerol monostearate, glycerol distearate, glycerol monoacetomonolaurate, glycerol monoacetomonostearate, glycerol diacetomonooleate, and glycerol monoacetomonomontanate.
Polyvalent carboxylic acid plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellitic acid tributyl, trimellitic acid trioctyl, Trimellitic acid esters such as trihexyl meritate, isodecyl adipate, adipic acid esters such as adipate-n-decyl-n-octyl, citrate esters such as tributyl acetylcitrate, and bis (2-ethylhexyl) azelate Examples include sebacic acid esters such as azelaic acid ester, dibutyl sebacate, and bis (2-ethylhexyl) sebacate.

Examples of the phosphate ester plasticizer include tributyl phosphate, tris phosphate (2-ethylhexyl), trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylhexyl phosphate, and the like.
Polyalkylene glycol plasticizers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide.propylene oxide) block and / or random copolymers, ethylene oxide addition polymers of bisphenols, tetrahydrofuran addition polymers of bisphenols, etc. And end-capping compounds such as a terminal epoxy-modified compound, a terminal ester-modified compound, and a terminal ether-modified compound.
Examples of the epoxy plasticizer include an epoxy triglyceride composed of alkyl epoxy stearate and soybean oil, and an epoxy resin using bisphenol A and epichlorohydrin as raw materials.

Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol-bis (2-ethylbutyrate), and fatty acids such as stearamide. Examples thereof include fatty acid esters such as amide and butyl oleate, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.
As the plasticizer, at least one selected from polyester-type plasticizers and polyalkylene-type plasticizers can be preferably used, and only one type may be used, or two or more types may be used in combination.
The content of the plasticizer is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, still more preferably 0.1 to 10 parts by weight per 100 parts by weight of polylactic acid (component A). is there. In the present invention, each of the crystal nucleating agent and the plasticizer may be used alone, or more preferably used in combination.

<Impact resistance improver>
The impact resistance improver used in the present invention can be used to improve the impact resistance of thermoplastic resins, 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 salt (so-called ionomer) ethylene-glycidyl (meth) acrylate copolymer, ethylene-acrylate copolymer (for example, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer), 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) , Styrene-a A random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene grafted with styrene, butadiene-acrylonitrile copolymer), polyisobutylene, isobutylene and butadiene or Examples include copolymers with isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber, and the like.

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, any of the various (co) polymers mentioned in the above specific examples can be used as the impact resistance improver of the present invention, such as a randomum copolymer, a block copolymer, and a block copolymer.
The content of 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 polylactic acid (component A).

<Others>
Moreover, in this invention, you may contain thermosetting resins, such as a phenol resin, a melamine resin, a thermosetting polyester resin, a silicone resin, an epoxy resin, in the range which is not contrary to the meaning of this invention. In the present invention, flame retardants such as bromine, phosphorus, silicone, and antimony compounds may be included within the scope 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, chromophthal yellow, phthalocyanine type such as phthalocyanine blue and fast sky blue, and condensed polycyclic colorants such as indanthrone blue In addition, additives such as slidability improvers such as graphite and fluorine resin may be added. These additives can be used alone or in combination of two or more.

A composition containing these additives can be prepared by mixing the respective components. For the mixing, a tumbler, a V-type blender, a super mixer, a nauter mixer, a Banbury mixer, a kneading roll, a monoaxial or biaxial extruder can be used. The resulting composition can be molded as it is or after being once pelletized with a melt extruder.
The shape of the pellet may be any shape such as a spherical shape, a die shape, a linear shape, a curved shape, and a cross-sectional shape such as a round shape, an oval shape, a flat shape, a triangular shape, a polygon shape having a square shape or a star shape. However, it is preferable to have a shape suitable for molding the pellets by various molding methods. Specifically, the pellet length is preferably 1 to 7 mm, the major axis is 3 to 5 mm, and the minor axis is 1 to 4 mm. Further, it is preferable that the shape does not vary.

<Melformed product>
The melt-molded product comprising the composition of the present invention is an injection-molded product, an extrusion-molded product, a vacuum, a pressure-molded product, a blow-molded product, etc., specifically, a composite with pellets, fibers and cloth, and other materials. It includes compression molded products such as fiber structures, films, sheets, and sheet nonwoven fabrics. The melt-molded product is preferably a film, fiber, fiber structure or injection-molded product.
As for the pellet of the present invention, the melt molding method is not limited at all, and those produced by a known pellet production method can be suitably used. That is, the polylactic acid (component A) composition laid out in the form of a strand or plate is in the air after the resin is completely solidified or not completely solidified and still in a molten state, or Methods such as cutting in water are conventionally known, but any of them can be suitably applied in the present invention.
Conventionally known molding methods can be applied to the injection molded product of the present invention without any limitation. 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 more, more preferably Is 60 ° C. or higher, more preferably 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.
In addition, these molded products include various housings, gears, gears, etc. Electronic parts, building members, civil engineering members, agricultural materials, automobile parts (interior and exterior parts, etc.), daily parts and the like can be mentioned.

<Fiber and fiber structure>
For the polylactic acid fiber and fiber structure of the present invention, materials obtained by ordinary melt spinning and subsequent post-processing steps can be preferably used. That is, after the polylactic acid (component A) is melted by an extruder type or pressure melter type melt extruder, it is measured by a gear pump, filtered in a pack, and then monofilament through a nozzle provided in 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, added with oil, and wound. The winding speed is not particularly limited, but is preferably in the range of 300 m / min to 5,000 m / min because a stereocomplex crystal is easily formed.

Further, from the viewpoint of stretchability, a winding speed at which the stereo ratio 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.
Following the stretching, it is preferable that the heat treatment be performed at a temperature of 170 ° C. or higher and lower than the melting point of polylactic acid A before winding. In addition to the hot roller, any method such as a contact heater or a non-contact hot plate can be adopted for the heat treatment. The stretching temperature is preferably in the range of 70 to 140 ° C., particularly preferably 80 to 130 ° C., from the polylactic acid glass temperature. After stretching, by heat-setting at 170 ° C. to 220 ° C. under tension, a polylactic acid fiber having a high stereo ratio and low heat shrinkability and a strength of 3.5 cN / dTex or more can be obtained.

The fiber having high strength and excellent heat resistance and heat-and-moisture resistance stability according to the present invention can take the form of various fiber structures such as molded articles such as fiber knitted fabrics, nonwoven fabrics and cups. Specifically, thread form products such as sewing thread, embroidery thread, string, fabric such as woven fabric, knitting, nonwoven fabric, felt, outer clothes such as shirt, blouson, pants, coat, sweater, uniform, underwear, pantyhose, socks, Lining, interlining, sports clothing, high value-added clothing products such as women's clothing and formal wear, clothing products such as cups and pads, curtains, carpets, chair upholstery, mats, furniture, baskets, furniture upholstery, wall materials, etc. Products for daily use such as belts and slings, as well as various textile products such as canvas, belts, nets, ropes, heavy cloth, bags, industrial materials such as felts and filters, vehicle interior products, and artificial leather products.
The fiber and fiber structure of the present invention may be used alone with polylactic acid (component A) fiber, or may be mixed with other types of fibers. In addition to various combinations with fiber structures composed of other types of fibers, mixed modes include mixed yarns with other fibers, composite false twisted yarns, mixed spun yarns, long and short composite yarns, fluid processed yarns, covering yarns, and twisted yarns. Examples thereof include union, union, pile, pile, mixed cotton, mixed non-woven fabric of long fibers and short fibers, and felt. When mixed, the mixing ratio is selected to be 1% by weight or more, more preferably 10% by weight or more, and further preferably 30% by weight or more in order to exhibit the characteristics of polylactic acid (component A). Examples of other fibers to be mixed include cellulose fibers such as cotton, hemp, rayon, and tencel, wool, silk, acetate, polyester, nylon, acrylic, vinylon, polyolefin, and polyurethane.

<Film, sheet>
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 the case of forming a film, if a material obtained by melt-kneading polylactic acid (component A) and various components previously treated can be used, it can be molded through melt-kneading at the time of extrusion molding. When extruding an unstretched film, an unstretched film with few surface defects can be obtained by blending a molten resin with an electrostatic adhesive such as a sulfonic acid quaternary phosphonium salt.
Moreover, an unstretched film can also be cast-molded by melt | dissolving, casting, and drying-solidifying polylactic acid (A component) 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 orthogonal 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, tubular stretching, or the like. 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.
As described above, the “solution treatment” of a film or sheet can be carried out continuously or batchwise. However, a mode in which the film or sheet is continuously carried out in a morphological production process, that is, a mode of coating can be exemplified as a preferred example.

  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, although an Example demonstrates this invention further more concretely, this invention does not receive any limitation by this. The physical properties were measured by the following methods.

(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer
The weight average molecular weight and number average molecular weight of the polymer were measured by gel permeation chromatography (GPC) and converted to standard polystyrene.
As a GPC measuring instrument, a differential refractometer, Shimadzu Corporation RID-6A, was used as a detector. As columns, Tosoh Corp. TSKgelG3000HXL, TSKgelG4000HXL, TSKgelG5000HXL and TSKguardcocumHXL-L were arranged in series. A sample having a concentration of 1 mg / ml (chloroform containing 1% hexafluoroisopropanol) was analyzed and measured using chloroform as an eluent at a temperature of 40 ° C., a flow rate of 1.0 ml / min.

(2) Hue The color b * value of the hue of the sample was measured with a Z-1001DP color difference meter manufactured by Nippon Denshoku Industries Co., Ltd. The color b value is a parameter of yellowness of the sample, and the smaller this value, the better. If the color b value is large, the commercial value may be reduced. In the present invention, a b value of 4 or less was determined to be acceptable.

(3) Lactide content The sample was dissolved in hexafluoroisopropanol and quantified by C13 method NMR.

(4) Carbodiimide content The content was measured by comparison between resin characteristic absorption and carbodiimide characteristic absorption using a Magna-750, Fourier transform infrared spectrophotometer manufactured by Thermo Nicolet.

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

(6) Stereo ratio (Sc)
Using a ROTA FLEX RU200B type X-ray diffractometer manufactured by RIKEN, the diffraction intensity profile in the equator direction was determined, and each of the stereocomplex crystals derived from 2θ = 12.0 °, 20.7 °, and 24.0 ° From the total intensity ΣISCi of the integrated intensity of diffraction peaks and the integrated intensity IHM of diffraction peaks derived from homophase crystals appearing in the vicinity of 2θ = 16.5 °, the stereo ratio (Sc ratio) was determined according to the following formula (2).
Measurement conditions X-ray source Cu-Kα ray (confocal mirror)
Output 45kV x 70mA
Slit 1mmΦ-0.8mmΦ
Camera length 120mm
Integration time 10 minutes Sc (%) = [ΣISCi / (ΣISCi + IHM)] × 100 (2)
Here, ΣISCi = ISC1 + ISC2 + ISC3 and ISCi (i = 1 to 3) are integrated intensities of diffraction peaks in the vicinity of 2θ = 12.0 °, 20.7 °, and 24.0 °, respectively.

(7) Degree of stereoization (S), measurement of crystal melting temperature of stereocomplex polylactic acid In the present invention, the degree of stereomation and crystal melting temperature of stereocomplex polylactic acid are determined by DSC (TA Instrument, TA-2920). The crystal melting temperature and the crystal melting enthalpy were measured, and the enthalpy was determined from the enthalpy according to the following formula (1).

S (%) = [ΔHms / (ΔHmh + ΔHms)] × 100 (1)
(ΔHms = melting enthalpy of complex phase crystal, ΔHmh = melting enthalpy of homocrystal)

(8) Hydrolysis resistance stability Hydrolysis resistance stability is passed when the reduced viscosity retention is 80% or higher when treated in a pressure cooker at 120 ° C. and 100% RH for 2 hours, and 85% or higher is excellent. When it was less than 80%, it was determined to be rejected.
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. .

(9) Melt stability The sample was determined by the melt viscosity retention after holding at 260 ° C. for 10 minutes, and 80% or more was determined to be acceptable. The melt stability is a parameter of the stability of the resin staying in the apparatus at the time of resin molding, and it was determined that molding can be performed without problems when the melt stability exceeds 80%. When the retention rate was more than 85%, it was judged to be excellent and when it was less than 80%, it was judged to be unacceptable. The melt viscosity was measured at 260 ° C. according to JIS K7199 with Capillograph 10 manufactured by Toyo Seiki Seisakusho.

(10) Quality of work environment When the process worker did not feel the isocyanate odor particularly, it was judged acceptable.

(11) The silylcarbodiimide compound was analyzed by the following method.
(A) Average polymerization degree of polymer (n)
The average degree of polymerization (n) of the polymer is the integral of R (R1 to R4) bonded to the terminal Si by ¹ H-NMR, the peaks derived from X and Y, and R ¹ and R ² bonded to Si in the repeating unit. Quantified from the ratio. For NMR, JNR-EX270 manufactured by JEOL Ltd. was used. Deuterated chloroform was used as the solvent.
(A) Presence / absence of carbodiimide skeleton in silylcarbodiimide compound The presence / absence of carbodiimide skeleton in silylcarbodiimide compound was confirmed by FT-IR at 2100-2200 cm ⁻¹ characteristic of carbodiimide. For FT-IR, Magna-750 manufactured by Thermo Nicolet was used.
(U) Trimethylsilyl group content in silylcarbodiimide compound The trimethylsilyl group content in the silylcarbodiimide compound was quantified by a gas chromatograph mass spectrometer. As a gas chromatograph mass spectrometer, HP5973 manufactured by Yokogawa Analytical Co., Ltd. was used.
(D) Hydrolyzable halogen content in silylcarbodiimide compound The hydrolyzable halogen content in the silylcarbodiimide compound was quantified with a gas chromatograph mass spectrometer. As a gas chromatograph mass spectrometer, HP5973 manufactured by Yokogawa Analytical Co., Ltd. was used.

[Production Example 1] Prepolymer; P1- (10)
Bistrimethylsilylcarbodiimide (a) (10.25 parts by weight, 0.055 mole) and diphenyldichlorosilane (b) (12.66 parts by weight, 0.05 mole) are thermometer, stirring device, distillation device and heating device. Was allowed to react at 155 to 160 ° C. for 2.5 hours until trimethylchlorosilane distilled out (10, 7 parts by weight, 0.099 mol). Further, at the same temperature, the degree of vacuum was strengthened to 0.67 kPa, and the reaction was performed for 3 hours to produce a rubber-like prepolymer. ^The average degree of polymerization was 10 from ¹ H-NMR, IR, and hydrolyzable halogen content analysis. In P1- (10), P1 represents the prepolymer structure, and (10) represents the degree of polymerization.

[Production Examples 2-3] Prepolymer; P1- (18), P1- (5)
In Production Example 1, the molar ratio of (a) and (b) was 1: 1.01 (Production Example 2) and 1: 1.3 (Production Example 3), respectively. Prepolymers having an average degree of polymerization of 18 and 5: P1- ( 18), P1- (5) was produced.

[Production Examples 4 to 5] Prepolymer: P2- (9), P3- (11)
In Production Example 1, diphenyldichlorosilane was replaced with methyloctadecyldichlorosilane (Production Example 4; P-2- (9)) and cyclohexylmethyldichlorosilane (Production Example 5; P3- (11)), respectively. 9 and 11 prepolymers; P2- (9) and P-3- (11) were prepared.

[Production Example 6]
0.5 parts by weight of P1- (10) produced in Production Example 1 was dissolved in 5 parts by weight of THF, mixed with 10 parts by weight of stearyl alcohol having a large excess molar ratio, and charged into the reactor used in Production Example 1. And reacted at 100 ° C. for 10 hours. After the reaction, the lower phase polysilylcarbodiimide-containing layer was taken out, dissolved in chloroform, and washed with pure water until neutral.
After the chloroform solution of polysilylcarbodiimide is dried over anhydrous sodium sulfate, the solvent is distilled off under vacuum to have a chloro content as hydrolyzable halogen of 10 ppm and a trimethylsilyl group content of 50 ppm. In the formula (i), R ¹ to R ⁴ is a phenyl group, X, Y is the average degree of polymerization 10 stearyl group poly (diphenylsilane diyl - carbodiimide-1,3-diyl): S1- (10) was obtained. In S1- (10), S1 represents the polymer structure, and (10) represents the degree of polymerization.

[Production Examples 7 to 8]
The prepolymers of Production Examples 2 and 3 were treated in the same manner as in Example 1 to obtain poly (diphenylsilanediyl-carbodiimide-1,3-diyl): S1- (18 having a chloro content of 11 ppm and a trimethylsilyl group content of 45 ppm ), Poly (diphenylsilanediyl-carbodiimide-1,3-diyl): S1- (5).

[Production Examples 9 to 10]
Using Prepolymers of Production Examples 4 and 5; P2- (9), P3- (11) and using phenol and isopropyl alcohol as hydroxy compounds, as in Production Example 1, except for Production Example 10 The reaction temperature was changed to 50 ° C., R ¹ and R ² were methyl groups, R ³ and R ⁴ were octadecyl groups, X and Y were phenoxy groups, and poly [(methyl) having an average degree of polymerization of 9 (Octadecyl) silanediyl-carbodiimide-1,3-diyl]: S2- (9) in which R ¹ and R ² are methyl groups, R ³ and R ⁴ are cyclohexyl groups, and X and Y are isopropoxy groups. Of poly [(methyl) (cyclohexyl) silanediyl-carbodiimide-1,3-diyl]: S3- (11).

[Production Example 11]
Prepolymer produced in Production Example 1: 1 part by weight of P1- (10) and 0.5 weight of dimethyldodecylsilane chloride were reacted at 100 ° C. for 24 hours. The reaction mixture was dissolved in chloroform and washed with pure water until neutral.
After drying a chloroform solution of polysilylcarbodiimide with anhydrous sodium sulfate, the solvent was distilled off under vacuum to have a chloro content of 10 ppm and a trimethylsilyl group content of 10 ppm. In formula (i), R ¹ and R ² are phenyl Poly (diphenylsilanediyl-carbodiimide-1,3-diyl) having an average polymerization degree of 10 wherein X is a dimethyldodecylsilyl group, R ³ and R ⁴ are methyl groups, and Y is a dodecyl group: S11- (10) Obtained.

[Production Example 100-1] (Production of poly L-lactic acid: PLLA1)
To 100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory Co., Ltd., optical purity 100%), 0.005 part by weight of tin octylate was added, and the reactor was stirred at 180 ° C. in a nitrogen atmosphere with a stirring blade. For 2 hours, adding 1.2 equivalents of phosphoric acid as a catalyst deactivator to tin octylate, and then removing the remaining lactide at 13.3 Pa to obtain chips to obtain poly L-lactic acid It was. The obtained L-lactic acid had a weight average molecular weight of 152,000, a glass transition point (Tg) of 55 ° C., a melting point of 175 ° C., a carboxyl group content of 14 eq / ton, and a lactide content of 350 wtppm.

[Production Example 100-2] (Production of poly-D-lactic acid: PDLA1)
The L-lactide of Production Example 1-1 was changed to D-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%), and polymerization was performed under the same conditions to obtain poly-D-lactic acid. The resulting poly-D-lactic acid had a weight average molecular weight of 151,000, a glass transition point (Tg) of 55 ° C., a melting point of 175 ° C., a carboxyl group content of 15 eq / ton, and a lactide content of 450 wtppm. The results are summarized in Table 1.

[Example 1]
100 parts by weight of poly L-lactic acid (PLLA1) obtained in Production Example 100-1, 0.3 parts by weight of metal phosphate (“ADEKA STAB” NA-11, manufactured by ADEKA Corporation) and a crystallization nucleating agent (MAP6) : Nippon Talc Co., Ltd., fine talc, “Micro Ace” P-6) 0.5 parts by weight was mixed with a blender, vacuum dried at 110 ° C. for 5 hours, and then from the first supply port of the biaxial kneader, 1 part by weight of carbodiimide S1- (10) of Production Example 6 was supplied from the second supply port, melt kneaded and extruded while evacuating at a cylinder temperature of 240 ° C. and a vent pressure of 13.3 Pa, and stranding into the water tank Was taken and converted into a chip with a chip cutter to obtain a silylcarbodiimide compound-containing polylactic acid composition (A1) resin of Production Example 6. The obtained resin showed a single melting peak of a stereocomplex crystal composed of poly-L-lactic acid and poly-D-lactic acid in a differential scanning calorimeter (DSC) measurement, and the melting point was 220 ° C.
The hue, carboxyl group concentration, melt viscosity stability, and heat-and-moisture stability of the resulting resin are summarized in Table 2. During the pellet manufacturing operation, the working environment was maintained well with almost no isocyanate odor.

[Example 2]
In Example 1, polylactic acid: PLLA was changed to PDLA, and other conditions were similarly used to prepare polylactic acid (A2) composition pellets. During the pellet manufacturing operation, the working environment was maintained well with almost no isocyanate odor. Table 2 summarizes the hue, carboxyl group concentration, melt viscosity stability, heat-and-moisture stability, and working environment of the obtained resin.

[Comparative Example 1]
The carbodiimide compound in Example 1 was changed to LA1, and other conditions were the same, and pellets of a polylactic acid (CA) composition were prepared. The hue of the pellet was poor, and an isocyanate odor was strongly felt during pelletization, and the working environment was judged to be poor. Table 2 summarizes the color tone, carboxyl group concentration, lactide content, melt viscosity stability, moist heat resistance stability, and working environment of the obtained resin.

[Comparative Example 2]
A pellet of the composition was prepared in the same manner as in Comparative Example 1 except that no carbodiimide was added. The results are summarized in Table 2. At this time, it is clear that there is a problem in the melt stability and wet heat resistance of the composition.

[Example 3]
After 50 parts by weight of each of the pellets of Example 1 and Example 2 were vacuum dried at 110 ° C. for 5 hours, they were melt kneaded and extruded while being evacuated at 230 ° C. and a vent pressure of 13.3 Pa in a biaxial kneader. Strands were taken in a water tank and chipped with a chip cutter to produce polylactic acid (A3) composition pellets.

[Example 4]
In the same manner as in Example 3, except that 50 parts by weight of PLLA1 and PDLA1 and 0.3 part by weight of a phosphoric acid ester metal salt (“ADEKA STAB” NA-11 or NA71 manufactured by ADEKA) were mixed with a blender, 110 ° C., After vacuum drying for 5 hours, 1 part by weight of the carbodiimide compound shown in Table 3 is supplied from the second supply port from the first supply port of the kneader, and melt-kneaded and extruded while evacuating at a vent pressure of 13.3 Pa. Strands were taken in a water tank and formed into chips with a chip cutter to produce polylactic acid (A4) composition pellets. When producing the pellets, the working environment was maintained well with almost no isocyanate odor. Table 3 summarizes the degree of stereoification, carboxyl group concentration, melt viscosity stability, moist heat resistance stability, and working environment of the obtained resin.

[Examples 5 to 9]
In the same manner as in Example 4, except that the amounts and types of additives listed in Table 3 were applied to produce polylactic acid (A5-9) composition pellets. Various physical properties and others are summarized in Table 3. These compositions passed the conditions of the present invention, and the working environment was well maintained with almost no isocyanate odor during working.

[Comparative Examples 3 to 4]
The pellets of the polylactic acid (CA3, CA4) composition were produced in the same manner as in Example 4 except that the amounts and types of additives listed in Table 3 were applied. Various physical properties and others are summarized in Table 3. In Comparative Example 3, the working environment was judged to be poor while the odor of isocyanate was felt during the pelletization work, and the hue of the composition was judged to be poor. Moreover, in Comparative Example 4, the melt stability and the moist heat resistance itself are inferior and are out of the question.

  As can be easily understood from Tables 2 and 3, it is understood that the object of the present invention is suitably achieved by applying a silylcarbodiimide compound.

[Example 10]
The polylactic acid (A6) composition of Example 6 was melted at 260 ° C. using a melt spinning machine with a single-screw rudder and discharged from a 0.25Φ, 36-hole die at 40 g / min. The temperature under the pack immediately after discharge was 230 ° C., cooled by a spinning cylinder, converged, an oil agent was added, and the undrawn yarn was wound at a speed of 500 m / min. This undrawn yarn having a Sc conversion rate of 0% and a stereolation degree of 95% was drawn 4.9 times at 90 ° C. and then heat-set at 180 ° C. to obtain 160 dtex / 36 fil polylactic acid fibers. The obtained drawn yarn showed a single melting peak of a stereocomplex crystal composed of poly-L-lactic acid and poly-D-lactic acid in a differential scanning calorimeter (DSC) measurement, and the melting point was 222 ° C. Further, the Sc conversion ratio in wide-angle X-ray diffraction measurement was 45%, the strength of the fiber was 4.5 cN / dtex, and the elongation was 30%, so that practically sufficient strength and iron resistance were retained. The hue of the fiber was good, the heat and humidity resistance was 95%, and the working environment was judged to be good in the spinning and drawing processes.

[Comparative Example 5]
The polylactic acid (CA3) composition pellets of Comparative Example 3 were melted at 260 ° C. using a melt spinning machine with a uniaxial rudder and discharged from a 0.25Φ, 36-hole die at 40 g / min. The temperature under the pack immediately after discharge was 230 ° C., cooled by a spinning cylinder, converged, an oil agent was added, and the undrawn yarn was wound at a speed of 500 m / min. This undrawn yarn having a Sc conversion rate of 0% and a stereolation degree of 95% was drawn 4.9 times at 90 ° C. and then heat-set at 180 ° C. to obtain a 160 dtex / 36 fil polylactic acid fiber. The obtained drawn yarn showed a single melting peak of a stereocomplex crystal composed of poly-L-lactic acid and poly-D-lactic acid in a differential scanning calorimeter (DSC) measurement, and the melting point was 222 ° C. Further, the Sc conversion ratio in wide-angle X-ray diffraction measurement was 45%, the strength of the fiber was 4.5 cN / dtex, and the elongation was 34%. The fiber has a strong yellowish hue and heat and humidity resistance of 82%, which is considerably lower than that of Example 10. In the spinning and drawing processes, particularly when packed, the isocyanate odor is felt strongly, and the working environment is also good. It was judged as bad.

[Example 11]
0.5 parts by weight of tetrabutylphosphonium 3,5-dicarboxybenzenesulfonate per 100 parts by weight of the polylactic acid (A6) of Example 6 was mixed with a Henschel mixer, dried at 110 ° C. for 5 hours, and then biaxially extruded. The mixture was melt kneaded at a cylinder temperature of 230 ° C. in a machine, melt-extruded into a film at a die temperature of 230 ° C., and adhered and solidified to the surface of the mirror-cooled drum by electrostatic casting using a platinum-coated linear electrode.
The unstretched film was stretched at a stretching temperature of 100 ° C., stretched 2.0 times in the longitudinal direction, 2.3 times in the transverse direction, and further heat-set at 145 ° C. to obtain a biaxially stretched film having a thickness of about 50 μm. These films were successfully formed, stretched and heat-set without problems.
The obtained film had good breaking strength (MD / TD was 57/57 MPa, breaking elongation (MD / TD) 81/73%, and total light transmittance was 90% or more. The thermal stability was 95%, and the working environment in the film forming process was judged to be good.

[Comparative Example 6]
Using the polylactic acid (CA3) composition pellet of Comparative Example 3, a film was formed and formed in the same manner as in Example 11.
The resulting film had good breaking strength (MD / TD was 57/57 MPa, breaking elongation (MD / TD) 81/73%, and total light transmittance was 90% or more. Hue of the film. Has a strong yellowishness and a heat and humidity resistance of 85%, which is a lower level than in Example 11. Also, in the film forming process, particularly in the periphery of the die, the isocyanate odor is strong, and the working environment is It was judged as bad.

[Examples 12 to 14]
Using the pellets produced in Examples 7 to 9, injection molding was performed at a mold temperature of 110 ° C. and a clamping time of 2 minutes, and the obtained molded product was white and a molded piece having a good shape was obtained. All of these molded articles had good heat and heat resistance of 98%, and there was no isocyanate odor at the time of molding, and it was judged that the molding work environment was good.

Claims (12)

A composition containing 100 parts by weight of polylactic acid (component A) and 0.001 to 10 parts by weight of a silylcarbodiimide compound (component B). A compound in which the silylcarbodiimide compound (component B) mainly comprises a repeating unit represented by the following formula (i), has a polymerization degree of 1 to 20, and has a substituent represented by X or the following formula (ii) at the terminal. The composition according to claim 1.

(R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. X and Y are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Alkyloxy groups, cycloalkyloxy groups having 5 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, or polyalkylenes whose ends are sealed with ester groups or ether groups It is an oxy group.) In formulas (i) and (ii), the silylcarbodiimide compound (component B) has a total number of carbon atoms of R ¹ and R ² of 10 or more, and a total number of carbon atoms of R ³ and R ⁴ of 10 or more. The composition of claim 1. The composition according to claim 2 or 3, wherein the degree of polymerization of the silylcarbodiimide compound (component B) is 6-12. The composition according to any one of claims 2 to 4, wherein the content of the trimethylsilyl group of the silylcarbodiimide compound (component B) is 0.1 to 200 ppm. The composition according to any one of claims 2 to 5, wherein the hydrolyzable halogen content of the silylcarbodiimide compound (component B) is 0.01 to 100 ppm. Polylactic acid (component A) is composed of units other than 90 to 100 mol% L-lactic acid units and 0 to 10 mol% L-lactic acid units, and 90 to 100 mol% D-lactic acid units The composition according to any one of claims 1 to 6, comprising poly D-lactic acid composed of units other than 0 to 10 mol% of D-lactic acid. The composition according to claim 7, wherein the polylactic acid (component A) is crystalline polylactic acid that exhibits a crystal melting peak of 160 ° C. or higher by differential scanning calorimetry (DSC) measurement. The composition according to claim 7 or 8, comprising 0.001 to 5 parts by weight of a phosphoric acid ester metal salt represented by the following formula (I) or (II) per 100 parts by weight of polylactic acid (component A). .

(In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₁ is an alkali. A metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom, p is 1 or 2, q is 0 when M ₁ is an alkali metal atom, an alkaline earth metal atom or a zinc atom, and when it is an aluminum atom 1 or 2)

Wherein R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₂ is an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. Is 1 or 2, q is 0 when M ₁ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₁ is an aluminum atom.) Polylactic acid (component A) shows a crystal melting peak of 200 ° C. or higher by differential scanning calorimetry (DSC) measurement, and the ratio of the crystal melting peak of 200 ° C. or higher of the crystal melting peak is 80 to 100%. Item 10. The composition according to any one of Items 7 to 9. A melt-molded article comprising the composition according to any one of claims 1 to 10. The melt-molded product according to claim 11, which is a film, a fiber, a fiber structure, or an injection-molded product.