JP2010037379A - Polylactic acid-containing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a heat-stabilized polylactic acid-containing composition having a good hue. <P>SOLUTION: The polylactic acid-containing composition contains polylactic acid and phosphorous acid esters and satisfies the following requirements (a) to (c) at the same time: (a) a color b value measured as a 10% solution in chloroform is <2.5, (b) a color b value measured as a 10% solution in chloroform after retention at 260°C in an air atmosphere for 20 min is <2.5, and (c) a degree of stereo-complex crystallinity (S) defined by the expression (1) of S=[ΔH<SB>msc</SB>/(ΔH<SB>mh</SB>+ΔH<SB>msc</SB>)]×100 in DSC measurement is ≥80%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polylactic acid-containing composition. More specifically, the present invention relates to a stabilized polylactic acid-containing composition that does not deteriorate in hue even when reused.

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 a biodegradable polymer, polyhydroxybutyrate, polycaprolactone, aliphatic polyester, polylactic acid and the like are known.
Among them, polylactic acid is expected as a bio-based polymer using lactic acid obtained from a raw material derived from a living body or a derivative thereof as a raw material, and not as a biodegradable polymer but as an environmentally friendly polymer material.

Therefore, the use as a general-purpose polymer is also examined, and application to the casing of electronic parts such as relays and connectors as well as stretched films and fibers as well as injection-molded products is being studied.
However, the polylactic acid resin has a low crystal melting temperature of about 160 ° C. and a low crystallization speed, and therefore requires a long time for molding, and has a problem in heat resistance such as melting and deformation.

  On the other hand, poly-L-lactic acid (hereinafter sometimes abbreviated as PLLA) composed of L-lactic acid units and poly-D-lactic acid (sometimes abbreviated as PDLA) composed of D-lactic acid units are in solution or in a molten state. It is known that a stereocomplex polylactic acid is formed by mixing in the above. (Patent Document 1 and Non-Patent Document 1) This stereocomplex polylactic acid has a melting point as high as 200 to 250 ° C. compared to PLLA and PDLA, and an interesting phenomenon such as high crystallinity has been discovered.

  However, polylactic acid is a characteristic of aliphatic polyester that is easily metamorphically colored at high temperatures. If you try to use it, it may be colored so that it is difficult to use it as a product, and an urgent solution is awaited.

  On the other hand, as stabilizers for polylactic acid, for example, Patent Document 2 proposes various hindered phenol compounds, phosphite compounds, and other thioether compounds. However, application of these proposed agents has failed to obtain a polylactic acid composition having good hue and stable hue.

JP 2002-138188 A JP 2003-321601 A Degradation and discoloration mechanism of polymer materials and its stabilization technology-Know-how-Technical Information Association 2006

The object of the present invention is to propose a hue-stabilized polylactic acid-containing composition that solves the above-mentioned drawbacks of the conventional methods, has a good hue, and retains a good hue even after heat treatment, and a molded article comprising the same. .
Another object of the present invention is to propose a method for recovering the composition of the present invention having a good hue and a stable hue, and a recovered molded product.

  The present invention has found that a polylactic acid-containing composition having a good hue and a stable hue can be obtained by blending phosphites with polylactic acid, and the present invention has been completed.

That is, the object of the present invention is to
This is achieved by a polylactic acid-containing composition comprising polylactic acid and phosphites represented by the following general formula (1) and simultaneously satisfying the following requirements (a) to (c).

〔式中、Ｒ^１、Ｒ^２、Ｒ^４およびＲ^５はそれぞれ独立に水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基またはフェニル基を示し、Ｒ^３は水素原子または炭素数１〜８のアルキル基を示し、Ｘは単結合、硫黄原子または式（１−１）で示される２価の残基を示し、

（式中、Ｒ^６は水素原子、炭素数１〜８のアルキル基または炭素数５〜８のシクロアルキル基を示す。）
Ａは炭素数２〜８のアルキレン基または式（１−２）で示される２価の残基を示し、

（式中、Ｒ^７は単結合または炭素数１〜８のアルキレン基を示し、＊は酸素原子側に結合していることを示す。）、
Ｙ、Ｚはいずれか一方がヒドロキシル基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシル基または炭素数７〜１２のアラルキルオキシ基を示し、他の一方が水素原子または炭素数１〜８のアルキル基を示す。〕で表される少なくとも１種の化合物。
（ａ）クロロホルムの１０％溶液として測定したカラーｂ値が２．５未満であること。
（ｂ）空気雰囲気中、２６０℃、２０分間保持した後のクロロホルムの１０％溶液として測定したカラーｂ値が２．５未満であること。
（ｃ）ＤＳＣ測定で、下記式（１）で定義されるステレオコンプレックス結晶化度（Ｓ）が８０％以上であること。
［数１］
［Ｓ＝｛△Ｈ_ｍｓｃ／（△Ｈ_ｍｈ＋△Ｈ_ｍｓｃ）｝×１００ （１）
△Ｈ_ｍｓｃ，△Ｈ_ｍｈはＤＳＣ測定において、各々、ポリ乳酸ホモ結晶の融解に対応するピーク温度１６０から１９０℃の結晶融解熱（Ｊ／ｇ）、ステレオコンプレックスポリ乳酸結晶の融解に対応するピーク温度１９０℃以上の結晶融解熱（Ｊ／ｇ）を表す。］

[Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl having 6 to 12 carbon atoms. A group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X is a single bond, a sulfur atom or a formula (1-1). Indicates a divalent residue,

(In the formula, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.)
A represents an alkylene group having 2 to 8 carbon atoms or a divalent residue represented by the formula (1-2);

(In the formula, R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents that it is bonded to the oxygen atom side),
Y or Z is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or a carbon number. 1-8 alkyl groups are shown. ] At least 1 type of compound represented by this.
(A) The color b value measured as a 10% solution of chloroform is less than 2.5.
(B) The color b value measured as a 10% solution of chloroform after being kept at 260 ° C. for 20 minutes in an air atmosphere is less than 2.5.
(C) In DSC measurement, the stereocomplex crystallinity (S) defined by the following formula (1) is 80% or more.
[Equation 1]
[S = { _{ΔH msc} / ( _{ΔH mh} + _{ΔH msc} )} × 100 (1)
ΔH _msc and ΔH _mh are the DSC measurement, peak heat corresponding to melting of polylactic acid homocrystals from 160 to 190 ° C. (J / g), peak corresponding to melting of stereocomplex polylactic acid crystals, respectively. This represents the heat of crystal fusion (J / g) at a temperature of 190 ° C. or higher. ]

Furthermore, the following aspects are also included in the present invention.
1. The composition described above that satisfies the following requirements.
(A) 'Color b value measured as a 10% solution of chloroform is less than 1.5.
(B) Color b value measured as a 10% solution of chloroform in a composition held at 260 ° C. for 20 minutes in an air atmosphere is less than 2.

2. The composition described above that satisfies the following requirements.
(A) Color b value measured as a 10% solution of chloroform is less than 1.
(B) The color b value measured as a 10% chloroform solution of the composition held in an air atmosphere at 260 ° C. for 20 minutes is less than 1.5.

  3. The composition according to the above, comprising 0.01 to 5 parts by weight of the phosphite per 100 parts by weight of polylactic acid.

  4). The composition as described above, wherein only a peak having a peak temperature of 190 ° C. or higher corresponding to melting of the stereocomplex crystal is substantially detected by DSC measurement.

  5. When the carboxyl group concentration is 10 equivalents / ton or less, and the heat-and-moisture stability expressed by the retention rate (%) of the reduced viscosity (ηsp / c) when held at 80 ° C. and 90% RH for 11 hours is 80% or more A composition as described above.

  6). The composition as described above, containing 0.01 to 5 parts by weight of a phosphite represented by the general formula (1) per 100 parts by weight of polylactic acid.

  7). The composition as described above, comprising 0.001 to 10 parts by weight of a stereocomplex crystallization accelerator per 100 parts by weight of polylactic acid.

  8). The composition as described above, containing 5 to 300 parts by weight of a carboxyl end-group blocking agent per 100 parts by weight of polylactic acid.

  9. The composition as described above, containing 5 to 300 parts by weight of a thermoplastic resin other than polylactic acid per 100 parts by weight of polylactic acid.

  10. Copolymers other than L-lactic acid having a crystalline polylactic acid (B) component having a D-lactic acid unit as a main component and a copolymer unit other than D-lactic acid consisting of 0 to 10 mol% and an L-lactic acid unit as main components A crystalline polylactic acid (C) component having a unit of 0 to 10 mol% was obtained by melt ring-opening polymerization of lactide in the presence of a metal-containing catalyst, and then (B) / (C) by weight ratio. = (10) / (90) to (90) / (10) When melt-mixing to obtain a polylactic acid composition, the crystalline polylactic acid (B) component and / or the crystalline polylactic acid (C) component A process for producing a polylactic acid-containing composition, wherein phosphites represented by the general formula (1) are added at an arbitrary stage until completion of the melt ring-opening polymerization.

〔式中、Ｒ^１、Ｒ^２、Ｒ^４およびＲ^５はそれぞれ独立に水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基またはフェニル基を示し、Ｒ^３は水素原子または炭素数１〜８のアルキル基を示し、Ｘは単結合、硫黄原子または式（１−１）で示される２価の残基を示し、

（式中、Ｒ^６は水素原子、炭素数１〜８のアルキル基または炭素数５〜８のシクロアルキル基を示す。）
Ａは炭素数２〜８のアルキレン基または式（１−２）で示される２価の残基を示し、

（式中、Ｒ^７は単結合または炭素数１〜８のアルキレン基を示し、＊は酸素原子側に結合していることを示す。）、
Ｙ、Ｚはいずれか一方がヒドロキシル基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシル基または炭素数７〜１２のアラルキルオキシ基を示し、他の一方が水素原子または炭素数１〜８のアルキル基を示す。〕で表される少なくとも１種の化合物。

[Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl having 6 to 12 carbon atoms. A group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X is a single bond, a sulfur atom or a formula (1-1). Indicates a divalent residue,

(In the formula, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.)
A represents an alkylene group having 2 to 8 carbon atoms or a divalent residue represented by the formula (1-2);

(In the formula, R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents that it is bonded to the oxygen atom side),
Y or Z is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or a carbon number. 1-8 alkyl groups are shown. ] At least 1 type of compound represented by this.

  11. The production method according to the above, wherein the phosphite is added when the weight average molecular weight of the polylactic acid component is less than 10,000.

  12 The production method according to the above, wherein the phosphite is added when the weight average molecular weight of the polylactic acid component is less than 1000.

  13. The production method according to the above, wherein the phosphite is added to the lactide before the melt ring-opening polymerization reaction.

  14 The manufacturing method as described above, wherein the addition of the phosphite ester represented by the general formula (1) is performed by containing the phosphite ester represented by the general formula (1) in the raw material lactide.

  15. The molded object which consists of a polylactic acid containing composition as described above.

  16. The molded article as described above, wherein the content of the compound represented by the general formula (1) is 0.01 parts by weight or more and 5 parts by weight per 100 parts by weight of polylactic acid.

  17. A method for reusing a polylactic acid molded product, wherein the molded product described above is melted and molded again.

  18. A recycled molded body obtained by the method described above.

The polylactic acid-containing composition of the present invention has a good hue and maintains a good hue after undergoing a heat of fusion history in an air atmosphere. A molded article made of the composition maintains a good hue even after undergoing a good hue and heat history.
Furthermore, since the composition containing the components recovered from the molded product also has good hue and hue stability, the polylactic acid-containing composition of the present invention can be recycled and reused.

  The polylactic acid-containing composition of the present invention contains a phosphoric acid ester represented by the formula (1), and has a good color tone with a color b value measured as a 10% solution of chloroform of less than 2.5. Even after holding the composition at 260 ° C. for 20 minutes in an air atmosphere, the color b value measured as a 10% chloroform solution is less than 2.5, and the composition has good hue stability. By having such a good color tone and color tone stability, a molded product made of the composition has a good color tone, and the molded product can be reused.

The polylactic acid-containing composition of the present invention is required to have a stereocomplex crystallinity (S) defined by the following formula (1) of 80% or more by DSC measurement.
[Equation 2]
[S = { _{ΔH msc} / ( _{ΔH mh} + _{ΔH msc} )} × 100 (1)
ΔH _msc and ΔH _mh are the DSC measurement, peak heat corresponding to melting of polylactic acid homocrystals from 160 to 190 ° C. (J / g), peak corresponding to melting of stereocomplex polylactic acid crystals, respectively. This represents the heat of crystal fusion (J / g) at a temperature of 190 ° C. or higher. ]

  By showing the stereocomplex crystallinity as high as S = 80% or more, the polylactic acid-containing composition of the present invention can suitably exhibit the high heat resistance inherent in stereocomplex polylactic acid.

  From the viewpoint of heat resistance of the polylactic acid-containing composition, it is particularly preferable that only a peak at 190 ° C. or higher, which is a peak temperature corresponding to melting of the stereocomplex crystal, is substantially detected by DSC measurement.

  Such a polylactic acid-containing composition has an L-lactic acid unit as a main component, a poly L-lactic acid component containing 0 to 10 mol% of components other than the L-lactic acid unit, and a D-lactic acid unit as a main component. A polylactic acid composition containing a stereocomplex polylactic acid composed of a poly D-lactic acid component containing 0 to 10 mol% of a component other than a lactic acid unit (hereinafter sometimes simply referred to as a polylactic acid component), and the above. It can be obtained by mixing the poly L-lactic acid component and the poly D-lactic acid component in the range of (10/90) to (90/10) by weight ratio.

  In order for the polylactic acid component of the present invention to have higher stereocomplex crystallinity and heat resistance, it is more preferable to mix in the range of (20/80) to (80/20) by weight ratio, more preferably (30/70) to (70/30), particularly preferably (40/60) to (60/40), and a weight ratio as close as possible to (50/50) or (50/50). Is preferred.

  Mixing of the poly L-lactic acid component and the poly D-lactic acid component can be obtained, for example, by mixing in the presence of a solvent. The solvent is not particularly limited as long as it dissolves poly L-lactic acid and poly D-lactic acid. For example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol or the like alone or a mixture of two or more thereof are preferred.

  Mixing can also be performed in the absence of a solvent. That is, a method of melt kneading after mixing a predetermined amount of a poly L-lactic acid component and a poly D-lactic acid component, or a method of adding and kneading one of them after melting one of them can be employed.

  In addition, as the polylactic acid-containing composition of the present invention, stereoblock polylactic acid in which a poly L-lactic acid segment and a poly D-lactic acid segment are bonded can also be suitably used. Stereoblock polylactic acid is a block polymer in which a poly L-lactic acid segment and a poly D-lactic acid segment are bonded in the molecule.

Such block polymers include, for example, a method of producing by 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. A block copolymer having the above-mentioned basic constitution such as a method of polymerizing L-lactic acid and poly-D-lactic acid and blending and then solid-phase polymerizing to chain-extend, a method of producing from racemic lactide using a stereoselective ring-opening polymerization catalyst, etc. Any polymer can be used regardless of the production method.
However, it is more preferable from the viewpoint of ease of production to use a high-melting stereoblock polymer obtained by sequential ring-opening polymerization and a polymer obtained by a solid phase polymerization method.

It is preferable to add a specific additive to the polylactic acid component used in the present invention in order to promote the formation of stereocomplex crystals stably and highly.
For example,
(1) Stereocomplex crystallization accelerator; metal phosphate represented by the following formula (3) and / or (4).

（式中、Ｒ_１１は水素原子または炭素数１〜４のアルキル基を表しＲ_１２、Ｒ_１３は各々独立に水素原子または炭素数１〜１２のアルキル基を表す。
Ｍ_１は、アルカリ金属原子、アルカリ土類金属原子、亜鉛原子またはアルミニウム原子を表す。アルカリ金属原子としてＮａ、Ｋ、Ｌｉ等が挙げられる。アルカリ土類金属原子としてＭｇ、Ｃａ等が挙げられる。ｐは、１または２を表す。ｑは、Ｍ_１がアルカリ金属原子、アルカリ土類金属原子、亜鉛原子の時は０を、Ｍ_１がアルミニウム原子のときは１または２を表す。）

(In the formula, R ₁₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₂ and R ₁₃ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
M ₁ represents an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. Na, K, Li etc. are mentioned as an alkali metal atom. Examples of alkaline earth metal atoms include Mg and Ca. p represents 1 or 2. q represents 0 when M ₁ is an alkali metal atom, alkaline earth metal atom, or zinc atom, and represents 1 or 2 when M ₁ is an aluminum atom. )

（式中Ｒ_１４、Ｒ_１５、Ｒ_１６は各々独立に水素原子または炭素数１〜１２のアルキル基を表す。Ｍ_２は、アルカリ金属原子、アルカリ土類金属原子、亜鉛原子またはアルミニウム原子を表す。ｐは、１または２を表す。ｑは、Ｍ_２がアルカリ金属原子、アルカリ土類金属原子、亜鉛原子の時は０を、Ｍ_２がアルミニウム原子のときは１または２を表す。）

(In the formula, R ₁₄ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₂ represents an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. P represents 1 or 2. q represents 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.)

(2) Block forming agent: at least one group selected from the group of (epoxy group, oxazoline group, oxazine group, isocyanate group, ketene group and carbodiimide group) (hereinafter sometimes abbreviated as a specific functional group) in the molecule. A compound having one.
In these metal phosphates, M ₁ and M ₂ are specifically Na, K, Al, Mg, Ca, etc., and K, Na, and Al can be particularly preferably used.

  Preferred examples of the phosphoric acid ester metal salt include compounds proposed in Japanese Patent No. 39609797, and “Adekastab” NA-10, NA-11, NA-21 and NA-71 commercially available from ADEKA Corporation. Can be used. The stereocomplex crystallization accelerator of the present invention may be applied alone or in combination of two or more.

  The phosphate metal salt is preferably used in an amount of 10 ppm to 2 wt%, more preferably 50 ppm to 0.5 wt%, and still more preferably 100 ppm to 0.3 wt% based on the polylactic acid component. If the amount is too small, the effect of improving the stereocomplex crystallinity is small, and if too large, the polylactic acid-containing composition itself is deteriorated, which is not preferable.

  Furthermore, it is preferable to use a so-called crystallization accelerator in combination to enhance the action of the phosphate metal salt. As such a crystallization accelerator, various agents described below in the item of crystallization accelerator are used, and among them, calcium silicate, talc, kaolinite, and montmorillonite are preferably selected.

  The amount of the crystallization accelerator used to enhance the action of the phosphoric acid ester metal salt is 0.05 to 5 parts by weight, more preferably 0.06 to 2 parts by weight, more preferably 0.06 per 100 parts by weight of the polylactic acid component. To 1 part by weight is selected.

  The block forming agent reacts with the molecular end of poly-L-lactic acid or poly-D-lactic acid, partially linking the poly-L-lactic acid unit and poly-D-lactic acid unit to promote the formation of blocked polylactic acid It is an agent.

  As the block forming agent, a carboxyl group sealing agent described below can be suitably applied. Especially, the agent which has a carbodiimide group as a specific functional group, and a carbodiimide compound are suitably selected from the preferable influence which has on the color tone of a polylactic acid and the resin composition of this invention, thermal decomposition property, hydrolysis resistance, etc.

  The amount of the block forming agent used is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight per 100 parts by weight of the polylactic acid component. If it is applied in a large amount beyond this range, there is a concern that the resin hue is deteriorated or plasticization occurs, which is not preferable.

If the amount is less than 0.001 part by weight, the effect is hardly recognized and industrial significance is small.
The methods (1) and (2) can be applied independently, but a method of applying them in combination is preferable because it can further effectively promote the formation of a stereocomplex crystal.

The color b value of the color tone parameter of the polylactic acid-containing composition of the present invention is preferably 2.5 or less, more preferably 2, particularly preferably 1.5 or less. The same is true for the sample after heat treatment at 260 ° C.
A molded article made of a polylactic acid-containing composition having a color b value exceeding 2.5 exhibits a very strong yellow color with poor sensory preference, and its use is limited.

In the polylactic acid-containing composition of the present invention, it is preferred that the polylactic acid has a sufficiently high weight average molecular weight and crystallinity because the molded product has sufficiently high heat resistance, for example, a high heat distortion temperature.
The polylactic acid-containing composition of the present invention preferably has a weight average molecular weight in the range of 100,000 to 500,000.
If the weight average molecular weight is less than 100,000, the mechanical strength and toughness of the molded product are low, which is not preferable. Further, if the weight average molecular weight exceeds 500,000, the melt viscosity is high, and melt molding becomes difficult.

Further, in the present invention, the polylactic acid-containing composition has a crystal melting peak (Tmh) between 150 and 190 ° C. as measured by differential scanning calorimetry (DSC), and the heat of crystal melting (ΔHmsc) is 10 J / It is preferable that it is more than g.
This is because the heat resistance is preferably enhanced by satisfying the range of the crystal melting point and the crystal melting heat.

  In the present invention, it is preferred that poly L-lactic acid and poly D-lactic acid, which are polylactic acid components in the polylactic acid-containing composition, consist essentially of L-lactic acid units and D-lactic acid units.

The poly-L-lactic acid is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and more preferably 99 to 100 mol% L-lactic acid units to achieve a high melting point. .
Examples of units other than L-lactic acid include D-lactic acid units and copolymerized units other than lactic acid. The content of D-lactic acid units and copolymer units other than lactic acid is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 2 mol%.

The poly-D-lactic acid is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and more preferably 99 to 100 mol% L-lactic acid units to achieve a high melting point. .
Examples of units other than D-lactic acid include L-lactic acid units and copolymerized units other than lactic acid. L-lactic acid units and copolymer units other than lactic acid are 0 to 10 mol%, preferably 0 to 5 mol%, 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 polyhydric alcohols include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. Or aromatic polyhydric alcohol etc., such as what added ethylene oxide to bisphenol, etc. are mentioned. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid. Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

  Said poly L-lactic acid and poly D-lactic acid can be manufactured by a well-known method. For example, L- or D-lactide can be produced by heating and ring-opening polymerization in the presence of a metal-containing catalyst. Moreover, after crystallizing the low molecular weight polylactic acid containing a catalyst, it can also be produced by heating and solid phase polymerization under reduced pressure or in an inert gas stream.

  The polymerization reaction can be carried out in a conventionally known reaction vessel. For example, 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 parallel. Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.

  Examples of the metal-containing catalyst used in the present invention include alkali metals, alkaline earth metals, rare earths, transition metals, aluminum, germanium, tin, antimony and other fatty acid salts, carbonates, sulfates, phosphates, oxides. , Hydroxides, halides, alcoholates and the like.

  The metal-containing catalyst is preferably a catalyst containing at least one selected from tin, aluminum, zinc, calcium, titanium, germanium, manganese, magnesium and a rare earth element. Specifically, stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, tin myristate, tin octylate, tin stearate, tetraphenyltin, tin methoxide, Tin ethoxide, tin butoxide, aluminum oxide, aluminum acetylacetonate, aluminum isopropoxide, aluminum-imine complex titanium tetrachloride, ethyl titanate, butyl titanate, glycol titanate, titanium tetrabutoxide, zinc chloride, zinc oxide, diethyl zinc And antimony trioxide, antimony tribromide, antimony acetate, calcium oxide, germanium oxide, manganese oxide, manganese carbonate, manganese acetate, magnesium oxide, yttrium alkoxide and the like.

  Considering the catalytic activity and few side reactions, stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, stannous myristate, stannous octoate, stannous stearate Tin-containing compounds such as tetraphenyltin and aluminum-containing compounds such as aluminum acetylacetonate, aluminum butoxide, and aluminum-imine complexes are preferred. More preferable examples include diethoxytin, dinonyloxytin, tin myristate, tin octylate, tin stearate, tin chloride, aluminum acetylacetonate, aluminum isopropoxide and the like.

The amount of the catalyst used is 0.42 × 10 ^{−4 to} 100 × 10 ⁻⁴ (mol) per 1 kg of lactide, and 1.68 × 10 ^{−4 in} consideration of reactivity, color tone and stability of the resulting polylactide. ~42.1 × ^{10 -4} (mol), particularly preferably from ^{0.5 × 10 -4 ~6.8 × 10 -4} ( mol).

  Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid, for example, monools such as decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, ethylene glycol, propanediol, hexanediol. A diol such as glycerol, a triol such as glycerol, and a tetraol such as pentaerythritol can be preferably used.

For polylactic acid, it is preferable to inactivate the metal-containing catalyst used during polymerization with a deactivator.
Examples of such a deactivator include an organic ligand consisting of a group of chelate ligands having an imino group and capable of coordinating to a polymerized metal catalyst, dihydridooxoline (I) acid, dihydridotetraoxodilin (II, II) Acid, hydridotrioxoline (III) acid, dihydridopentaoxodiphosphoric acid (III), hydridopentaoxodi (II, IV) acid, dodecaoxohexaphosphorus (III) III, hydridooctaoxotriphosphorus (III, IV, IV) acid, octaoxotriphosphoric acid (IV, III, IV), hydridohexaoxodiphosphoric acid (III, V) acid, hexaoxodiphosphoric acid (IV), decaoxotetraphosphoric acid (IV), IV) acid, Eneaokiso triphosphate (V, IV, IV) acid value 5 or less low oxidation number phosphoric acids such as acid, the formula _xH 2 O · y Is represented by _{2 O 5, x / y =} 3 of orthophosphoric acid, 2> a x / y> 1, diphosphate than the degree of condensation, triphosphate, tetraphosphate, polyphosphoric acid is called a five phosphoric acid And a mixture thereof, metaphosphoric acid represented by x / y = 1, in particular, trimetaphosphoric acid, tetrametaphosphoric acid, 1> x / y> 0, and a network structure in which a part of the phosphorus pentoxide structure is left. Ultraphosphoric acid (sometimes collectively referred to as metaphosphoric acid compounds), acidic salts of these acids, monovalent and polyhydric alcohols, partial esters of polyalkylene glycols, complete esters And phosphono-substituted lower aliphatic carboxylic acid derivatives.

From the catalyst deactivation ability, it is represented by the formula xH ₂ O · yP ₂ O ₅ , x / y = 3 orthophosphoric acid, 2> x / y> 1, and based on the degree of condensation, diphosphate, triphosphate, tetra Polyphosphoric acid called phosphoric acid, pentaphosphoric acid and the like and mixtures thereof, metaphosphoric acid represented by x / y = 1, especially trimetaphosphoric acid, tetrametaphosphoric acid, 1> x / y> 0, Ultraphosphoric acid having a network structure in which a part of the phosphorus oxide structure is left (these may be collectively referred to as metaphosphoric acid compounds), and acid salts of these acids, monovalent and polyhydric alcohols Alternatively, partial ester phosphorus oxoacids of polyalkylene glycols or acidic esters thereof, phosphono-substituted lower aliphatic carboxylic acid derivatives and the above-mentioned metaphosphoric acid 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 diethylhexylphosphonoacetate (hereinafter sometimes abbreviated as DHPA) and the like are preferably used.

The phosphites contained in the polylactic acid-containing composition of the present invention are the compounds represented by the general formula (1), wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, carbon number 1 An -8 alkyl group, an alicyclic group having 5 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or an aromatic group;

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, t- A pentyl group, i-octyl group, t-octyl group, 2-ethylhexyl group and the like can be mentioned.
Examples of the alicyclic group having 5 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-methylcyclopentyl group, a 1-methylcyclohexyl group, and a 1-methyl-4-i-propylcyclohexyl group. Groups and the like.

Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group and the like.
Examples of the aromatic group having 7 to 12 carbon atoms include phenyl group, naphthyl group, 2-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, and 2,6-dimethylphenyl group. .

R ¹ , R ² , and R ⁴ are preferably an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 5 to 12 carbon atoms, and the like.
R ¹ and R ⁴ are more preferably a t-alkyl group such as a t-butyl group, a t-pentyl group or a t-octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group.

R ² is preferably an alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group and t-pentyl group. , Methyl group, t-butyl group, t-pentyl group and the like are more preferable. R ⁵ is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a t-pentyl group, or the like. 1-5 alkyl groups are preferred.

R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. As the alkyl group having 1 to 8 carbon atoms, R ¹ , R ² , R ⁴ and R ⁵ are the same as those described above for R ¹ , R ² , R ⁴ and R ⁵ . 8 alkyl groups. R ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms as described above for R ² , more preferably a hydrogen atom, a methyl group, or the like.

X represents a single bond, a sulfur atom or a divalent residue represented by the formula (I-1). In the divalent residue represented by the formula (I-1), R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alicyclic group having 5 to 12 carbon atoms. Examples of the alkyl group having 8 and the alicyclic group having 5 to 12 carbon atoms include the same alkyl group and alicyclic group as described above for R ¹ , R ² , R ⁴ and R ⁵ .

R ⁶ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group or other alkyl group having 1 to 5 carbon atoms. X is preferably a single bond or a divalent residue represented by the formula (1-1), more preferably a single bond.

A represents an alkylene group having 2 to 8 carbon atoms or a divalent residue represented by the formula (1-2), and an alkylene group having 2 to 8 carbon atoms is preferable. , Propylene group, butylene group, pentamethylene group, hexamethylene group, octamethylene group, 2,2-dimethyl-1,3-propylene group and the like, and propylene group is more preferable. The divalent residue represented by the formula (1-2) is bonded to the oxygen atom and the benzene nucleus, but * indicates that it is bonded to the oxygen atom. R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms. Examples of the alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, and a hexamethylene group. Group, octamethylene group, 2,2-dimethyl-1,3-propylene group and the like. R ⁷ is preferably a single bond or an ethylene group.

Y or Z is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or a carbon number. 1-8 alkyl groups are shown. Here, examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above as R ¹ , R ² , R ⁴ and R ⁵ . Examples of the alkoxyl group having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, t- Examples include a pentoxy group, i-octoxy group, t-octoxy group, 2-ethylhexoxy group and the like. Examples of the aralkyloxy group having 7 to 12 carbon atoms include benzyloxy group, α-methylbenzyloxy group, α, α-dimethylbenzyloxy group and the like. Y and Z are Y is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and Z is a hydrogen atom or 1 to 8 carbon atoms. Z may be a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and Y may be a hydrogen atom or It may be an alkyl group having 1 to 8 carbon atoms.

Among the phosphites represented by the formula (I), R ¹ and R ⁴ are a t-alkyl group, cyclohexyl or 1-methylcyclohexyl group, and R ² is an alkyl group having 1 to 5 carbon atoms. , R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a single bond, and A is 2 to 8 carbon atoms. An alkylene group is particularly preferred.

Examples of such phosphites include 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d , F] [1, 3, 2] dioxaphosphine [“Sumilyzer GP” (manufactured by Sumitomo Chemical Co., Ltd.). 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] dibenzo [D, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -12H Dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di -T-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8 , 10-Tetra-t-butyl-6- (3,5-di-t-butyl-4- Roxybenzoyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t -Butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,10 -Diethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3 2] Dioxaphosphocin, 2,4,8,10-tetra-t-butyl Ru-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphine Etc.
A commercial item can also be used for such phosphites, for example, Sumilizer GP (registered trademark, manufactured by Sumitomo Chemical Co., Ltd.).

  In the polylactic acid-containing composition of the present invention, the content of phosphites is usually 0.01 to 5 parts by weight per 100 parts by weight of polylactic acid. If it is less than 0.01 part by weight, the coloration inhibiting ability of the polylactic acid-containing composition may be insufficient, preferably 0.03 part by weight or more, and more preferably 0.05 part by weight or more. Moreover, even if it uses exceeding 5 weight part, the effect corresponding to it does not appear, but it is economically disadvantageous, Preferably it is 3 weight part or less, More preferably, it is 1 weight part or less.

Such a polylactic acid-containing composition can be produced by mixing the above-described polylactic acid component and phosphites. Specifically, the powder of the polylactic acid component described above and phosphites may be mixed at a temperature lower than the melting temperature of polylactic acid.
Mixing can also be performed using a mixer such as a Henschel mixer. Thus, the polylactic acid-containing composition of the present invention can also be obtained as a mixture of polyester powder and phosphites.

  The polylactic acid component and phosphite may be kneaded at a temperature equal to or higher than the melting temperature of the polylactic acid component. Specifically, the polylactic acid component and phosphite ester at a temperature lower than the melting temperature of the polylactic acid component. After mixing the materials, the mixture may be heated to a temperature equal to or higher than the melting temperature of polylactic acid and kneaded. For kneading, a kneader such as a uniaxial kneader or a biaxial kneader is used. Thus, a polylactic acid-containing composition is obtained in which the phosphites are uniformly dispersed in the polylactic acid in a molten state, and the phosphites are uniformly dispersed in the polylactic acid component.

However, when the polylactic acid-containing composition of the present invention having a good hue is produced by melt ring-opening polymerization of polylactide, it is more preferable to add phosphite esters from the start of polymerization to the end of polymerization. Can be manufactured.
That is, by melt ring-opening polymerization in the presence of phosphites, not only can a polylactic acid-containing composition in which phosphites are uniformly dispersed in the polylactic acid-containing composition be obtained, By improving the hue of the lactic acid-containing composition, it is possible to suitably realize a color b value measured as a chloroform solution of less than 2.

When blending phosphites during the melt ring-opening polymerization of poly L-lactic acid and poly D-lactic acid before the production of polylactic acid component, when the weight average molecular weight of poly L-lactic acid and poly D-lactic acid is low The method of blending can exert a great effect of improving the hue and stability of the composition.
That is, blending phosphites at a stage where the weight average molecular weights of poly L-lactic acid and poly D-lactic acid are 10000 or less, more preferably 1000 or less, from the viewpoint of improving the hue and stability of the composition. Preferably selected.

Furthermore, in the present invention, a method of blending phosphites in a lactide polymerization apparatus at the time of charging and performing melt ring-opening polymerization in the presence of phosphites is also exemplified as one preferred embodiment.
Furthermore, it is exemplified as a preferred embodiment that phosphites are mixed in advance with the raw material lactide.
Thus, when blending phosphites with polylactic acid, a method of adding the phosphites as a lactide solution is preferably selected in order to surely blend polylactic acid into the polylactic acid component.

The polylactic acid-containing composition of the present invention may contain various additives.
Examples of the additive include amines and acid-bonded metal salts to enhance the action of the phosphite. These also have the effect of preventing hydrolysis of phosphites, and may be used by being premixed with phosphites.

  Examples of amines include trialkanolamines such as triethanolamine, tripropanolamine, and tri-i-propanolamine, diethanolamine, dipropanolamine, di-i-propanolamine, tetraethanolethylenediamine, and tetra-i-propanolethylenediamine. Dialkanolamines such as dibutylethanolamine, monoalkanolamines such as dibutyl-i-propanolamine, aromatic amines such as 1,3,5-trimethyl-2,4,6-triazine, dibutylamine, piperidine , 2,2,6,6-tetramethylpiperidine, alkylamines such as 4-hydroxy-2,2,6,6-tetramethylpiperidine, hexamethylenetetramine, triethylenediamine, triethylene Polyalkylene polyamines such as tetramine and tetraethylenepentamine, long-chain aliphatic amines described in JP-A-61-63686, compounds containing sterically hindered amine groups described in JP-A-6-329830, Examples include hindered piperidinyl light stabilizers described in JP-A-7-90270 and organic amines described in JP-A-7-278164.

Also, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ((2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6) , 6-Pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2,6,6-tetra Methyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2, -Bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidyldecanedioate, 2,2, 6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl ) Amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane Tetracarbo Silates, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2, Mixed esterified product of 2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetrabonic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1 -Mixed esterified product with tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1 -Dimethylethyl) -2,4,8,10-tetraoxaspiro [5 · 5] undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2, Mixed ester with 6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane Compound, polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, poly [(6-morpholino-1,3,5-triazine -2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl ((2,2,6,6-tetramethyl-4-piperidyl) imino ) Hexamethylene (2,2,6,6-tetramethyl-4-piperidyl) imino)], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2- Polycondensate with dibromoethane, N, N ′, 4,7-tetrakis [4,6-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino)- 1,3,5-triazin-2-yl] -4,7-diazadecane-1,10 diamine, N, N ′, 4-tris [4,6-bis (N-butyl-N- (2,2, 6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4,7-tetrakis [ 4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperi A) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4-tris [4,6-bis (N-butyl-N) -(1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and mixtures thereof And hindered amine light stabilizers. Such a hindered amine stabilizer also has a function as a light stabilizer.
When using amines, the usage-amount is 0.01 to 25 weight part normally per 100 weight part of phosphites.

（式中、Ｍ^２＋はＭｇ^２＋、Ｃａ^２＋、Ｓｒ^２＋、Ｂａ^２＋、Ｚｎ^２＋、Ｐｂ^２＋、Ｓｎ^２＋またはＮｉ^２＋で示される価数２のカチオンを示し、Ｍ^３＋はＡｌ^３＋、Ｂ^３＋またはＢｉ^３＋で示される価数３のカチオンを示し、ｎは１〜４の数値を示し、ｘは０〜０．５の数値を示し、ｐは０〜２の数値を示し、Ｄ^ｎ−は価数ｎのアニオンを示す。）で示される複塩化合物が挙げられる。 As an acid bond metal salt, for example, the formula (2)

( ^Wherein M ²⁺ represents a valence 2 cation represented by Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Zn ²⁺ , Pb ²⁺ , Sn ²⁺ or Ni ²⁺ , and M ³⁺ represents Al ³⁺ , B ³⁺ or Bi ³⁺ represents a cation having a valence of 3, n represents a value of 1 to 4, x represents a value of 0 to 0.5, p represents a value of 0 to 2, and D ⁿ⁻ represents a valence. A double salt compound represented by a number n).

Examples of the valence n anion represented by D ^n- include OH ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , HCO ₃ ⁻ , C ₆ H ₅ COO ⁻ , CO ₃ ²⁻ , SO ₂ ^{−. _{, - OOCCOO -, (CHOHCOo)}} 2 2-, C 2 H 4 (COO) 2 2-, (CH 2 COO) 2 2-, CH 3 CHOHCOO -, SiO 3 2-, SiO 4 4-, Fe (CN ) Anions such as ₆ ⁴⁻ , BO ₃ ⁻ , PO ₃ ³⁻ , and HPO ₄ ²⁻ are exemplified.

（式中、ｘ、ｐはそれぞれ前記と同じ意味を示す。）で示されるハイドロタルサイト類が好ましい。ハイドロタルサイト類は、天然物であってもよいし、合成品であってもよい。 Among such double salt compounds, the formula (2-1);

(Wherein, x and p each have the same meaning as described above) are preferred. Hydrotalcites may be natural products or synthetic products.

Moreover, the average particle diameter of hydrotalcites is about 0.01-100 micrometers normally, The crystal structure, crystal diameter, etc. are not specifically limited.
The acid-bonded metal salt may be an ultrafine zinc oxide described in JP-A-6-329830, an acid-bonded metal salt described in JP-A-7-278164, or the like. When an acid-bonded metal salt is used, the amount used is usually 0.01 parts by weight or more and 25 parts by weight or less per 100 parts by weight of phosphites.

In the present invention, in addition to the above-mentioned amines and acid-bonded metal salts, it is preferable to add various stabilizers in order to obtain a desired effect.
As the stabilizer used in the present invention, those usually used as stabilizers for thermoplastic resins can be used. For example, for example, phenol compounds, thioether compounds, phosphorus compounds, UV absorbers, light stabilizers, hydroxylamines, lubricants such as calcium stearate and higher aliphatic amides, plasticizers such as mineral oil and silicone oil, difficulty Examples include a release agent such as a flame retardant and higher fatty acid, an antistatic agent, a pigment, a dye, and a foaming agent. Furthermore, U.S. Pat. No. 4,325,853, U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312, U.S. Pat. No. 5216053, U.S. Pat. No. 5,252,463, DE-A- 4316611, German Patent No. 4316622, German Patent No. 4316876, European Patent Publication No. EP-A-589839, European Patent No. 591012, Canadian Patent No. CA-2132132, etc. Additives such as benzofuranones and indolines may be contained.
By blending these agents, it is possible to obtain a composition and a molded body excellent in mechanical properties, moldability, heat resistance and durability of the composition.

  Examples of the phenolic compound used in the present invention include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, and 2,6-di-t-butylphenol. 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di -T-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-diocudadecyl-4-methylphenol, 2 , 4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4- Methyl-6- (1′-methylundecyl-1′-yl) phenol, 2,4-dimethyl-6- (1′-methylheptadecyl-1′-yl) phenol, 2,4-dimethyl-6 Alkylated monophenols such as (1′-methyltridecyl-1′-yl) phenol and mixtures thereof, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6- Alkylthiomethylphenols such as methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol and mixtures thereof, 2,6-di-t-butyl-4 -Methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6-diphenyl -4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, Hydroquinones and alkylated hydroquinones such as bis (3,5-di-t-butyl-4-hydroxyphenyl) adipate and mixtures thereof, α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof Tocopherols such as 2,2′-thiobis (6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,2′-thiobis (4-octylphenol), 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-thiobis 2-methyl-6-t-butylphenol), 4,4′-thiobis (3,6-di-t-amylphenol), 4,4 ′-(2,6-dimethyl-4-hydroxyphenyl) disulfide, etc. Hydroxylated thiodiphenyl ethers, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis [4 -Methyl-6- (α-methylcyclohexyl) phenol)], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4-methyl-6-nonylphenol), 2, 2'-methylenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol) 2,2′-ethylidenebis (4-isobutyl-6-tert-butylphenol), 2,2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2′-methylenebis [6- (Α, α-dimethylbenzyl) -4-nonylphenol], 4,4′-methylenebis (6-tert-butyl-2-methylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol) 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-t-butyl-4-hydroxy-2-) Methylphenyl) butane, 2,6-bis (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-t- Til-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3 -Bis-3'-t-butyl-4'-hydroxyphenyl) butyrate], bis (3-t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-t- Butyl-2′-hydroxy-5′-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2- Bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-do Decyl mercaptobutane, 1,1,5,5-tetra (5-t-butyl-4-hydroxy-2-methylphenyl) pentane, 2-t-butyl-6- (3′-t-butyl-5′- Methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,4-di-t-pentyl-6- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] phenyl acrylate And alkylidene bisphenols and their derivatives, such as 3,5,3 ′, 5′-tetra-t-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethyl Benzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydro Cis-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate and O-benzyl derivatives, N-benzyl derivatives and S-benzyl derivatives such as mixtures thereof, dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) malonate, dioctadecyl- 2- (3-t-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecyl mercaptoethyl-2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate, bis [ 4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-t-butyl Hydroxybenzylated malonate derivatives such as 4-hydroxybenzyl) malonate and mixtures thereof, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) Benzene, 1,4-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-t- Aromatic hydroxybenzyl derivatives such as butyl-4-hydroxybenzyl) phenol and mixtures thereof, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2-n-octylthio-4,6-bis (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2- n-octylthio-4,6-bis (4-hydroxy-3,5-di-t-butylphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-t- Butyl-4-phenoxy) -1,3,5-triazine, tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tris (3,5-di-t-butyl-4 -Hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 2,4,6-tris (3 5-di-t-butyl-4-hydroxyphenylpropyl) -1,3,5-triazine, tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ′, 5′- J-t-B Tri-4'-hydroxycinnamoyloxy) ethyl] isocyanurate and mixtures thereof, dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di- t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, 3, Benzylphosphonate derivatives such as calcium salts of 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoester and mixtures thereof, 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, octyl-N- (3 , 5-Di-tert-butyl-4-hydro Acylaminophenol derivatives such as cyphenyl) carbanates and mixtures thereof, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, β- (5-tert-butyl-4-hydroxy-3) -Methylphenyl) propionic acid, β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid, 3,5-di-t-butyl-4-hydroxyphenylacetic acid and methanol, ethanol, octanol , Octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol triethylene Glycol, pentaerythrito , Tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -Esters with monohydric or polyhydric alcohols such as phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof, N, N'-bis [3- (3 ' , 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] hydrazine, N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] Hexamethylenediamine, N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] Such as Li diamine and amides of beta-(3,5-di -t- butyl-4-hydroxyphenyl) propionic acid such as mixtures thereof. Such phenol compounds may be used alone or in admixture of two or more.

  Examples of sulfur antioxidants include dilauryl 3,3′-thiodipropionate, tridecyl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thio. Dipropionate, lauryl stearyl 3,3′-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate) and the like may be used, and these may be used alone or in combination of two or more. You may mix and use.

  Examples of phosphorus antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl. Pentaerythritol diphosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butyl-6-methylphenyl) ) Pentaerythritol di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol di Phosphite, tristearyl sorbitol tri Sphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite 2,2′-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4 -Di-t-butyl-6-methylphenyl) methyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl) phosphites and their Mixing 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 diphosphite, tetrakis (2,6-di-t-butylphenyl) 4,4′-biphenylene phosphite and the like can be preferably used. These may be used alone or in combination of two or more.

  Specific examples of the light stabilizer used in the present invention include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds and hindered amine compounds. it can.

  Specific examples of the benzophenone compound 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-me Carboxymethyl-2'-carboxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methylcyclohexyl acryloxy-isopropoxyphenyl) benzophenone.

  Specific examples of benzotriazole compounds 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'Okutokishi 2'-hydroxyphenyl) benzotriazole and the like.

  Specific examples of the aromatic benzoate compounds include alkylphenyl salicylates such as pt-butylphenyl salicylate and p-octylphenyl salicylate.

  Specific examples of the oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, 2- And ethoxy-3′-dodecyl oxalic acid bisanilide.

  Specific examples of the cyanoacrylate compound include ethyl-2-cyano-3,3'-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, and the like.

  Specific 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-benzyl Oxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- ( Tylcarbamoyloxy) -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 Peridyloxy) -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-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2, , 6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethanol A condensate etc. can be mentioned.

  In this invention, the said stabilizer may be used by 1 type and may be used in combination of 2 or more type. Moreover, it is preferable to use a hindered phenol compound and / or a benzotriazole compound as the stabilizer. The blending amount of the stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of the polylactic acid component.

  In this invention, it is preferable to mix | blend a carboxyl group reactive terminal blocker. The carboxyl group-reactive end capping agent used in the present invention is not particularly limited as long as it is an agent capable of capping the carboxyl end group of the polymer. In the present invention, the carboxyl group-reactive end-capping agent not only seals the terminal carboxyl group of polylactic acid but also low molecular weight such as carboxy group, lactic acid, formic acid, etc. produced by the decomposition reaction of polylactic acid and various additives. The carboxyl group of the compound can be sealed. Moreover, it is preferable that the said sealing agent is a compound which can seal | block the hydroxyl group terminal which an acidic low molecular weight compound produces | generates not only by a carboxyl group but by thermal decomposition, or the water | moisture content which penetrate | invades into a resin composition.

  As such a carboxyl group-reactive end-capping agent, it is preferable to use at least one compound selected from a carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound, and an isocyanate compound, and among them, a carbodiimide compound, an epoxy compound, Oxazoline compounds and isocyanate compounds are preferred.

  The carbodiimide compound used in the present invention is a compound having one or more carbodiimide groups in the molecule, preferably containing 0.1 to 5% by weight of isocyanate groups, and having a carbodiimide equivalent of 200 to 500. By containing a small amount of an isocyanate group, the wet heat stability of the composition of the carbodiimide compound and the polylactic acid component is further improved, which is preferable for the purpose of the present invention. When the isocyanate group is present in the carbodiimide compound, not only the effect of the combined use of the isocyanate compound appears, but also the presence of the carbodiimide group and the isocyanate group more closely exhibits the effect of improving wet heat durability. When a polycarbodiimide compound is used, it is more preferable for the purpose of the present invention that a plurality of carbodiimide groups present in the molecule are placed at an appropriate distance from each other. That is, a carbodiimide equivalent of about 200 to 500 is preferable. Such a carbodiimide compound can be produced by a conventionally known method. For example, it can be produced by subjecting various organic isocyanates to a decarboxylation condensation reaction in a solvent-free or inert solvent at a temperature of 70 ° C. or higher using an organic phosphorus compound or an organometallic compound as a catalyst.

  Examples of the carbodiimide compound used in the present invention include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, octyldecylcarbodiimide, di-t-butylcarbodiimide, t-butylisopropylcarbodiimide, and dicarbodiimide compound. Benzylcarbodiimide, diphenylcarbodiimide, N-octadecyl-N′-phenylcarbodiimide, N-benzyl-N′-phenylcarbodiimide, N-benzyl-N′-tolylcarbodiimide, di-o-toluylcarbodiimide, di-p-tolylcarbodiimide, Bis (p-nitrophenyl) carbodiimide, bis (p-aminophenyl) carbodiimide, bis (p Hydroxyphenyl) carbodiimide, bis (p-chlorophenyl) carbodiimide, bis (o-chlorophenyl) carbodiimide, bis (o-ethylphenyl) carbodiimide, bis (p-ethylphenyl) carbodiimide bis (o-isopropylphenyl) carbodiimide, bis (p -Isopropylphenyl) carbodiimide, bis (o-isobutylphenyl) carbodiimide, bis (p-isobutylphenyl) carbodiimide, bis (2,5-dichlorophenyl) carbodiimide, p-phenylenebis (o-toluylcarbodiimide), p-phenylenebis ( Cyclohexylcarbodiimide, p-phenylenebis (p-chlorophenylcarbodiimide), 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide, hexa Tylene bis (cyclohexylcarbodiimide), ethylenebis (phenylcarbodiimide), ethylenebis (cyclohexylcarbodiimide), bis (2,6-dimethylphenyl) carbodiimide, bis (2,6-diethylphenyl) carbodiimide, bis (2-ethyl-6-isopropyl) Phenyl) 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-triisopropylphenyl) carbodiimide, bis (2,4,6-tributylphenyl) carbodiimide, di-β-naphthylcarbosiimide, N-tolyl-N ′ Cyclohexyl carbocyclylalkyl imides, mono- or di-carbodiimide compounds such as N- tolyl -N'- phenyl carbocyclylalkyl imide and the like.

  Of these, bis (2,6-diisopropylphenyl) carbodiimide and 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide are preferable from the viewpoint of reactivity and stability.

  Of these, industrially available dicyclohexylcarbodiimide and diisopropylcarbodiimide are also suitable. Moreover, what was manufactured by the various method can be used suitably for the polycarbodiimide compound contained in the said carbodiimide compound.

  Conventionally known methods for producing polycarbodiimide compounds, for example, US Pat. No. 2,941,956, Japanese Patent Publication No. 47-33279, Org. Chem. 28, 2069-2075 (1963), Chemical Review 1981, Vol. 81 no. 4, p619-621 etc. can be used.

  For example, poly (1,6-cyclohexanecarbodiimide), poly (4,4′-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4, 4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (m Examples thereof include polycarbodiimides such as p-tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyldisopropylphenylenecarbodiimide), and poly (triethylphenylenecarbodiimide).

  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., and HMV-8CA.

  As an epoxy compound that can be used as a carboxyl group-reactive end-capping agent in the present invention, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, a glycidyl amide compound, and an alicyclic epoxy compound are preferable. Can be used. By blending such an agent, it is possible to obtain a polylactic acid-containing composition and a molded body excellent in mechanical properties, moldability, heat resistance and durability.

  Examples of glycidyl ether compounds include, for example, butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether , Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol Bisphenol obtained by condensation reaction of bisphenols such as traglycidyl ether, other 2,2-bis- (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone and epichlorohydrin A diglycidyl ether type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, and the like. Of these, bisphenol A diglycidyl ether type epoxy resins are preferred.

  Examples of glycidyl ester compounds include benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, persic acid glycidyl ester, oleic acid glycidyl ester Ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, methyl terephthalic acid glycidyl ester, hexahydrophthalic acid diglycidyl ester , Tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl Ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, etc. Can be mentioned. Of these, glycidyl benzoate and glycidyl versatate are preferred.

  Examples of glycidylamine compounds include, for example, tetraglycidylamine diphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, Tetraglycidyl bisaminomethylcyclohexane, triglycidyl isocyanurate, etc. are mentioned.

  Examples of glycidylimide and glycidylamide compounds include, for example, N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-3-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl- 3,6-dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl-3,4,5,6-tetrabromo Phthalimide, N-glycidyl-4-n-butyl-5-bromophthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,4-tetrahydrophthalimide, N-glycidyl maleimide , N-G Sidyl-α, β-dimethylsuccinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidyl-α-ethylsuccinimide, N-glycidylbenzamide, N-glycidyl-p -Methylbenzamide, N-glycidylnaphthamide, N-glycidylstearylamide and the like. Of these, N-glycidylphthalimide is preferable.

  Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexyl-3,4-cyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl- 4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic And acid imide, N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-tolyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, and the like. 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.

  Examples of the oxazoline compound that can be used as the carboxyl group-reactive end-capping agent used in the present invention include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propyloxy-2-oxazoline, 2- Butoxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-decyloxy-2-oxazoline, 2-dodecyloxy-2-oxazoline, 2-stearyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-crotyloxy-2-oxazoline, 2-phenoxy-2-oxazoline, 2-benzyloxy-2- Oxazoline, 2-cresilo Ci-2-oxazoline, 2-o-ethylphenoxy-2-oxazoline, 2-o-propylphenoxy-2-oxazoline, 2-o-phenylphenoxy-2-oxazoline, 2-m-ethylphenoxy-2-oxazoline, 2-m-propylphenoxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl- 2-oxazoline, 2-heptyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline, 2-tridecyl-2-oxazoline, 2-myristyl-2-oxazoline, 2-oleyl-2- Oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyl-2-o Sazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-benzyl-2-oxazoline, 2-o-ethylphenyl-2-oxazoline, 2-o-propyl Phenyl-2-oxazoline, 2-o-phenylphenyl-2-oxazoline, 2-m-ethylphenyl-2-oxazoline, 2-m-propylphenyl-2-oxazoline, 2-p-phenylphenyl-2-oxazoline 2 -P-ethylphenyl-2-oxazoline, 2-p-propylphenyl-2-oxazoline, 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2 , 2'-bis (4,4'-dimethyl-2-oxazoline), 2,2'-bis (4-ethyl-2-oxazoline) ), 2,2′-bis (4,4′-diethyl-2-oxazoline), 2,2′-bis (4-propyl-2-oxazoline), 2,2′-bis (4-butyl-2) -Oxazoline), 2,2'-bis (4-hexyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline), 2,2'-bis (4-cyclohexyl-2-oxazoline) ), 2,2′-bis (4-benzyl-2-oxazoline), 2,2′-p-phenylenebis (2-oxazoline), 2,2′-m-phenylenebis (2-oxazoline), 2, 2'-o-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline) 2,2'-p-phenylenebis (4,4'-methyl-2-) Oxazoline), 2,2'-m-phenyle Bis (4,4′-methyl-2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylenebis ( 2-oxazoline), 2,2′-octamethylenebis (2-oxazoline), 2,2′-decamethylenebis (2-oxazoline), 2,2′-ethylenebis (4-methyl-2-oxazoline), 2,2′-tetramethylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-9,9′-diphenoxyethanebis (2-oxazoline), 2,2′-cyclohexylenebis ( 2-oxazoline), 2,2′-diphenylenebis (4-methyl-2-oxazoline) and the like. Furthermore, the polyoxazoline compound etc. which contain the said compound as a monomer unit are mentioned.

  Examples of oxazine compounds that can be used as carboxyl group-reactive end-capping agents used in the present invention include 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-ethoxy-5,6- Dihydro-4H-1,3-oxazine, 2-propyloxy-5,6-dihydro-4H-1,3-oxazine 2-butoxy-5,6-dihydro-4H-1,3-oxazine, 2-pentyloxy -5,6-dihydro-4H-1,3-oxazine, 2-hexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-heptyloxy-5,6-dihydro-4H-1,3 -Oxazine, 2-octyloxy-5,6-dihydro-4H-1,3-oxazine, 2-nonyloxy-5,6-dihydro-4H-1,3-oxazine, 2-decyloxy -5,6-dihydro-4H-1,3-oxazine, 2-cyclopentyloxy-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-methallyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy-5,6- And dihydro-4H-1,3-oxazine.

  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'-propylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-butylenebis (5 6-dihydro-4H-1,3-oxazine), 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylenebis (5,6 -Dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-naphthylene (5,6-dihydro- 4H-1,3-oxazine), 2,2'-P, P'- Phenylene bis (5,6-dihydro-4H-1,3-oxazine), and the like. 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.

  As an example of the isocyanate compound that can be used as the carboxyl group-reactive end-capping agent used in the present invention, for example, aromatic, aliphatic, alicyclic isocyanate compounds and mixtures thereof can be used.

  Examples of the monoisocyanate compound include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate. Specific examples of the diisocyanate include 1,5-naphthalene 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, hexamethylene diisocyanate, cyclohexane-4,4'-diisocyanate, xylylene diisocyanate , Isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2, - it can be exemplified diisopropylphenyl-1,4-diisocyanate, and the like. Of these isocyanate compounds, aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate and phenyl isocyanate are preferred.

The carboxyl group reactive end-capping agent can be used by appropriately selecting one or more compounds. The polylactic acid-containing composition of the present invention may be formed by sealing a polylactic acid component with a carboxyl group terminal or an acidic low molecular compound depending on the use to be used as a molded body. From the viewpoint of hydrolysis resistance, the acidic low molecular weight compound is preferably sealed in an amount of 20 equivalents / 10 ⁶ g or less, more preferably 10 equivalents / 10 ⁶ g or less. It is preferably 5 equivalents / 10 ⁶ g or less.

  The acid value of the polylactic acid component can be measured by dissolving the polylactic acid component in an appropriate solvent and titrating with an alkaline solution having a known concentration, or quantifying acidic protons by NMR. The amount of the carboxyl group reactive end-capping agent used is preferably 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight per 100 parts by weight of the polylactic acid component.

The polylactic acid-containing composition of the present invention preferably contains a crystallization accelerator.
The crystallization accelerator includes an organic type and an inorganic type. The crystallization accelerator improves the crystallization speed of the polylactic acid component and improves the moldability and heat resistance.
The total amount of the crystallization accelerator is 0.001 to 10 parts by weight, preferably 0.01 to 7 parts by weight, more preferably 0.1 to 7 parts by weight, particularly preferably 0.3, per 100 parts by weight of polylactic acid. ~ 7 parts by weight.

  When the amount of the crystallization accelerator used is less than 0.001 part by weight, the effect of promoting the crystallization rate is hardly recognized. When the amount exceeds 10 parts by weight, the effect of promoting the thermal decomposition of the resin composition is increased, and at the same time, the effect of reducing the rate of stereocomplex crystallinity is further increased, which is preferable for resin moldability, heat resistance, and wet heat resistance. Increased possibility of causing no side reactions.

  The crystallization accelerator used in the present invention can be selected from a wide variety of compounds, but the crystallization accelerator that promotes the formation of polymer crystal nuclei and the polymer can be softened and moved to facilitate crystal growth. Accelerating plasticizers can preferably be used. As the crystallization accelerator used in the present invention, those generally used as polymer crystallization accelerators can be used without particular limitation, and both inorganic crystallization accelerators and organic crystallization accelerators can be used. Can do.

  As an inorganic crystallization accelerator, talc, kaolin, silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide, boron nitride, montmorillonite , Neodymium oxide, aluminum oxide, phenylphosphonate metal salts, and the like. These inorganic crystallization accelerators are preferably treated with various dispersion aids in order to enhance the dispersibility in the composition.

  As organic crystallization accelerator calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, sodium laurate, Potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, barium stearate , Sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicylic acid , Aluminum dibenzoate, β-naphthoic acid sodium salt, β-naphthoic acid potassium salt, cyclohexanecarboxylic acid sodium salt and other organic carboxylic acid metal salts, p-toluenesulfonic acid sodium salt, sulfoisophthalic acid sodium salt, stearic acid, etc. Amide, ethylene bislauric acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, organic carboxylic acid amides such as trimesic acid tris (t-butylamide), low density polyethylene, high density polyethylene, polyisopropylene, polybutene, Polymers such as poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, and high melting point polylactic acid, and ethylene-acrylic acid copolymer sodium Salt, sodium salt of styrene-maleic anhydride copolymer (so-called ionomer), melamine resin, styrene resin, silicone resin, organophosphate metal salt, sodium phenylphosphonate, potassium phenylphosphonate, calcium phenylphosphonate, phenyl Examples include phosphonic acid metal salts such as zinc phosphonate, benzylidene sorbitol and its derivatives such as dibenzylidene sorbitol.

  Also, polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers may be used as crystallization accelerators. it can.

  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, adipate such as adipate-n-decyl-n-octyl, citrate such as acetyltributyl citrate, bis (2-ethylhexyl) azelate, etc. Examples thereof 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) blocks 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 an epoxy epoxy stearate and soybean oil, and other so-called epoxy resins using bisphenol A and epichlorohydrin as raw materials.

  Other plasticizers include benzoate esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol bis (2-ethylbutyrate), fatty acid amides such as stearamide, butyl oleate, etc. Examples thereof include fatty acid esters, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oil, and paraffins. Of these, those consisting of at least one selected from polyester plasticizers and polyalkylene plasticizers are preferred.

  At least one selected from the group consisting of phosphate ester metal salts, melamine resins, styrene resins and silicone resins is preferably used as the crystallization accelerator. As the phosphoric acid ester metal salt, the compound proposed in Japanese Patent No. 39609797, and “Adeka Stub” NA-10, NA-11 and NA-21, which are commercially available from ADEKA Corporation, are most preferable. The talc is most preferably talc having an average particle diameter of 1 to 10 μm. The crystallization accelerator of the present invention may be applied alone, or two or more kinds may be used in combination.

  Various organic and inorganic fillers can be blended in the polylactic acid-containing composition of the present invention. By blending such an agent, a composition and a molded body excellent in mechanical properties, heat resistance, and moldability can be obtained. The organic filler is not particularly limited as long as it satisfies the requirements of the present invention. Specifically, for example, rice husks, wood chips, okara, waste paper pulverized materials, chips of clothing pulverized materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute fibers, banana fibers, Plant fiber such as coconut fiber, or pulp or cellulose fiber processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, Angola, cashmere, camel, polyester fiber, nylon fiber, acrylic fiber, etc. Synthetic fibers, paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch, and other powdered materials. From the viewpoint of moldability, paper powder, wood powder, bamboo Powder, cellulose powder, kenaf powder, rice husk powder, fruit shell powder, chitin powder, chitosan powder, protein powder, starch and the like are preferable, Flour, wood flour, bamboo powder, cellulose powder, kenaf powder is more preferred, and paper powders, wood flour, particularly paper dust are preferable.

  These organic fillers may be those collected directly from natural products, but may also be those obtained by recycling waste materials such as waste paper, waste wood, and old clothes. Waste paper is newspaper, magazines, other recycled pulp, or cardboard, cardboard, paper tube, etc., and any paper processed from plant fiber may be used. To newspaper paper and cardboard pulverized products such as corrugated cardboard, cardboard and paper tubes are preferred. The wood may be any kind of softwood such as pine, cedar, firewood or fir, or hardwood such as beech, shii or eucalyptus.

  The paper powder is not particularly limited as long as the requirements of the present invention are satisfied, but it is preferable to contain an adhesive from the viewpoint of moldability. The adhesive is not particularly limited as long as it is usually used when processing paper, and emulsion adhesives such as vinyl acetate resin emulsion and acrylic resin emulsion. Examples thereof include polyvinyl alcohol-based adhesives, cellulose-based adhesives, natural rubber-based adhesives, starch paste, and hot-melt adhesives such as ethylene-vinyl acetate copolymer resin adhesives and polyamide-based adhesives. Of these, emulsion adhesives, polyvinyl alcohol adhesives and hot melt adhesives are preferred, and emulsion adhesives and polyvinyl alcohol adhesives are more preferred.

  Such an adhesive is also used as a binder for paper processing. Such adhesives include clay, talc, kaolin, montmorillonite, mica, synthetic mica, zeolite, silica, graphite, carbon black, magnesium oxide, calcium oxide, titanium oxide, aluminum oxide, neodymium oxide, calcium sulfide, magnesium carbonate, carbonic acid. Inorganic fillers such as calcium, barium carbonate and barium sulfate are preferably contained, and clay, talc, kaolin, montmorillonite, mica, synthetic mica, zeolite and silica are more preferable.

  As paper powder, chemicals generally used as a papermaking raw material from the viewpoint of formability, for example, sizing agents such as rosin type, alkyl ketene dimer type, alkenyl succinic anhydride type, paper strength enhancer such as polyacrylamide type, polyethyleneimine Yield improvers such as polymer coagulants, filterability improvers, deinking agents such as nonionic surfactants, slime control agents such as organic halogens, pitch control agents such as organic or enzyme systems, and peroxides Detergents such as hydrogen, organic substances such as antifoaming agents, pigment dispersants and lubricants, aluminum sulfate used as a fixing agent for sizing agents, and other sodium hydroxide and magnesium hydroxide used as raw materials for papermaking Contains inorganic substances such as sodium sulfate, sodium silicate, aluminum chloride, sodium chlorate Preferred.

  In the present invention, the blending amount of the organic filler is not particularly limited, but from the viewpoint of moldability and heat resistance, it is preferably 1 to 300 parts by weight per 100 parts by weight of the polylactic acid component, and 5 to 200 parts by weight. Part is more preferable, more preferably 10 to 150 parts by weight, and particularly preferably 15 to 100 parts by weight. When the blending amount of the agent is less than 1 part by weight, the effect of improving the moldability of the polylactic acid-containing composition is small, and when it exceeds 300 parts by weight, uniform dispersion of the filler becomes difficult, or the moldability, heat resistance In addition to the properties, the strength and appearance of the material may decrease, which is not preferable. In the present invention, it is preferable to use various inorganic fillers other than the organic filler. By blending the inorganic filler, a molding composition and a molded article having excellent mechanical properties, heat resistance and moldability can be obtained.

  As the inorganic filler used in the present invention, a fibrous, plate-like, or powder-like one used for reinforcing ordinary thermoplastic resins can be used. Specifically, for example, glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, imogolite, sepiolite, slag fiber, zonolite, elestite, Fibrous inorganic fillers such as gypsum fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, layered silicate, layered silicate exchanged with organic onium ions, glass flakes, 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 carbonate, magnesium carbonate Um, 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.

  A layered silicate exchanged with organic onium ions is an inclusion compound in which exchangeable cations existing between layers are exchanged with organic onium ions. A layered silicate having an exchangeable cation between layers has a structure in which plate-like materials having a width of 0.05 to 0.5 μm and a thickness of 6 to 15 Å are laminated, and exchangeable cations are provided between the layers of the plate-like material. Has ions. The cation exchange capacity is 0.2 to 3 meq / g, and the cation exchange capacity is preferably 0.8 to 1.5 meq / g.

  Specific examples of the layered silicate 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, Examples thereof include swelling mica such as Na-type fluorine teniolite, LI-type tetrasilicon fluorine mica, and Na-type tetrasilicon fluorine mica, which 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. Examples of the exchanged cation and organic onium ion include ammonium ion, phosphonium ion, and sulfonium ion. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred because of their high ion exchange properties. The ammonium ion may be any of primary to quaternary ammonium ions.

  In the present invention, the amount of the organic onium ion used for the layered silicate is the cation exchange capacity of the layered silicate from the viewpoint of the dispersibility of the layered silicate, the thermal stability during melting, the gas generated during molding, the generation of odor, and the like. On the other hand, it is in the range of 0.4 to 2 equivalents, more preferably 0.8 to 1.2 equivalents.

  These layered silicates are preferably pretreated with a coupling agent having a reactive functional group in addition to the organic onium salt in order to obtain better mechanical properties. Examples of the coupling agent having a reactive functional group include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

  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 ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, and may be treated with a coupling agent such as aminosilane or epoxysilane. Also good.

  The blending amount of the inorganic filler of the present invention is preferably used in the range of 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 50 parts by weight based on 100 parts by weight of the polylactic acid component. Parts, particularly preferably 1-30 parts by weight, most preferably 1-20 parts by weight.

  If desired, the polylactic acid-containing composition of the present invention may contain a thermoplastic resin other than the polylactic acid component. The thermoplastic resin is not particularly limited, and is not limited to polyester resin other than polylactic acid, polyamide resin, polyacetal resin, polyolefin resin such as polyethylene resin and polypropylene resin, polystyrene resin, acrylic resin, polyurethane resin, chlorinated polyethylene. Resin, chlorinated polypropylene resin, aromatic and aliphatic polyketone resin, fluorine resin, polyphenylene sulfide resin, polyetherketone resin, polyimide resin, thermoplastic starch resin, AS resin, ABS resin, AES resin, ACS resin, polychlorination Vinyl resin, polyvinylidene chloride resin, vinyl ester resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenyle Oxide resin, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, and thermoplastic resins such as polyvinyl alcohol resins. Among them, at least selected from polyacetal resins, polyester resins other than polylactic acid, for example, polyester resins such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyamide resins. It is recommended to add one kind. By blending these resins, it becomes possible to obtain compositions and molded articles having the excellent characteristics of these resins.

  The polyacetal resin may be a polymer having an oxymethylene unit as a main repeating unit and a so-called polyacetal homopolymer made of formaldehyde or trioxane as a raw material, or mainly composed of oxymethylene units and having 2 to 8 adjacent groups in the main chain. It may be any of so-called polyacetal copolymers containing 15 mol% or less of oxyalkylene units having carbon atoms, and may be any of copolymers containing other structural units, that is, block copolymers, terpolymers, and crosslinked polymers. These may be used alone or in combination of two or more.

  These may be used alone or in combination of two or more. By blending a thermoplastic resin other than polylactic acid in the present invention, a resin composition and a molded article excellent in surface property, moldability, mechanical properties, heat resistance and toughness can be obtained.

  Further, in the present invention, if desired, an impact resistance improving agent can be blended. 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 various 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 Soprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene graft copolymerized with styrene, butadiene-acrylonitrile copolymer), polyisobutylene, isobutylene and butadiene Alternatively, a copolymer with isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber, and the like can be given.

  In addition, it is composed of various cross-linking degrees, various micro structures such as cis structure, trans structure, etc., a core layer and one or more shell layers covering it, and adjacent layers are composed of heterogeneous polymers. A so-called core-shell type multi-layer structure polymer can also be used. Further, the various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers, block copolymers and the like, and can be used as the impact resistance improver of the present invention. In producing these (co) polymers, it is also possible to copolymerize monomers such as other olefins, dienes, aromatic vinyl compounds, (meth) acrylic acid, (meth) acrylic acid esters, etc. is there.

  Among these impact modifiers, a polymer containing an acrylic unit and a copolymer containing an acid anhydride and / or a unit having a glycidyl group are preferred. Preferred examples of the (meth) acrylic unit here include a methyl methacrylate unit, an ethyl acrylate unit, a methyl acrylate unit and a butyl acrylate unit. Preferable examples include maleic anhydride units and glycidyl methacrylate units.

  The impact resistance improver is preferably a multi-layered polymer called a so-called core-shell type, which is composed of a core layer and one or more shell layers covering the core layer, and the adjacent layer is composed of a different polymer. It is more preferable that it is a multilayer structure polymer which contains a methyl (meth) acrylate unit in a shell layer. Such a multilayer structure polymer preferably contains a (meth) acrylic unit, or a unit having an acid anhydride group and / or a glycidyl group, and a suitable example of the (meth) acrylic unit is methacrylic acid. Examples thereof include a methyl unit, an ethyl acrylate unit, and a methyl acrylate unit. Preferred examples of the unit having an acid anhydride group or a glycidyl group include a maleic anhydride unit and a glycidyl methacrylate unit. In particular, the shell layer contains at least one selected from (meth) acrylmethyl units, maleic anhydride units and glycidyl methacrylate groups, and selected from butyl acrylate units, ethylhexyl acrylate units, styrene units and butadiene units. A multilayer structure containing at least one of the above in the core layer can be preferably used. The glass transition temperature of the impact resistance improver is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.

  In the present invention, the amount of thermoplastic resin other than polylactic acid is preferably in the range of 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, relative to 100 parts by weight of polylactic acid. The amount is more preferably 3 to 70 parts by weight, and particularly preferably 5 to 50 parts by weight.

  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. Further, in the present invention, a colorant containing a brominated flame retardant, a phosphorus flame retardant, a silicone flame retardant, a flame retardant such as an antimony compound, an organic or inorganic dye, or a pigment within the scope not departing from the gist of the present invention. For example, oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as bitumen, chromates such as zinc chromate, sulfates such as barium sulfate, calcium carbonate, etc. Examples thereof include carbonates, silicates such as ultramarine blue, phosphates such as manganese violet, carbon such as carbon black, and metal colorants such as bronze powder and aluminum powder.

  Nitroso series such as naphthol green B, nitro series such as naphthol yellow S, azo series such as naphthol red, chromophthal yellow, phthalocyanine series such as phthalocyanine blue and fast sky blue, condensed polycyclic colorants such as indanthrone blue, etc. Additives such as slidability improvers such as graphite and fluorine resin may be contained. These additives can be used alone or in combination of two or more.

  Furthermore, in the present invention, it is preferable to blend a release agent. As the mold release agent used in the present invention, those used for ordinary thermoplastic resins can be used. Specifically, fatty acids, fatty acid metal salts, oxy fatty acids, paraffin 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 polyhydric alcohol esters, fatty acid higher alcohols Examples include esters, fatty acid polyhydric alcohol partial esters, fatty acid polyglycol esters, and modified silicones. By blending these, a polylactic acid-containing composition and a molded body excellent in mechanical properties, moldability, and heat resistance can be obtained.

  In the present invention, the release agent may be used alone or in combination of two or more. The blending amount of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, based on 100 parts by weight of the polylactic acid component.

  In the present invention, it is also preferable to add an antistatic agent. Examples of the antistatic agent include quaternary ammonium salts such as (β-lauramidopropionyl) trimethylammonium sulfate and sodium dodecylbenzenesulfonate, sulfonate compounds, and alkyl phosphate compounds. In the present invention, the antistatic agent may be used alone or in combination of two or more. The blending amount of the antistatic agent is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polylactic acid component.

  The various additives can be blended in the period from the beginning of the production of polylactic acid to the production of the molded product. The blending method of these agents can be performed according to a conventionally known method. For example, it can be charged and blended in a polymerization apparatus in the polymerization stage of polylactic acid, or polymer pellets obtained by melt polymerization and these agents are tumbler, V-type blender, super mixer, nauter mixer, Banbury mixer, kneading roll. A method of mixing with a monoaxial or biaxial extruder is appropriately used. A method of molding the polylactic acid-containing composition thus obtained can be preferably employed as it is or once in the form of pellets with a melt extruder. The shape of the pellet preferably has a shape suitable for molding the pellet by various molding methods. Specifically, the pellet length is preferably 1 to 7 mm, the major axis 3 to 5 mm, and the minor axis 1 to 4 mm. Further, it is preferable that the shape does not vary.

  A molded product can be obtained by heating the polylactic acid-containing composition of the present invention in the same manner as ordinary polylactic acid and molding it in a molten state. Since the polylactic acid-containing composition of the present invention is sufficiently suppressed from being thermally deteriorated and colored when melted, it is difficult for the hue to deteriorate even in a molten state, and a molded article having a good hue can be obtained.

  In the molded product of the present invention, the polylactic acid-containing composition of the present invention is a mixture of a granular material of a polylactic acid component and a phosphite ester, or the phosphite ester is uniformly dispersed in the polylactic acid component In the case of a polylactic acid-containing composition that has been prepared, this may be heated to be molded into a molten state. Also, when the polylactic acid-containing composition of the present invention is obtained by kneading polylactic acid and phosphites at a temperature higher than the melting temperature of polylactic acid, the obtained polylactic acid-containing composition is cooled. Alternatively, it may be molded in a molten state by supplying it to a molding machine. The molding method is not particularly limited, and the molding can be performed by a molding method such as an injection molding method, an extrusion molding method, an extrusion blow molding method, an injection blow molding method, or a biaxial stretch blow molding method.

  By cooling after molding, a polylactic acid molded article comprising the polylactic acid-containing composition of the present invention is obtained. Examples of polylactic acid molded bodies that can be obtained in this way include coil bobbins, connectors, switches, resistor parts, sockets, relays, capacitor cases, fuses, motors, microwave ovens, printed boards, IC manufacturing devices, electronic parts such as lamps, Auto parts such as air outlet garnish, hood vent, distributor cap, exhaust gas control valve, mechanical parts such as gear and cam, watch parts such as base plate, camera parts such as bottom cover, lens barrel and lever, leisure goods such as reel Parts, home appliance housing, lighting and wiring equipment, films, bottles, fibers, septic tanks, toilets, bathtubs, unit baths, water tanks, ships, chemical tanks, pipes, corrugated plates, flat plates, paints, decorative plates, electrical parts enclosed Wood, resin concrete, etc.

  Such a molded body is composed of the polylactic acid-containing composition of the present invention, and the content of phosphites is usually 0.01 parts by weight or more, preferably 0.03 parts by weight or more per 100 parts by weight of the polylactic acid component, The amount is preferably 0.05 parts by weight or less, usually 5 parts by weight or less, preferably 3 parts by weight or less, and more preferably 1 part by weight or less.

  In such a polylactic acid molded body, heat degradation and coloring of polylactic acid are sufficiently prevented, and deterioration of hue is suppressed even when heated again to a molten state. For example, the molded body is heated to a molten state. By molding, a recycled polylactic acid molded body having a good hue can be obtained easily and reused.

  Here, the description “It is possible to obtain a recycled polylactic acid molded article having a good hue by heating and molding the molded article in a molten state.” In order to obtain a regenerated polylactic acid remolded product in a molten state by coexisting with an unmolded resin composition that has not yet been molded after polymerization, or to be molded after polymerization. It also includes that a molded product can be obtained by partially coexisting components from the molded product when melt molding an unmolded resin composition.

  The economic effect by enabling the reuse of the molded product from the polylactic acid-containing composition of the present invention is great, and the development of the polylactic acid-containing composition of the present invention in a new area is expected.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Each physical property value was also determined by the following method.

1. Measuring method (1) Weight average molecular weight and number average molecular weight (Mn) of polylactic acid:
The weight average molecular weight and number average molecular weight (Mn) of polylactic acid were converted to standard polystyrene by gel permeation chromatography (GPC).
GPC measurement equipment
Detector; differential refractometer Shimadzu RID-6A
Column: Toso-TSKgelG3000HXL, TSKgelG4000HXL, TSKgelG5000HXL and TSKguardcocumHXL-L connected in series, or Toso-TSKgelG2000HXL, TSKgelG3000HXL and TSKguardLumX used. Chloroform was used as an eluent, flowed at a temperature of 40 ° C. and a flow rate of 1.0 ml / min, and 10 μl of a sample having a concentration of 1 mg / ml (chloroform containing 1% hexafluoroisopropanol) was injected and measured.

(2) Hue Hue of polylactic acid-containing composition;
The color b value of the solution was measured with a Z-1001DP color difference meter manufactured by Nippon Denshoku Industries Co., Ltd., using the polylactic acid-containing composition as a 10% chloroform solution. A larger color b value indicates a worse hue. A composition having a chloroform solution color b value exceeding 3.5 was judged to be unsuitable for commercial use.

(3) Measurement of crystal melting point and melting enthalpy:
It measured using the Shimadzu Corporation DSC-60 differential scanning calorimeter DSC.
A 10 mg sample was heated from room temperature to 250 ° C. under a nitrogen atmosphere at a rate of temperature increase of 10 ° C./min. The crystal melting temperature (Tmh) and heat of crystal melting (ΔHmh) of a polylactic acid homo-single crystal having a peak temperature of 190 ° C. or less. ) And stereocomplex polylactic acid crystals were determined for crystal melting temperature (Tm) and heat of crystal melting (ΔHmh).

[Production Example 1-1] Production of phosphite-containing poly L-lactic acid:
In Production Example 1-1, a vertical stirring tank (120 L) equipped with a vertical fistula blade equipped with a vacuum pipe, a nitrogen gas pipe, a catalyst, an L-lactide solution addition pipe, and an alcohol initiator addition pipe was placed in nitrogen. After substitution, 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine (hereinafter referred to as PES1) 0.3 kg, L-lactide 60 kg, stearyl alcohol 0.27 kg (0.017 mol / kg-LD), tin octylate 3.6 g (1.5 × 10 ⁻⁴ mol / 1 kg LD) was charged, and the temperature was raised to 150 ° C. under an atmosphere of nitrogen pressure 106.4 kPa. When the contents were dissolved, stirring was started and the internal temperature was reduced. 19 more The temperature was raised to 0 ° C. After the reaction was carried out for 1 hour while maintaining the internal temperature at 180 ° C. to 190 ° C., the stirring was stopped, and then the internal pressure was increased from 2 to 3 atm with nitrogen pressure and the prepolymer was extruded into a chip cutter, and the weight average molecular weight was 170,000, A prepolymer having a molecular weight dispersion of 1.8 was pelletized.

  The prepolymer is fed to the first non-axial vertical stirring blade polymerization apparatus having a capacity of 60 L by a loader at a rate of 20 kg / hr, transferred to the non-axial vertical stirring blade polymerization apparatus at 190 to 210 ° C., and at the inlet 20 mol of DHPA as a deactivator was added per 1 mol of the catalyst, and after performing a lactide reduction treatment with an internal pressure of 1.33 kPa and a residence time of 0.5 hour, it was transferred to a chip cutter with a metering pump to form a chip. The lactide-reduced polylactic acid composition had a weight average molecular weight of 160,000, a molecular weight dispersion of 1.8, and a lactide content of 0.005% by weight. The polylactic acid produced in this production example is referred to as B1.

[Production Example 1-2] Production of phosphite-containing poly-D-lactic acid:
In Production Example 1-1, poly D-lactic acid (C1) was obtained in the same manner as in Example 1-1 except that L-lactide was used and D-lactide having an optical purity of 99% or more was used.

[Production Examples 2, 3, 4-1, 4-2] Production of phosphite-containing poly L-lactic acid and phosphite-containing poly D-lactic acid:
In Production Example 1-1, the addition time of PES1 was changed so that the weight average molecular weight of poly L-lactic acid was 1000 (Production Example 2-1), 10000 (Production Example 3-1), and 1650,000 (Production Example 4-1). At this point, the polymer was added to the polymerization apparatus and polymerized to obtain polylactic acids B2, B3, and B4 each having a weight average molecular weight of 165,000, a molecular weight dispersion of 1.8, and a lactide content of 0.005% by weight. It was.

  Moreover, it replaced with L-lactide in manufacture example 2-1, and the weight average molecular weight of polylactic acid is 1000 (manufacture example 2-2) 10000 (manufacture example 3-2) as D-lactide with 99% or more of optical purity. Polylactic acid C2, C3, and C4 were produced in Production Examples 2-2, 3-2, and 4-2 performed at the time of reaching 1650,000 (Production Example 4-2).

[Production Examples 5-1, 5-2] Production of phosphite-containing poly L-lactic acid and phosphite-containing poly D-lactic acid:
In Production Example 1-1 or Production Example 1-2, PES1 was added when liquid was fed to a polymerization apparatus equipped with a non-axial saddle blade with a prepolymer ruder, and the same treatment was performed thereafter, starting from a weight average molecular weight of 161,000. Polylactic acids B5 and C5 having a molecular weight dispersion of 1.8 to 1.9 and a lactide content of 0.005% by weight were obtained.

[Production Examples 6-1 and 6-2] Production of phosphite-containing poly L-lactic acid and phosphite-containing poly D-lactic acid:
100 parts by weight of polylactic acid having a weight average molecular weight of 166,000, a molecular weight dispersion of 1.9 and a lactide content of 0.005% by weight and PES1, 0 produced without the addition of PES1 in Production Example 1-1 or 1-2 The polylactic acid B6 and C6 were produced by kneading 0.01 wt.

[Production Examples 7-1 and 7-2] Production of poly-L-lactic acid and poly-D-lactic acid:
In Production Example 1, using L-lactide (Production Example 7-1) or D-lactide (Production Example 7-2), without using PES1, poly L-lactic acid; B7 or poly D-lactic acid; C7 Manufactured.

[Production Examples 8, 9-1, 9-2]
In Production Example 2-1 / 2, PES1 is replaced with tetrakis (2,4-di-t-butylphenyl) -4,4′-diphenylenediphosphonite) (hereinafter sometimes abbreviated as PES2) or bis. Each was changed to (2,4-di-t-butylphenyl) pentaerythritol diphosphite (may be abbreviated as PES3), and the others were treated in the same manner to obtain a weight average molecular weight of 1610,000 to 16.6. Poly (L-lactic acid) having a molecular weight dispersion of 1.8 to 1.9 and a lactide content of 0.005% by weight; B8, B9 and poly (D-lactic acid); C8,9 were obtained.
Table 1 summarizes the production conditions for the polylactic acids (B) and (C) produced in the above production examples.

[Example 1] Production of polylactic acid-containing composition:
50 parts by weight of each of the polylactic acid B1 and C1 pellets obtained in Production Example 1 and 0.3 part by weight of “ADEKA STAB” NA-21 manufactured by ADEKA Corporation per 100 parts by weight of the total pellets are uniformly mixed using a tumbler. After drying at 110 ° C. for 5 hours, the “Carbodilite” LA-1 manufactured by Nisshinbo Industries Co., Ltd. is used as above by a first supply port of a twin screw extruder with a 30 mmφ vent (KTX-30 manufactured by Kobe Steel). On the same basis, 1 part by weight is supplied from the second supply port, kneaded while degassing at a cylinder temperature of 220 ° C., a residence time of 3 minutes, and a vacuum of 1.33 kPa (10 mmHg), and extruded into cold water from a nozzle. Turned into.
The obtained pellet showed only the melting peak of the stereocomplex polylactic acid crystal by DSC measurement, and the stereocomplex crystallinity was 100%.
The color b value of a 10% solution of chloroform is 0.8, the color b value of a 10% solution of chloroform of a sample heat-treated at 260 ° C. for 20 minutes in an air atmosphere is 1.5, and the carboxyl group concentration is 0.1. Equivalent / ton, moist heat resistance was 95%.
This pellet was dried at 110 ° C. for 5 hours, and measured using an injection molding machine (SG150U type, manufactured by Sumitomo Heavy Industries, Ltd.) with a cylinder temperature of 240 ° C. and a mold temperature of 100 ° C. for 3 mm thick ASTM measurement. A molded piece (first molded product) was prepared. This molded product had a good hue.
The molded product was pulverized, mixed with the initially obtained pellets at a ratio of 2/8 by weight, dried at 110 ° C. for 5 hours, and a second molded piece was produced under the above conditions.
There was no significant difference in hue between the first and second molded products by visual judgment, and it was found that a molded product of good quality could be obtained by recovery and reuse.

[Example 2]
50 parts by weight of each of the polylactic acid B2 pellets and the polylactic acid C2 pellets obtained in Production Example 2, and talc (fine talc, Micro Ace P6 (average particle size, 4 μm) manufactured by Nippon Talc Co., Ltd.) 1 per 100 parts by weight of the total pellets Part by weight and 0.3 part by weight of “ADEKA STAB” NA-21 manufactured by ADEKA Co., Ltd. were uniformly mixed using a tumbler, dried at 110 ° C. for 5 hours, and then a twin screw extruder with a 30 mmφ vent (Kobe Steel Co., Ltd.) Using KTX-30), the mixture was kneaded while being deaerated at a cylinder temperature of 220 ° C., a residence time of 3 minutes, and a vacuum of 1.33 kPa (10 mmHg), and extruded into cold water from a nozzle to be pelletized.
The obtained pellet showed only the melting peak of stereocomplex polylactic acid crystal by DSC measurement, and the stereocomplex crystallinity was 100%. The color b value of a 10% solution of chloroform is 0.9, the color b value of a 10% solution of chloroform of a sample heat-treated at 260 ° C. for 20 minutes in an air atmosphere is 1.7, and the carboxyl group concentration is 0.1 equivalent. / ton, moist heat resistance was 95%.
The pellets were dried at 110 ° C. for 5 hours and then used for an ASTM measurement with a thickness of 3 mm using an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 100 ° C. A molded piece (first molded product) was prepared. This molded product had a good hue.
The molded product was pulverized, mixed with the pellets initially obtained in Example 2 in a weight ratio of 2/8, dried at 110 ° C. for 5 hours, and then a second molded piece was produced under the above conditions. .
There was no significant difference in hue between the first and second molded products by visual judgment.

[Example 3]
50 parts by weight of each of the polylactic acid B3 pellets and polylactic acid C3 pellets obtained in Production Example 3, and talc (fine talc by Japan Talc Co., Ltd., Micro Ace P6 (average particle size, 4 μm)) per 100 parts by weight of the pellets 1 The parts by weight are uniformly mixed using a tumbler, dried at 110 ° C. for 5 hours, and subjected to a 30 mmφ vented twin screw extruder (KTX-30 manufactured by Kobe Steel, Ltd.) with a cylinder temperature of 240 ° C. and a residence time of 3 The mixture was kneaded while being degassed at a vacuum of 1.33 kPa (10 mmHg), extruded from a nozzle into cold water, and pelletized.
The obtained pellets had a stereocomplex crystallinity of 87% as measured by DSC. The color b value of a 10% solution of chloroform is 1.0, the color b value of a 10% solution of chloroform of a sample heat-treated at 260 ° C. for 20 minutes in an air atmosphere is 1.8, the carboxyl group concentration is 0.1, The heat and humidity resistance was 95%.
The pellets were dried at 110 ° C. for 5 hours and then used for an ASTM measurement with a thickness of 3 mm using an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 100 ° C. A molded piece (first molded product) was prepared. This molded product had a good hue.
The molded product was pulverized, mixed with the pellets initially obtained in Example 3 in a weight ratio of 2/8, dried at 110 ° C. for 5 hours, and then a second molded piece was produced under the above conditions. .
There was no significant difference in hue between the first and second molded products by visual judgment.

[Example 4]
50 parts by weight of each of polylactic acid B4 pellets and polylactic acid C4 pellets obtained in Production Example 4, and talc per 100 parts by weight of the total pellets (fine powder talc manufactured by Nippon Talc Co., Ltd., Micro Ace P6 (average particle size, 4 μm)) 1 Part by weight and 0.3 part by weight of Asahi Denka Adeka Ab NA21 using a tumbler are uniformly mixed, dried at 110 ° C. for 5 hours, and a twin screw extruder with a 30 mmφ vent (KTX-30 manufactured by Kobe Steel, Ltd.) The mixture was kneaded while being deaerated at a cylinder temperature of 220 ° C., a residence time of 3 minutes, and a vacuum of 1.33 kPa (10 mmHg), and extruded into cold water from a nozzle to be pelletized.
The obtained pellet showed only the melting peak of stereocomplex polylactic acid crystal by DSC measurement, and the stereocomplex crystallinity was 100%. The color b value of a 10% solution of chloroform is 2.1, the color b value of a 10% solution of chloroform of a sample heat-treated at 260 ° C. for 20 minutes in an air atmosphere is 3.3, and the carboxyl group concentration is 0.1 equivalent. / Ton, moist heat resistance was 95%.
The pellets were dried at 110 ° C. for 5 hours and then used for an ASTM measurement with a thickness of 3 mm using an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 100 ° C. A molded piece (first molded product) was prepared. This molded product was slightly yellow but had a usable hue.
The molded product was pulverized, mixed with the pellets obtained in Example 4 at a ratio of 2/8 by weight, dried at 110 ° C. for 5 hours, and then a second molded piece was produced under the above conditions.
There was no significant difference in hue between the first and second molded products by visual judgment.

[Example 5]
Using 50 parts by weight of each of the polylactic acid B5 pellets and the polylactic acid C5 pellets obtained in Production Example 5, the same treatment as in Example 2 was performed to obtain pellets.
The obtained pellet showed only the melting peak of stereocomplex polylactic acid crystal by DSC measurement, and the stereocomplex crystallinity was 100%. The color b value of a 10% solution of chloroform is 1.5, the color b value of a 10% solution of chloroform of a sample heat-treated at 260 ° C. for 20 minutes in an air atmosphere is 2.0, and the carboxyl group concentration is 0.1 equivalent. / ton, moist heat resistance was 95%.
The pellets were dried at 110 ° C. for 5 hours and then used for an ASTM measurement with a thickness of 3 mm using an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 100 ° C. A molded piece (first molded product) was prepared. This molded product had a good hue.
The molded product was pulverized, mixed with the pellets obtained in Example 5 at a ratio of 2/8 by weight, dried at 110 ° C. for 5 hours, and then a second molded piece was prepared under the above conditions.
There was no significant difference in hue between the first and second molded products by visual judgment.

[Example 6]
Using 50 parts by weight of each of the polylactic acid B6 pellets and the polylactic acid C6 pellets obtained in Production Example 6, the same treatment as in Example 2 was performed to obtain pellets.
The obtained pellet showed only the melting peak of the stereocomplex polylactic acid crystal by DSC measurement, and the stereocomplex crystallinity was 100%. The color b value of a 10% solution of chloroform is 2.4, the color b value of a 10% solution of chloroform of a sample heat-treated at 260 ° C. for 20 minutes in an air atmosphere is 3.4, and the carboxyl group concentration is 0.1. Equivalent / ton, moist heat resistance was 95%.
The pellets were dried at 110 ° C. for 5 hours and then used for an ASTM measurement with a thickness of 3 mm using an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 100 ° C. A molded piece (first molded product) was prepared. This molded product showed a faint yellow color, but had a hue that could be used as a stereocomplex polylactic acid molded product.
The molded product was pulverized, mixed with the pellets obtained in Example 6 at a ratio of 2/8 by weight, dried at 110 ° C. for 5 hours, and then a second molded piece was prepared under the above conditions.
There was no significant difference in hue between the first and second molded products by visual judgment.

[Comparative Example 1]
Using 50 parts by weight of each of the polylactic acid B7 pellets and polylactic acid C7 pellets obtained in Production Example 7, the same treatment as in Example 2 was performed to obtain pellets.
The obtained pellet showed only the melting peak of the stereocomplex polylactic acid crystal by DSC measurement, and the stereocomplex crystallinity was 100%. The color b value of a 10% solution of chloroform is 4.5, the color b value of a 10% solution of chloroform of a sample heat-treated at 260 ° C. for 20 minutes in an air atmosphere is 4.8, and the carboxyl group concentration is 0.1. Equivalent / ton, moist heat resistance was 95%.
This composition was judged to be unusable due to poor hue.

[Comparative Examples 2 and 3]
50 parts by weight of each of polylactic acid B8 pellets and polylactic acid C8 pellets obtained in Production Example 8 (Comparative Example 2), polylactic acid B9 pellets obtained in Production Example 9 and polylactic acid C9 pellets (Comparative Example 3) Used and processed into pellets as in Example 2.
The obtained pellet showed only the melting peak of the stereocomplex polylactic acid crystal by DSC measurement, and the stereocomplex crystallinity was 100%. The color b value of a 10% solution of chloroform was 3.4, which was a reasonable hue in Comparative Examples 2 and 3, but the color b value of a 10% solution of chloroform of a sample heat-treated at 260 ° C. for 20 minutes in an air atmosphere. Were 4.2 and 4.3 in Comparative Examples 2 and 3, respectively. The carboxyl group concentration was 0.1 equivalent / ton, and the heat and humidity resistance was 95%.
This composition was molded in the same manner as in Example 2, and a clear hue difference was recognized by visual judgment between the first and second molded articles, and it was determined that there was a problem in recovery and reuse.

  According to the present invention, it is possible to obtain a polylactic acid-containing composition having a good hue and hue stability and a molding comprising the composition. Furthermore, the molded article of the present invention can be recycled and used without significant deterioration in hue, and the effect of suppressing the economic cost by using the polylactic acid composition of the present invention is great.

Claims (18)

A polylactic acid-containing composition comprising polylactic acid and phosphites represented by the following general formula (1) and simultaneously satisfying the following requirements (a) to (c):

[Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl having 6 to 12 carbon atoms. A group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X is a single bond, a sulfur atom or a formula (1-1). Indicates a divalent residue,

(In the formula, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.)
A represents an alkylene group having 2 to 8 carbon atoms or a divalent residue represented by the formula (1-2);

(In the formula, R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents that it is bonded to the oxygen atom side),
Y or Z is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or a carbon number. 1-8 alkyl groups are shown. ] At least 1 type of compound represented by this.
(A) The color b value measured as a 10% solution of chloroform is less than 2.5.
(B) The color b value measured as a 10% solution of chloroform after being kept at 260 ° C. for 20 minutes in an air atmosphere is less than 2.5.
(C) In DSC measurement, the stereocomplex crystallinity (S) defined by the following formula (1) is 80% or more.
[Equation 1]
[S = { _{ΔH msc} / ( _{ΔH mh} + _{ΔH msc} )} × 100 (1)
ΔH _msc and ΔH _mh are the DSC measurement, peak heat corresponding to melting of polylactic acid homocrystals from 160 to 190 ° C. (J / g), peak corresponding to melting of stereocomplex polylactic acid crystals, respectively. This represents the heat of crystal fusion (J / g) at a temperature of 190 ° C. or higher. ] The composition according to claim 1, which satisfies the following requirements (a ') and (b').
(A ′) Color b value measured as a 10% solution of chloroform is less than 1.5.
(B ′) The color b value measured as a 10% chloroform solution of the composition held at 260 ° C. for 20 minutes in an air atmosphere is less than 2. The composition according to claim 1, which satisfies the following requirements (a '') and (b '').
(A ″) Color b value measured as a 10% solution of chloroform is less than 1.
(B ″) The color b value measured as a 10% chloroform solution of the composition held at 260 ° C. for 20 minutes in an air atmosphere is less than 1.5.   The composition according to claim 1, wherein only a peak having a peak temperature of 190 ° C or higher corresponding to melting of the stereocomplex crystal is substantially detected by DSC measurement.   When the carboxyl group concentration is 10 equivalents / ton or less, and the heat-and-moisture stability expressed by the retention rate (%) of the reduced viscosity (ηsp / c) when held at 80 ° C. and 90% RH for 11 hours is 80% or more The composition according to any one of claims 1 to 4, wherein:   The composition according to any one of claims 1 to 5, comprising 0.01 to 5 parts by weight of a phosphite represented by the general formula (1) per 100 parts by weight of polylactic acid.   The composition according to any one of claims 1 to 6, comprising 0.001 to 10 parts by weight of a stereocomplex crystallization accelerator per 100 parts by weight of polylactic acid.   The composition according to any one of claims 1 to 7, comprising 5 to 300 parts by weight of a carboxyl end group blocking agent per 100 parts by weight of polylactic acid.   The composition according to any one of claims 1 to 8, comprising 5 to 300 parts by weight of a thermoplastic resin other than polylactic acid per 100 parts by weight of polylactic acid. Copolymers other than L-lactic acid having a crystalline polylactic acid (B) component having a D-lactic acid unit as a main component and a copolymer unit other than D-lactic acid consisting of 0 to 10 mol% and an L-lactic acid unit as main components A crystalline polylactic acid (C) component having a unit of 0 to 10 mol% was obtained by melt ring-opening polymerization of lactide in the presence of a metal-containing catalyst, and then (B) / (C) by weight ratio. = (10) / (90) to (90) / (10) When melt-mixing to obtain a polylactic acid composition, the crystalline polylactic acid (B) component and / or the crystalline polylactic acid (C) component A process for producing a polylactic acid-containing composition, wherein phosphites represented by the general formula (1) are added at any stage until the completion of the melt ring-opening polymerization.

[Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl having 6 to 12 carbon atoms. A group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X is a single bond, a sulfur atom or a formula (1-1). Indicates a divalent residue,

(In the formula, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.)
A represents an alkylene group having 2 to 8 carbon atoms or a divalent residue represented by the formula (1-2);

(In the formula, R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents that it is bonded to the oxygen atom side),
Y or Z is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or a carbon number. 1-8 alkyl groups are shown. ] At least 1 type of compound represented by this.   The production method according to claim 10, wherein the addition of phosphites is performed when the weight average molecular weight of the polylactic acid component is less than 10,000.   The production method according to claim 10, wherein the addition of phosphites is performed when the polylactic acid component has a weight average molecular weight of less than 1000.   The production method according to claim 10, wherein the phosphites are added to the lactide before the melt ring-opening polymerization reaction.   The production method according to claim 10, wherein the addition of the phosphites represented by the general formula (1) is carried out by containing the phosphites represented by the general formula (1) in the raw material lactide.   The molded object which consists of a polylactic acid containing composition in any one of Claim 1 to 9.   The molded product according to claim 15, wherein the content of the compound represented by the general formula (1) is 0.01 parts by weight or more and 5 parts by weight per 100 parts by weight of polylactic acid.   A method for reusing a polylactic acid molded product, wherein the molded product according to claim 15 is melted and molded again.   The reproduction | regeneration molded object obtained by the method of Claim 17.