JP2009249517A - Polylactic acid composition excellent in hue and moist heat stability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polylactic acid composition having a high degree of stereo-specificity formation, and excellent in transparency, hue and moist heat stability. <P>SOLUTION: This polylactic acid composition comprises a polylactic acid (B) containing D-lactic acid unit as a main component and a 0 to 10 mol% copolymerization unit other than the D-lactic acid, and the polylactic acid (C) containing L-lactic acid unit as a main component and a 0 to 10 mol% copolymerization unit other than the L-lactic acid, having the (10/90) to (90/10) weight ratio (B/C) of the polylactic acid (B) to the polylactic acid (C), and also having (a) the ≥80% degree of stereospecificity formation (S), (b) a ≥80% moist heat stability, (c) a ≤15 color difference b* value, and (d) a ≤1,000 ppm lactide content. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polylactic acid composition having a high stereogenicity and excellent in hue, transparency and wet heat stability, a molded product thereof, and a method for producing the poly milk composition.

Due to environmental problems such as global warming, concerns over oil depletion and supply conditions in oil-producing countries, oil prices have soared and the development of non-petroleum resins is required. Among them, polylactic acid has not only the possibility of being a substitute for petroleum-based resin, but also has characteristics in optical properties such as transparency and low refractive index, and application development utilizing this is expected.
However, polylactic acid usually has a low melting point of about 160 ° C., and there is a problem in heat resistance such as melting and deformation. In addition, biodegradability and degradation under wet heat environment proceed at a relatively fast rate, and despite the application of catalyst deactivators such as phosphoric acid, there are problems in stability of physical properties, so there is a disadvantage that its use is limited. Had.

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 stereocomplex polylactic acid is formed by mixing in (Patent Document 1 and Non-Patent Document 1). This stereocomplex polylactic acid has a melting point as high as 200 to 230 ° C. as compared with PLLA and PDLA, and an interesting phenomenon such as high crystallinity has been discovered.
However, when producing stereocomplex polylactic acid, if the weight average molecular weight of PLLA and PDLA is as high as 100,000 or more, stereocomplex polylactic acid is difficult to obtain by the method of heat treatment, and even if it is obtained, It takes a long time to produce, and there is a drawback that industrial implementation becomes difficult. On the other hand, it is well known that a molecular weight of 100,000 or more is necessary to develop practical strength as a molded body.

Further, in solution blending, attempts have been made to form a stereocomplex from high molecular weight PLLA and PDLA having a molecular weight of 100,000 or more. However, there is a problem in productivity because it needs to be maintained in a solution state for a long period of time.
In addition, such a stereocomplex polylactic acid does not show a single phase of stereocomplex polylactic acid, but a single phase of poly L-lactic acid and poly D-lactic acid (hereinafter sometimes referred to as a homo phase), and a stereocomplex polylactic acid phase. A composition comprising a composite phase (hereinafter sometimes referred to as a complex phase), and a differential melting calorimeter (DSC) measurement usually has a low melting crystal melting peak with a peak temperature of 190 ° C. or less corresponding to melting of a homophase crystal. Two peaks of a high melting point crystal melting peak having a peak temperature of 190 ° C. or higher corresponding to the melting of the complex phase crystal are measured. When homophase crystals coexist in stereocomplex polylactic acid, there also exists a problem that it is difficult to sufficiently exhibit the heat resistance inherent in stereocomplex polylactic acid.
In order to solve this problem, a method for producing stereocomplex polylactic acid by high-temperature treatment of a composition comprising PLLA and PDLA having a specific molecular weight range has been proposed and a desired result has been obtained (Patent Document 3). However, there is room for further improvement in hue and wet heat stability.

In order to promote the formation of a stereocomplex polylactic acid phase, catalyst deactivation by a phosphoric acid compound and application of a crystallization nucleating agent such as a phosphoric acid ester metal salt have been proposed, and a complex having a crystal melting point of 209 ° C. does not contain a homophase crystal. A heat-resistant composition and a molded product containing only phase crystals have been proposed (Patent Document 2). However, when a crystallization nucleating agent is used, the polylactic acid composition may be reduced in weight average molecular weight, deterioration in wet heat stability, deterioration in hue and transparency. The decrease in the transparency of the resin limits the use of the polylactic acid resin and becomes a factor limiting the product development. Similarly to PLLA and PDLA, stereocomplex polylactic acid is also classified into the category of aliphatic polyesters. As a feature of aliphatic polyesters, it has the disadvantage that it is easily decomposed by humidity. The problem that the trend is further promoted has also become apparent.
Application of carbodiimide compounds has been proposed to improve the wet heat stability of stereocomplex polylactic acid, and some results have been observed (Patent Documents 4 and 5). However, the carbodiimide compound may be decomposed by various additives, particularly a phosphate metal salt, and the desired effect may not be obtained. In addition, decomposition of carbodiimide compounds, particularly aliphatic or cycloaliphatic carbodiimides, may cause new problems such as coloring the resin composition and making it difficult to use as a commercial product.
JP 63-24014 A Macromolecules, 24, 5651 (1991). JP 2003-192894 A International Publication No. 2006-009285 Pamphlet JP 2004-332166 A JP 2005-350829 A

  An object of the present invention is to provide a polylactic acid composition having a high stereocomplex polylactic acid phase content (degree of stereoification). Another object of the present invention is to provide a polylactic acid composition excellent in transparency, hue and wet heat stability. Furthermore, the objective of this invention is providing the manufacturing method of this polylactic acid composition. Another object of the present invention is to provide a molded article comprising the polylactic acid composition.

  The present inventor has intensively studied to achieve the above-mentioned object, and when poly-D-lactic acid and poly-L-lactic acid are melt-kneaded to produce a polylactic acid composition, poly-D-lactic acid and poly-L-lactic acid are not yet used. When polylactic acid containing an inactive polymerization catalyst is used, and a catalyst deactivator and a carbodiimide compound are added in this order when melt-kneading, a high degree of stereonation, transparency, hue, and wet heat stability The present inventors have found that a lactic acid composition can be obtained and completed the present invention.

That is, the present invention
1. A polylactic acid (B) containing a D-lactic acid unit as a main component and a copolymer unit other than D-lactic acid in an amount of 0 to 10 mol% and an L-lactic acid unit as a main component and a copolymer unit other than L-lactic acid as 0 to 10 Containing polylactic acid (C) containing mol%, and the weight ratio (B / C) of polylactic acid (B) to polylactic acid (C) is from 10/90 to 90/10,
A) Stereoization degree (S) is 80% or more,
B) Wet heat stability is 80% or more,
C) Color difference b * value is 15 or less,
D) Lactide content of 1000 ppm or less,
{However, the degree of stereogenicity (S) is a value defined by the following formula (1).
S = [ΔHmsc / (ΔHmh + ΔHmsc)] × 100 (1)
ΔHmh represents the heat of crystal fusion (J / g) of the polylactic acid homophase in the differential scanning calorimeter (DSC) measurement. ΔHmsc represents the heat of crystal fusion (J / g) of the stereocomplex polylactic acid phase in the differential scanning calorimeter (DSC) measurement.
The wet heat stability (%) is the retention rate (%) of the reduced viscosity (η _sp / c) when the sample is held at 80 ° C. and 90% RH for 11 hours. }
A polylactic acid composition,
2. A) Stereoization degree is 90% or more,
B) Wet heat stability is 85% or more,
C) Color difference b * value is 10 or less,
D) Lactide content of 500 ppm or less,
The polylactic acid composition according to claim 1, wherein
3. A) Stereoization degree is 95% or more,
B) Wet heat stability is 85% or more,
C) Color difference b * value is 8 or less,
E) Lactide content of 100 ppm or less,
The polylactic acid composition according to claim 1, wherein
4). The polylactic acid composition according to any one of 1 to 3 above, wherein the haze is 7% or less,
5. The polylactic acid composition according to any one of the above items 1 to 3, wherein the haze is 5% or less,
6). A polylactic acid (B) containing a D-lactic acid unit as a main component and a copolymer unit other than D-lactic acid in an amount of 0 to 10 mol% and an L-lactic acid unit as a main component and a copolymer unit other than L-lactic acid as 0 to 10 A method for producing a polylactic acid composition by melt kneading polylactic acid (C) containing mol%, wherein polylactic acid (B) and polylactic acid (C) contain an inactivated polymerization catalyst, and are melt kneaded. A method for producing a polylactic acid composition, comprising adding a catalyst deactivator and a carbodiimide compound in this order,
7). The production method according to 6 above, wherein the catalyst deactivator is a metaphosphoric acid compound or phosphoric acid,
8). The production method according to 6 above, wherein the melt kneading is performed at 230 to 300 ° C.
9. The production method according to 6 above, wherein the melt kneading is performed at 240 ° C to 280 ° C.
10. The production method according to 6 above, wherein the lactide contents of polylactic acid (B) and polylactic acid (C) are each 80,000 ppm or less,
11. The production method according to 6 above, wherein the melt kneading is performed while degassing
12 A molded article comprising the polylactic acid composition according to any one of 1 to 5,
13. 13. The molded article according to the above 12, which is a film, sheet, injection molded article, blow molded article, fiber or fiber structure,
Is included.

  In the polylactic acid composition of the present invention, a stereocomplex polylactic acid phase is highly formed, and is excellent in wet heat stability and hue. The polylactic acid composition of the present invention also has a low haze. Moreover, according to the manufacturing method of this invention, a polylactic acid composition can be manufactured.

  The present invention will be described in detail below.

[Polylactic acid composition]
<Polylactic acid (B) and (C)>
The polylactic acid composition of the present invention has a D-lactic acid unit as a main component, a polylactic acid (B) containing 0 to 10 mol% of copolymer units other than D-lactic acid as a main component, and an L-lactic acid unit as a main component. -Polylactic acid (C) containing 0 to 10 mol% of copolymerized units other than lactic acid is contained.
The polylactic acid (B) and (C) is preferably composed of 95-100 mol% D-lactic acid units and 0-5 mol% units other than D-lactic acid, or 95-100 mol% L-lactic acid. It consists of units and units other than 0-5 mol% L-lactic acid.

The polylactic acid (B) and (C) must have crystallinity, and the melting point thereof is preferably 150 ° C. or higher and 190 ° C. or lower, and more preferably 160 ° C. or higher and 190 ° C. or lower. Is more preferable. When stereocomplex polylactic acid is formed from polylactic acid (B) and (C) that fall within the melting point range, a complex crystal phase having a higher melting point can be formed and the crystallinity can be increased. The crystallinity of the polylactic acid component can be easily confirmed by detecting a crystal melting peak in the above range in a differential scanning calorimeter (DSC) measurement.
The polylactic acids (B) and (C) preferably have a weight average molecular weight in the range of 80,000 to 500,000, more preferably 90,000 to 300,000. The range of 100,000 to 250,000 is particularly preferable. By using polylactic acid having such a weight average molecular weight range, stereocomplex polylactic acid can be produced industrially and efficiently, and the moldability and mechanical properties of the polylactic acid composition of the present invention can be balanced. .

The crystal melting enthalpy of the polylactic acid (B) or (C) is preferably 20 J / g or more, more preferably 30 J / g or more.
The weight ratio (B / C) of polylactic acid (B) to polylactic acid (C) is preferably 90/10 to 10/90. More preferably, it is in the range of 80/20 to 20/80, more preferably 30/70 to 70/30, and particularly preferably 40/60 to 60/40. Theoretically, the one closer to 50/50 as much as possible is stereo. It is preferably selected to improve the degree of conversion.

It is important that the polylactic acid (B) and the polylactic acid (C) are not deactivated. By using polylactic acid (B) or (C) in which such a polymerization catalyst is not deactivated, it becomes possible for the first time to obtain a polylactic acid composition that has advanced to a degree of stereogenicity of 80% or higher. If the polymerization catalyst of polylactic acid (B) and polylactic acid (C) is deactivated before melt-kneading, it is difficult to obtain a polylactic acid composition having a stereogenicity of 80% or more only by melt-kneading. In order to obtain a polylactic acid composition having a degree of stereoization of 80% or more, application of a phosphate metal salt is inevitable as described above, but it is difficult to avoid the disadvantages caused by blending a phosphate metal salt. is there.
The polylactic acid (B) or (C) used in the present invention may contain an L-lactic acid or D-lactic acid unit and other copolymerization components as desired as long as the crystallinity is not impaired.

  The copolymer component other than the lactic acid unit is not particularly limited. For example, dihydric alcohols such as ethylene glycol, propylene glycol, propanediol, butanediol, heptanediol, hexanediol, octanediol, and nonanediol. , Decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, etc., trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, etc. , Aromatic hydroxy compounds such as hydroquinone, resorcin, bisphenol A, etc., divalent carboxylic acids such as succinic acid, succinic acid, adipic acid, sebacic acid, azerai Acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (4-carboxyphenyl) methane, anthracene dicarboxylic acid, bis (4-carboxyphenyl) ether Trivalent or higher polyvalent carboxylic acids such as sodium 5-sulfoisophthalate, such as trimellitic acid, pyromellitic acid, oxyacids other than lactic acid such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycapron Examples thereof include lactones such as acid and hydroxybenzoic acid, such as caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

Such constituents other than lactic acid can be copolymerized in order to achieve a desired purpose within a range that does not impair the biodegradability and heat resistance of the polylactic acid composition. The upper limit should be 10 mol%, preferably 0 to 5 mol%, more preferably 0 to 3 mol%.
The method for producing the polylactic acid (B) or (C) used in the present invention is not particularly limited, and a conventionally known method can be suitably used. For example, a method of directly dehydrating and condensing D- or L-lactic acid, a method of synthesizing D- or L-lactic acid oligomer by direct polycondensation and then solid-phase polymerizing, and once dehydrating and cyclizing D- or L-lactic acid with lactide Then, a method of melt ring-opening polymerization is exemplified.
Of these, polylactic acid obtained by a direct dehydration condensation method or a melt ring-opening polymerization method is preferable from the viewpoint of quality and production efficiency, and a melt ring-opening polymerization method of lactides is most preferably selected.
In these production methods, a catalyst is usually used, and any of them can be used as long as the polylactic acid (B) and (C) can be polymerized so as to have the above-mentioned predetermined characteristics.

  Alcohol may be used as a polymerization initiator. Such an alcohol-based initiator is preferably non-volatile without inhibiting the polymerization of polylactic acid. For example, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, divalent alcohols such as ethylene glycol , Propylene glycol, propanediol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene A trihydric or higher polyhydric alcohol such as glycol such as glycerin, trimethylolpropane, pentaerythritol and the like can be suitably used.

  The amount of alcohol-based initiator used is primarily determined in consideration of the desired weight average molecular weight (Mw). For example, in the case of monohydric alcohol, when producing a polylactic acid resin having Mw of 70,000 to 110,000, 0.009 to 0.03 mol, particularly preferably 0.014 to 0.021 mol, per 1 kg of lactide. Is used. Further, when producing a polylactic acid resin having an Mw of 100,000 to 200,000, 0.009 to 0.02 mol, particularly preferably 0.01 to 0.018 mol is used per 1 kg of lactide.

  In the melt ring-opening polymerization, the mixture of lactide, catalyst and alcohol-based initiator removes heat of reaction in a temperature range of 180 to 230 ° C., more preferably in a temperature range of 185 ° C. to 220 ° C., according to a conventionally known method. On the other hand, a reaction time of 0.5 to 10 hours is applied, and polymerization is carried out by using a vertical polymerization tank, a horizontal polymerization tank, a tubular polymerization tank, or a combination thereof by a continuous or batch process. The reaction time and reaction temperature need to be appropriately selected by judging the progress of polymerization.

That is, as a catalyst for polymerization by melt ring-opening reaction of lactide, fatty acid salts such as alkali metals, alkaline earth metals, rare earths, transition metals, aluminum, germanium, tin, antimony, carbonates, sulfates, phosphates, oxidations Products, hydroxides, halides, alcoholates and the like are well known. In view of the catalytic activity and the small number of side reactions, a catalyst containing tin is particularly preferably selected. Specifically, stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, tin myristate, tin octylate, tin stearate, tetraphenyltin, tin methoxide, Preferred examples include tin-containing compounds such as tin alkoxide and aluminum-containing compounds such as aluminum acetylacetonate, aluminum butoxide, and aluminum-imine complexes. More preferably, the following are illustrated. In other words, diethoxytin, dinonyloxytin, tin myristate, tin octylate, tin stearate, tin chloride, aluminum acetylacetonate, aluminum isopropoxide, etc. Illustrated as preferred.
The amount of the catalyst used is 0.42 × 10 ⁻⁴ to 100 × 10 ⁻⁴ mol per 1 kg of lactide, and 1.2 × 10 ⁻⁴ to 42 in consideration of reactivity, color tone and stability of the resulting polylactide. 0.1 × 10 ⁻⁴ mol, particularly preferably 1.3 × 10 ⁻⁴ to 9.4 × 10 ⁻⁴ mol are used.

The degree of stereoification (S) of the polylactic acid composition of the present invention is preferably 80% or more, more preferably 90% or more, and still more preferably 95%. The stereoization degree (S) is a value defined by the following formula (1).
S = [ΔHmsc / (ΔHmh + ΔHmsc)] × 100 (1)
ΔHmh represents polylactic acid homophase crystal heat of fusion (J / g) in differential scanning calorimetry (DSC) measurement. ΔHmsc represents stereocomplex polylactic acid phase crystal heat of fusion (J / g) in differential scanning calorimetry (DSC) measurement.
The wet heat stability of the polylactic acid composition of the present invention is preferably 80% or more, more preferably 85% or more, still more preferably 85% to 99%, and particularly preferably 90% to 98%. Wet heat stability is a stability parameter when a sample is exposed to a wet heat condition, and is expressed as a retention rate of reduced viscosity when the sample is held at 80 ° C. and 90% RH for 11 hours. Is done. If the parameter is 80% or more, it is judged that the molded article made of the composition can be used for a practical time under normal wet heat conditions.
The color difference b * value of the polylactic acid composition of the present invention is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The lactide content of the polylactic acid composition of the present invention is preferably 1000 ppm or less in order to suppress coloring of the polylactic acid composition and its molded product, and to improve the melt stability or wet heat stability. More preferably, it is 500 ppm or less, More preferably, it is 100 ppm or less.
The polylactic acid composition of the present invention is excellent in transparency. That is, the haze value of the polylactic acid composition of the present invention is preferably 7% or less, more preferably 5% or less. From the polylactic acid composition of the present invention, it is possible to obtain injection molded products and blow molded products having a haze value of 10% or less, and films and sheets having a 5% or less haze value.
In the polylactic acid composition of the present invention, in the differential scanning calorimeter (DSC) measurement, the ratio of the melting peak at 195 ° C. or higher due to the melting of the stereocomplex polylactic acid crystal among the melting peaks in the temperature rising process is 80% or higher. More preferably, it is 90% or more, More preferably, it is 95% or more. The melting point of the stereocomplex polylactic acid crystal is in the range of 195 to 250 ° C, more preferably in the range of 200 to 230 ° C.

The crystal melting enthalpy of the polylactic acid composition of the present invention is 20 J / g or more, preferably 30 J / g or more. Polylactic acid composition with low crystal melting enthalpy and poor crystallinity has low heat resistance because the crystal structure of the molded product is weaker than the composition. It is difficult to achieve speed.
The melt stability of the polylactic acid composition of the present invention is preferably 80% or more, more preferably 85% to 99%, and still more preferably 90% to 98%. Melt stability is a stability parameter at the time of melting of the resin, and the sample is evaluated by the retention rate of reduced viscosity after holding the sample at 260 ° C. for 10 minutes. If the melt stability is 80% or more, melt molding such as normal injection molding and extrusion molding can be performed by appropriately setting conditions.
The weight average molecular weight of the polylactic acid composition of the present invention is preferably 80,000 to 500,000, more preferably considering the balance between moldability and mechanical properties of the molded product It is 100,000 to 300,000, more preferably 100,000 to 250,000.

[Method for producing polylactic acid composition]
The production method of the present invention is a method for producing a polylactic acid composition by melt-kneading polylactic acid (B) and polylactic acid (C), wherein polylactic acid (B) and polylactic acid (C) are not deactivated. The catalyst deactivator and the carbodiimide compound are added in this order when melt-kneading.
As described above, the polylactic acid (B) contains 0 to 10 mol% of a copolymer unit other than the D-lactic acid having a D-lactic acid unit as a main component. As mentioned above, polylactic acid (C) contains L-lactic acid units as a main component and 0 to 10 mol% of copolymer units other than L-lactic acid.
It is important that the polylactic acids (B) and (C) contain an inactivated polymerization catalyst. By using the polylactic acid (B) and (C) in which the polymerization catalyst is not deactivated, it becomes possible to obtain a polylactic acid composition having a stereolation degree of 80% or more. If the polymerization catalyst of polylactic acid (B), (C) is deactivated before melt kneading, a polylactic acid composition having a stereogenicity of 80% or more is obtained only by heat treatment of polylactic acid (B), (C). It is difficult. In the method of the present invention, a polylactic acid composition having a high degree of stereolation can be obtained without using a phosphoric acid ester metal salt, and defects due to the phosphoric acid ester metal salt can be eliminated. The lactide contents of polylactic acid (B) and polylactic acid (C) are each preferably 80,000 ppm or less.

<Melting and kneading>
The temperature for melt kneading is preferably 230 ° C. to 300 ° C., more preferably 240 ° C. to 280 ° C. When producing stereocomplex polylactic acid by melt-kneading polylactic acid, a temperature range of about 200 to 260 ° C. is usually selected in the prior art from the viewpoint of preventing coloration of polylactic acid. In the present invention, polylactic acid (B) and (C) in which the polymerization catalyst is not deactivated is used in order to advance the degree of stereoization to 80% or higher without blending a phosphoric acid ester metal salt. It is preferable to perform heat treatment at a high temperature of 230 to 300 ° C. By melt-kneading at a high temperature, the degree of stereoification can be advanced to a high degree in a relatively short time, and the hue and transparency of the composition can be improved.

As the melt kneading method, a conventionally known batch type or continuous type melt mixing apparatus is preferably used. For example, a melt-stirred tank, a single-screw or twin-screw extruder, a kneader, a non-shaft vertical stirring tank, "Vibolac" manufactured by Sumitomo Heavy Industries, N-SCR manufactured by Mitsubishi Heavy Industries, a spectacle blade manufactured by Hitachi, a lattice blade, or a Kenix type stirrer, Alternatively, a Sulzer type SMLX type static mixer equipped pipe type polymerization apparatus can be used. In view of productivity, polylactic acid quality, especially color tone, a self-cleaning type polymerization apparatus which is a self-cleaning type agitation tank, N-SCR, twin-screw extruder, etc. are preferably used.
The melt kneading is performed for a time sufficient to bring the composition to a stereogenic degree of 80% or more. Thereafter, melt kneading (post kneading) is preferably performed at a low temperature of 220 to 240 ° C. as close as possible to the crystal melting temperature of the obtained stereocomplex polylactic acid. The quencher is preferably added at the time of post-kneading in order to suppress deterioration of hue and transparency of the polylactic acid composition.

<Deaeration>
The melt kneading (including post-kneading) is preferably performed while degassing. In order to reduce the lactide content of the polylactic acid composition, it is preferable to perform deaeration at least once during melt-kneading. The lactide content of the polylactic acid composition obtained by the method of the present invention is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 100 ppm or less in order to suppress coloring. The haze value of the obtained polylactic acid composition is preferably 7% or less, more preferably 5% or less.

<Catalyst deactivator>
In the present invention, the catalyst deactivator is added when melt-kneading. The catalyst deactivator is preferably added in an amount of 0.3 to 20 equivalents per equivalent of the metal element of the metal catalyst.
Examples of the catalyst deactivator include a metaphosphoric acid compound, phosphoric acid, an imine compound, a phosphorus oxo acid, a phosphorus oxo acid ester, and an organic phosphorus oxo acid compound represented by the formula (2).
_{X 1 -P (= O) m} (OH) n (OX 2) 2-n (2)
(In the formula, m is 0 or 1, n is 1 or 2, and X ₁ and X ₂ each independently represents a hydrocarbon group optionally having a substituent having 1 to 20 carbon atoms.)
As the catalyst deactivator, a metaphosphoric acid compound and phosphoric acid are preferable.

  The imine compound used in the present invention is a tetradentate chelate ligand having an imino group in its structure and capable of coordinating with a metal polymerization catalyst. Since the imine compound of the present invention is not a Bronsted acid or a base like conventional catalyst deactivators, it is possible to improve the thermal stability without deteriorating the hydrolysis resistance of the polylactic acid resin composition. is there. Particularly preferred examples of such imine compounds include N, N′-bis (salicylidene) ethylenediamine and N, N′-bis (salicylidene) propanediamine.

Examples of the phosphorus oxoacid include dihydridooxoline (I) acid, dihydridotetraoxodiphosphorus (II, II) acid, hydridotrioxoline (III) acid, dihydridopentaoxodiphosphoric acid (III), and hydridopentaoxodioxy (II, IV) acid, dodecaoxohexaline (III) III, hydridooctaoxotriphosphate (III, IV, IV) acid, octaoxotriphosphate (IV, III, IV) acid, hydridohexaoxodiline (III, V) ) Low oxidation number phosphorus having an acid number of 5 or less, such as acid, hexaoxodiphosphorus (IV) acid, decaoxotetralin (IV) acid, hendecaoxotetralin (IV) acid, eneoxooxo triphosphoric acid (V, IV, IV) acid Examples are acids. Further, orthophosphoric acid represented by the formula xH ₂ O · yP ₂ O ₅ , x / y = 3, 2> x / y> 1, and diphosphoric acid, triphosphoric acid, tetraphosphoric acid, five Polyphosphoric acid called phosphoric acid and a mixture thereof, metaphosphoric acid represented by x / y = 1, especially trimetaphosphoric acid, tetrametaphosphoric acid, 1> x / y> 0, phosphorous pentoxide structure Examples thereof include ultraphosphoric acid having a partly network structure, monovalent and polyhydric alcohols of these acids, partial esters of polyalkylene glycols, and complete ester. From the catalyst deactivation ability, acids or acidic esters are preferably used.
There are no particular restrictions on the alcohol that forms the ester of the phosphorus oxoacid, but monovalent alcohols optionally having 1 to 22 carbon atoms and substituents having 2 to 22 carbon atoms Examples thereof may include polyhydric alcohols and sugar alcohols.

  The metaphosphoric acid compound used as a catalyst deactivator in the present invention is a compound in which about 3 to 200 phosphoric acid units are condensed, and has the ability to form a complex with a metal or water molecule. Metaphosphate compounds are cyclic polydentate ligands, which are complex stability constants compared to monodentate or chain polydentate ligands such as phosphoric acid, phosphorous acid, pyrophosphoric acid, polyphosphoric acid and their esters. Therefore, it is possible to supplement metal elements such as catalysts and additives and moisture efficiently and robustly. The metaphosphoric acid compound is selected from the metaphosphoric acid represented by the formula (3), the ultra-region metaphosphoric acid having a three-dimensional network structure, or their (alkal metal salt, alkaline earth metal salt, onium salt). Those containing at least one kind are preferably selected.

(Wherein r is an integer of 1 to 200)
Examples of the alkali metal salt of metaphosphoric acid include sodium salt and potassium salt of metaphosphoric acid. Examples of the alkaline earth metal salt of metaphosphoric acid include calcium salt and magnesium salt of metaphosphoric acid. Examples of the onium salt of metaphosphoric acid include tetraethylammonium metaphosphate, tetra-n-butylammonium metaphosphate, tetraethylphosphonium metaphosphate, and tetra-n-butylphosphonium metaphosphate. Among them, sodium metaphosphate has been established as a food additive and is exemplified as a preferable one for safety. Furthermore, sodium metaphosphate is solid at room temperature, has a lower melting point than polylactic acid, and even when added to a polylactic acid composition as a solid, it melts at a lower temperature than polylactic acid and can be uniformly dispersed in the polylactic acid composition. Since it has an advantage, it is not necessary to use it as a solution such as an aqueous solution, and it can be preferably used because the corrosiveness of the apparatus is small compared to metaphosphoric acid which shows strong acidity.

A normal metaphosphoric acid compound is not a single compound, but usually a mixture of n = 1 to 200 compounds. Among them, a mixture in which n is about 1 to 100 is preferable, more preferably 1 to 50, and still more preferably 1 to 12, or a large proportion of those in such a range.
In view of compatibility with the polylactic acid composition, prevention of hue deterioration of the composition when carbodiimide is applied, and ease of handling, the metaphosphate compound is dissolved in 100 ml of pure water. The pH is preferably 6 or less, more preferably 4 or less, and still more preferably 2 or less. Of these, metaphosphoric acid or a sodium salt thereof satisfying such a pH range is preferably exemplified.

The metaphosphoric acid-based compound preferably has a P (═O) OH moiety in the molecule in order to effectively suppress deterioration of the color tone of the composition when blended with carbodiimide. That is, when the pH of the aqueous metaphosphoric acid solution is 6 or less, it is determined that at least one P (═O) OH site exists in the molecule. When the pH exceeds 6, the ability to effectively prevent the deterioration of the color tone of the composition when blended with carbodiimide is lowered, and it is judged that it is not preferable as the metaphosphate compound of the present invention.
The metaphosphoric acid compounds are known in various shapes such as liquid and solid. Further, the metaphosphoric acid compounds of the present invention have a glass transition temperature of 100 ° C. or higher, particularly 130 to 150 ° C. Those having a glass transition temperature of 5 are preferably selected because of their purity, ease of handling, and suitability for the present invention.

In the present invention, the catalyst deactivator is added during melt kneading. It is important to add the catalyst deactivator at a stage that is not later than the time of addition of the carbodiimide compound.
The catalyst deactivator is preferably added by an extruder or a kneader in consideration of uniform dispersion in the polylactic acid composition and ability to prevent hue deterioration. That is, it is preferable to connect the polymer discharge port of the reaction tank to a uniaxial or multiaxial extruder and add the catalyst deactivator from the extruder addition port. At this time, the quenching agent is metered directly into the extruder or kneader as a molten liquid, an aqueous solution or an organic solvent solution, or a dispersion in water or an organic solvent, or added to the polylactic acid composition from a so-called side feeder. You can also Examples of such organic solvents include polar organic solvents such as ethers such as dimethoxyethane and tetrahydrafuran, and alcohols such as methanol and ethanol.

It is also a preferred embodiment to mix and knead the polylactic acid composition with an extruder or kneader as a chip or fine powder masterbatch.
The addition amount of the quenching agent is used in the range of 0.0001 to 10 parts by weight per 100 parts by weight of the total of polylactic acid (B) and (C). When the amount of the deactivator exceeds this range, the polylactic acid composition is plasticized and causes an increase in water absorption, which is not preferable. In addition, an increase in water absorption may cause a problem of reducing resistance to hydrolysis during long-term storage or use.
Also, if the addition amount is small, the deactivation of the catalyst proceeds only inadequately, and the ability to prevent hue deterioration is sufficiently exhibited, or the dispersion of the catalyst deactivator in the composition becomes non-uniform and uniform throughout the composition May not progress to
Therefore, the amount of the catalyst deactivator added is preferably about 100 parts by weight of the total of the polylactic acid (B) and (C) in consideration of the hue of the entire composition of the catalyst deactivator and the suppression of physical properties. The amount is 0.0002 to 5 parts by weight, more preferably 0.0005 to 1 part by weight, still more preferably 0.001 to 0.5 part by weight.

<Carbodiimide compound>
In the production method of the present invention, after adding the catalyst deactivator, the carbodiimide compound is added. Carbodiimide compounds improve the wet heat stability of polylactic acid compositions.
The carbodiimide compound used in the present invention is a compound having one or more carbodiimide groups in the molecule. The carbodiimide compound preferably contains a small amount of isocyanate groups in the molecule. By containing a small amount of an isocyanate group, the wet heat stability of the polylactic acid composition can be improved. That is, when an isocyanate group is present in the carbodiimide compound, not only the effect of the combined use of the isocyanate compound appears but also the wet heat stability is further improved by the closer presence of the carbodiimide group and the isocyanate group.
When a polycarbodiimide compound is used, it is preferable that a plurality of carbodiimide groups present in the molecule are placed at an appropriate distance from each other. That is, those having a carbodiimide equivalent of about 200 to 500 are preferable. The carbodiimide compound is preferably a compound containing 0.1 to 5% by weight of an isocyanate group and having a carbodiimide equivalent of 200 to 500.

  Examples of the carbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, octyldecylcarbodiimide, di-t-butylcarbodiimide, t-butylisopropylcarbodiimide, dibenzylcarbodiimide, N-octadecylimide '-Phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, bis (p-nitrophenyl) carbodiimide, bis ( p-aminophenyl) carbodiimide, bis (p-hydroxyphenyl) carbodiimide, bis (p-chloro) Enyl) 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-phenylenenebis ( p-chlorophenylcarbodiimide), 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide, hexamethylenebis (cyclohexylcarbodiimide), ethyl Bis (phenylcarbodiimide), ethylenebis (cyclohexylcarbodiimide), bis (2,6-dimethylphenyl) carbodiimide, bis (2,6-diethylphenyl) carbodiimide, bis (2-ethyl-6-isopropylphenyl) carbodiimide, bis ( 2-butyl-6-isopropylphenyl) carbodiimide, bis (2,6-diisopropylphenyl) carbodiimide, bis (2,6-di-t-butylphenyl) carbodiimide, bis (2,4,6-trimethylphenyl) carbodiimide, Bis (2,4,6-triisopropylphenyl) carbodiimide, bis (2,4,6-tributylphenyl) carbodiimide, di-β-naphthylcarboimide, N-tolyl-N′-cyclohexylcarbosiimide, N— Trill-N ' Mono- or di-carbodiimide compounds such as phenyl carbocyclylalkyl imide and the like.

Of these, bis (2,6-diisopropylphenyl) carbodiimide and 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide are preferable from the viewpoints of reactivity and stability. Of these, industrially available dicyclohexylcarbodiimide and diisopropylcarbodiimide are also suitable.
Also, 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 And polycarbodiimides such as (p-toluylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyldisopropylphenylenecarbodiimide), and poly (triethylphenylenecarbodiimide).

Examples of commercially available polycarbodiimide compounds include Carbodilite LA-1 sold under the trade name of Carbodilite marketed by Nisshinbo Co., Ltd., or Stabuxol marketed by HMV-8CA Line Chemie Japan Co., Ltd. can do.
The carbodiimide compound can be produced by a conventionally known method. For example, it can be produced by subjecting an organic isocyanate 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. The polycarbodiimide compound may be a conventionally known method for producing a polycarbodiimide compound, for example, US Pat. No. 2,941,956, Japanese Examined Patent Publication No. 47-33279, J. Pat. Org. Chem. 28, 2069-2075 (1963), Chemical Review 1981, Vol. 81 no. 4, p619-621 and the like.

A carbodiimide compound, when incorporated in a polylactic acid composition, has a strong tendency to decompose and color at high temperatures, but its decomposition and coloration are suppressed by the presence of the deactivator of the present invention, particularly a metaphosphoric acid compound. It is preferably selected after addition of the active agent.
Among carbodiimide compounds, aliphatic or alicyclic carbodiimide compounds have a large tendency to deteriorate the hue of polylactic acid composition, especially color b * value, when contacted with a phosphate ester metal salt. In this case, the deactivator, particularly the metaphosphoric acid compound, is effective in suppressing the deterioration of the hue of the composition.

When the carbodiimide compound is applied to the polylactic acid composition, the method of applying the catalyst deactivator of the present invention after applying the metaphosphoric acid compound is particularly effective for suppressing coloration. That is, it is preferable to avoid the coexistence of the phosphoric acid ester metal salt and the carbodiimide compound in the absence of the metaphosphoric acid compound in order to prevent the composition from being colored.
The addition amount of the carbodiimide compound is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5.0 parts by weight, still more preferably 0 per 100 parts by weight of the total of polylactic acid (B) and (C). 0.5 to 2.0 parts by weight.

<Oxazoline compound>
In the production method of the present invention, an oxazoline compound may be added after adding a catalyst deactivator. Oxazoline compounds improve the wet heat stability of polylactic acid compositions.

  Examples of oxazoline compounds that can be used in the present invention include, for example, 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, 2-butoxy-2-oxazoline, 2- Pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-nonyloxy-2-oxazoline, 2-decyloxy-2-oxazoline, 2-cyclopentyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-crotyloxy-2-oxazoline, 2-phenoxy-2- Oxazoline, 2-Credit 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-propyl-2-oxazoline, 2-butyl-2 -Oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline 2-cyclopentyl-2-oxazoline, 2-cyclohexyl-2- Xazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-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, etc. Is mentioned.

Furthermore, 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′-dimethyl-)
2-oxazoline), 2,2′-m-phenylenebis (4-methyl-2-oxazoline), 2,2′-m-phenylenebis (4,4′-dimethyl-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 (2-oxazoline) Such And the like. Furthermore, a polyoxazoline compound containing the above-described compound as a monomer unit, such as a styrene-2-isopropenyl-2-oxazoline copolymer, can be mentioned. Among these oxazoline compounds, one or more compounds are preferably used.

  The polylactic acid composition of the present invention further comprises a thermoplastic resin other than polylactic acid, a stabilizer, a crystallization accelerator, a filler, a mold release agent, an antistatic agent, a carboxyl group-reactive end-end capping agent, and a plasticizer. And at least one selected from the group consisting of impact-resistant stabilizers.

<Thermoplastic resin>
If desired, the polylactic acid composition of the present invention can contain a thermoplastic resin other than polylactic acid. The thermoplastic resin is not particularly limited, and is not limited to polyester resin other than polylactic acid resin, polyamide resin, polyacetal resin, polyolefin resin such as polyethylene resin and polypropylene resin, polystyrene resin, acrylic resin, polyurethane resin, chlorinated resin. Polyethylene resin, chlorinated polypropylene resin, aromatic and aliphatic polyketone resin, fluorine resin, polyphenylene sulfide resin, polyether ketone resin, polyimide resin, thermoplastic starch resin, AS resin, ABS resin, AES resin, ACS resin, poly Vinyl chloride resin, polyvinylidene chloride resin, vinyl ester resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polypheny resin Emissions oxide resin, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, and thermoplastic resins such as polyvinyl alcohol resins. Among them, polyester resin other than polyacetal resin and polylactic acid resin, for example, selected from polyester resins such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyamide resin. It is preferable to blend at least one kind.

By blending these resins, a molded product having excellent surface properties, moldability, mechanical properties, durability, toughness and the like can be obtained.
The content of the thermoplastic resin other than polylactic acid milk is preferably 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, even more preferably, per 100 parts by weight of the total of polylactic acid (B) and (C). Is from 3 to 70 parts by weight, more preferably from 5 to 50 parts by weight. By blending these resins, a composition and a molded product having excellent characteristics can be obtained.

<Stabilizer>
The polylactic acid composition of the present invention preferably contains a stabilizer. As a stabilizer, what is used for the stabilizer of a normal thermoplastic resin can be used. For example, an antioxidant, a light stabilizer, etc. can be mentioned. By blending these agents, it is possible to obtain a composition and a molded article excellent in the mechanical properties, moldability, heat resistance and durability of the composition organism.
Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphite compounds, thioether compounds, and the like.

  Examples of hindered phenol compounds include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5 ′). -T-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -Propionate], 2,2'-methylene-bis (4-methyl-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl- -Hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3- t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane and the like.

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

  As the phosphite compound, those in which at least one P—O bond is bonded to an aromatic group are preferable. Specifically, tris (2,6-di-t-butylphenyl) phosphite, tetrakis ( 2,6-di-t-butylphenyl) 4,4′-biphenylene phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-t-butylphenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris ( Nylphenyl) phosphite, 4,4′-isopropylidenebis (phenyl-dialkylphosphite), 6- [3- (3t-butyl-4-hydroxy5-methyl) propoxy] 2,4,8,10-tetrat -Butyl dibenz [d, f] [1,3,2] -dioxaphosphine and the like.

  Among them, tris (2,6-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl) -4-methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,6-di-t-butylphenyl) 4,4'-biphenylene phosphite, 6- [3- (3t-butyl-4-hydroxy-5) -Methyl) propoxy] 2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] -dioxaphosphine and the like can be preferably used.

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

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

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

  Examples of the benzotriazole compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5- Di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-t-butyl-4′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (3,5- Di-t-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-t-butyl-2-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (Α, α-dimethylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] 2H- benzotriazole, 2- (4'-octoxy-2'-hydroxyphenyl) benzotriazole.

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

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

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

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

<Crystallization accelerator>
The polylactic acid of the present invention can contain an organic or inorganic crystallization accelerator. By containing a crystallization accelerator, the action of the phosphate metal salt can be further enhanced, and a composition excellent in mechanical properties, heat resistance, and moldability can be obtained.
The polylactic acid composition of the present invention contains a crystallization accelerator, whereby the crystallinity of the composition is improved, and a composition excellent in moldability and heat resistance can be obtained. Crystallized products with excellent heat resistance can be obtained. In addition, the manufacturing time of the molded product can be greatly shortened, and the economic effect is great.
As the crystallization accelerator used in the present invention, those generally used as polymer crystal nucleating agents can be used, and any of inorganic crystal nucleating agents and organic crystal nucleating agents can be used.

  As inorganic crystal nucleating agents, phosphate metal salt, talc, kaolin, silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, sulfide Calcium, boron nitride, montmorillonite, neodymium oxide, aluminum oxide, phenyl phosphonate metal salt and the like can be mentioned. These inorganic crystal nucleating agents are preferably treated with various dispersing aids in order to enhance the dispersibility in the composition.

  Organic nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, lauric acid Sodium, potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearin Barium acid, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicylic acid Organic carboxylic acid metal salts such as lead, aluminum dibenzoate, sodium β-naphthoate, potassium β-naphthoate, sodium cyclohexanecarboxylate, etc., organic sulfonic acid metal salts such as sodium p-toluenesulfonate, sodium sulfoisophthalate, etc. It is done.

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

By applying a soluble organic crystallization accelerator to these polylactic acid compositions, a polylactic acid composition having both transparency and crystallinity can be obtained.
Among these crystallization accelerators, a crystallization accelerator comprising at least one selected from talc, phosphate metal salt, and trimesic acid tris (t-butylamide) is preferably used. Only one type of crystallization accelerator may be used in the present invention, or two or more types may be used in combination. The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight per 100 parts by weight of polylactic acid.

<Filler>
The polylactic acid of the present invention can contain an organic or inorganic filler. By containing the filler component, a composition excellent in mechanical properties, heat resistance, and moldability can be obtained.
Organic fillers such as rice husks, wood chips, okara, waste paper ground materials, clothing ground materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute fibers, banana fibers, coconut fibers Plant fibers such as pulp or cellulose fibers processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, angora, cashmere and camel, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers , Paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like. From the viewpoint of moldability, powdery materials such as paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, and starch are preferred. Powder, bamboo powder, cellulose powder and kenaf powder are preferred. Paper powder and wood powder are more preferable. Paper dust is particularly preferable.

These organic fillers may be collected directly from natural products, or recycled from waste materials such as waste paper, waste wood, and old clothes.
The paper powder preferably contains an adhesive usually used when processing paper from the viewpoint of formability. The adhesive is not particularly limited, and emulsion adhesives such as vinyl acetate resin emulsion and acrylic resin emulsion, polyvinyl alcohol adhesive, cellulose adhesive, natural rubber adhesive, starch paste and Examples thereof include hot melt adhesives such as ethylene vinyl acetate copolymer resin adhesives and polyamide adhesives.
As paper powder, chemicals generally used as a papermaking raw material from the viewpoint of formability, for example, sizing agents such as rosin, alkyl ketene dimer, alkenyl succinic anhydride, paper strength enhancer such as polyacrylamide, polyethyleneimine Yield improver such as, polymer flocculant, filterability improver, deinking agent such as nonionic surfactant, slime control agent such as organic halogen, pitch control agent such as organic or enzyme, peroxide It preferably contains an organic substance such as a cleaning agent such as hydrogen, an antifoaming agent, a pigment dispersant and a lubricant, and a fixing agent such as a sizing agent.

The blending amount of the organic filler of polylactic acid of the present invention is not particularly limited, but from the viewpoint of moldability and heat resistance, it is preferably 1 per 100 parts by weight of the total of polylactic acid (B) and (C). It is -300 weight part, More preferably, it is 5-200 weight part, More preferably, it is 10-150 weight part, Especially preferably, it is 15-100 weight part. If the blending amount of the organic filler is less than 1 part by weight, the effect of improving the moldability of the composition is small, and if it exceeds 300 parts by weight, uniform dispersion of the filler becomes difficult, or other than moldability and heat resistance In addition, the strength and appearance of the material may decrease, which is not preferable.
The polylactic acid composition of the present invention preferably contains an inorganic filler. A composition excellent in mechanical properties, heat resistance and moldability can be obtained by the inorganic filler. As the inorganic filler used in the present invention, a fibrous, plate-like, or powder-like material used for reinforcing ordinary thermoplastic resins can be used.

  Specifically, for example, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, imogolite, sepiolite, asbestos, slag fiber , Zonolite, Elestite, Gypsum fiber, Silica fiber, Silica. Fibrous inorganic fillers such as alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, layered silicate, layered silicate exchanged with organic onium ions, glass flake, non-swellable 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, barium sulfate, calcium oxide, aluminum oxide, Examples thereof include plate-like and granular inorganic fillers such as titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dosonite, and clay.

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

Examples of the cation and organic onium ion to be exchanged 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.
Those having a reactive functional group and those having high affinity are preferred, and ammonium ions derived from 12-aminododecanoic acid, polyalkylene glycol having an amino group at the terminal, and the like are also preferred.
In addition to the above organic onium salt, these layered silicates are preferably pretreated with a coupling agent having a reactive functional group 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 an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane. Also good.
The blending amount of the inorganic filler is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, and still more preferably 1 with respect to 100 parts by weight of the total of polylactic acid (B) and (C). -50 parts by weight, particularly preferably 1-30 parts by weight, most preferably 1-20 parts by weight.

<Release agent>
The polylactic acid of the present invention preferably contains a release agent. As the release agent component used in the present invention, those used for ordinary thermoplastic resins can be used. Specific examples of the release agent component include fatty acid, fatty acid metal salt, oxy fatty acid, paraffin, low molecular weight polyolefin, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid partial saponified ester, fatty acid lower alcohol ester, Examples thereof include monohydric alcohol esters, fatty acid polyglycol esters, and modified silicones. By blending these, a polylactic acid resin composition and a molded product excellent in mechanical properties, moldability, and heat resistance can be obtained.

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

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

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

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

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

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

Examples of the modified silicone include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.
Of these, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferred. Of these, montanic acid ester, montanic acid partial saponified ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferred, and particularly, montanic acid partial saponified ester and ethylene bisstearic acid amide are preferred. preferable.
A mold release agent may be used by 1 type and may be used in combination of 2 or more type. The content of the release agent is preferably 0.01 to 3 parts by weight, and more preferably 0.03 to 2 parts by weight with respect to 100 parts by weight of the total of polylactic acid (B) and (C).

<Antistatic agent>
The polylactic acid composition of the present invention preferably contains 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 content of the antistatic agent is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total of polylactic acid (B) and (C).

<Carboxyl group reactive end-capping agent>
The polylactic acid composition of the present invention preferably contains a carboxyl group-reactive end capping agent. The carboxyl group-reactive end-capping agent 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 terminal blocking agent not only seals the terminal carboxyl group of the polylactic acid resin, but also includes a carboxyl group generated by the decomposition reaction of the polylactic acid resin and various additives, lactic acid, formic acid and the like. The carboxyl group of a low molecular 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 the end-capping agent, it is preferable to use at least one compound selected from an epoxy compound, an oxazine compound, and an isocyanate compound, and an epoxy compound, an oxazine compound, and an isocyanate compound are particularly preferable.

  As an epoxy compound, 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 can be preferably used. By containing the terminal blocking agent, not only the action of the carbodiimide compound can be improved, but also a composition and a molded product excellent in mechanical properties, moldability, heat resistance, and durability can be obtained.

  As glycidyl ether compounds, 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 di Glycidyl ether, polypropylene glycol diglycidyl ether, neopentylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglyci Bisphenol A diester obtained by condensation reaction of bisphenols such as ether, other 2,2-bis- (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone and the like with epichlorohydrin Examples thereof include glycidyl ether type epoxy resins, bisphenol F diglycidyl ether type epoxy resins, and bisphenol S diglycidyl ether type epoxy resins. Of these, bisphenol A diglycidyl ether type epoxy resins are preferred.

  As the glycidyl ester compound, 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, oleic acid glycidyl ester, linol 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, tetrahydrophthal Acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester , Adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedioic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, etc. . 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 compounds and glycidylamide compounds include 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-tetrabromophthalimide N-glycidyl-4-n-butyl-5-bromophthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,4-tetrahydrophthalimide, N-glycidyl maleimide, N-Guri Dil-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.

  As the oxazine compound, 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- , 6-dihydro-4H-1,3-oxazine, 2-cyclohexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-allyloxy-5,6-dihydro-4H-1,3-oxazine, Examples include 2-methallyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy-5,6-dihydro-4H-1,3-oxazine, and the like.

  Further, 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′- Ethylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-propylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-butylene bis (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 the isocyanate compound, aromatic, aliphatic, and 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.

As the diisocyanate, 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, 2,6-diisopropylphenyl-1 , 4-diisocyanate and the like.
Among these isocyanate compounds, aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate and phenyl isocyanate are preferable.

As the terminal blocking agent, one or more compounds can be appropriately selected and used. The composition of the present invention may be sealed with a carboxyl group terminal or an acidic low molecular compound depending on the use used as a molded product. Specifically, the carboxyl group terminal or acidic low molecular compound is sealed. From the viewpoint of hydrolysis resistance, the acid value of the composition is preferably 20 equivalents / 106 g or less, more preferably 10 equivalents / 106 g or less, and particularly preferably 5 equivalents / 106 g or less. The acid value of the composition can be measured by dissolving the resin composition in a suitable solvent and titrating with an alkali solution having a known concentration, or quantifying acidic protons by NMR.
The content of the terminal blocking agent 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 total of polylactic acid (B) and (C).

When using terminal blocker in this invention, you may use the reaction catalyst of terminal blocker. The reaction catalyst is a compound having an effect of accelerating the reaction between the terminal blocking agent component and the polymer terminal or the carboxyl group of the acidic low molecular weight compound, and a compound capable of accelerating the reaction with a small amount of addition is preferable. Examples of such compounds include alkali (earth) metal compounds, tertiary amines, imidazole compounds, quaternary ammonium salts, phosphine compounds, phosphonium compounds, phosphate esters, organic acids, Lewis acids, and the like.
These can be used alone or in combination of two or more. It is preferable to use an alkali metal compound, an alkaline earth metal compound, or a phosphoric acid ester, and an alkali or alkaline earth metal acid salt is particularly preferable. Particularly preferred are sodium stearate, potassium stearate, calcium stearate, magnesium stearate, sodium benzoate, sodium acetate, potassium acetate, calcium acetate and megnesium acetate.
The addition amount of the reaction catalyst is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and still more preferably 0 per 100 parts by weight of the total of polylactic acid (B) and (C). 0.01 to 0.1 parts by weight.

<Plasticizer>
The polylactic acid composition of the present invention preferably contains a plasticizer. As the plasticizer used in the present invention, generally known plasticizers can be used. For example, a polyester plasticizer, a glycerin plasticizer, a polyvalent carboxylic ester plasticizer, a phosphoric ester plasticizer, a polyalkylene glycol plasticizer, and an epoxy plasticizer.

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

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

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

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

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

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

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

<Impact resistance improver>
The polylactic acid composition of the present invention preferably contains an impact resistance improver. The impact resistance improver used in the present invention can be used to improve the impact resistance of thermoplastic resins, and is not particularly limited. For example, at least one selected from the following impact resistance improvers can be used.

  Specific examples of impact modifiers include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers and their Alkali metal salt (so-called ionomer) ethylene-glycidyl (meth) acrylate copolymer, ethylene-acrylate copolymer (for example, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer), modified ethylene- Propylene copolymer, diene rubber (eg, polybutadiene, polyisoprene, polychloroprene), diene and vinyl copolymer (eg, styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer) , Styrene-a A random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene grafted with styrene, butadiene-acrylonitrile copolymer), polyisobutylene, isobutylene and butadiene or Examples include copolymers with isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber, and the like.

In addition, those having various cross-linking degrees, various micro structures such as those having a cis structure, a trans structure, etc., a core layer and one or more shell layers covering the core layer, and adjacent layers are composed of heterogeneous polymers. A so-called core-shell type multi-layered polymer can also be used.
Further, the various (co) polymers mentioned in the above specific examples may be any of randomand 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 and the like. is there.

Among these impact modifiers, a polymer containing an acrylic unit and a copolymer containing a unit having an acid anhydride and / or a glycidyl group are preferred. Preferred examples of the (meth) acrylic unit mentioned here include a methyl methacrylate unit, an ethyl acrylate unit, a methyl acrylate unit and a butyl acrylate unit, and a unit having an acid anhydride group or a glycidyl group. Preferable examples include maleic anhydride units and glycidyl methacrylate units.
The impact resistance improving material is preferably a multilayer polymer called a so-called core shell, which is composed of a core layer and one or more shell layers covering the core layer, and an adjacent layer is composed of different polymers. It is more preferred that the polymer is a multilayer structure polymer containing methyl acrylate units in the shell layer.

Such a multilayer structure polymer preferably contains a (meth) acryl unit, or a unit having an acid anhydride group and / or a glycidyl group. As a suitable example of the (meth) acryl unit, 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 modifier is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.
The impact resistance improver is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, and still more preferably 10 to 20 parts by weight with respect to 100 parts by weight of the total of polylactic acid (B) and (C). is there.

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

A composition containing these additives can be prepared by mixing the respective components. For the mixing, a tumbler, a V-type blender, a super mixer, a nauter mixer, a Banbury mixer, a kneading roll, a monoaxial or biaxial extruder can be used. The resulting composition can be molded as it is or after being once pelletized with a melt extruder.
The shape of the pellet 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 is 3 to 5 mm, and the minor axis is 1 to 4 mm. Further, it is preferable that the shape does not vary.

<Molded product>
The composition of the present invention can be processed into a molded product by a method such as injection molding or extrusion molding. The mold temperature is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and further preferably 70 ° C. or higher from the viewpoint of increasing the crystallization of the molded product and the molding cycle during injection molding. However, in order to prevent deformation of the molded product, the mold temperature is preferably 140 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.
Molded products comprising the polylactic acid composition of the present invention include injection molded products, extrusion molded products, vacuum, compressed air molded products, blow molded products, etc., films, sheets, sheet nonwoven fabrics, fibers, fiber structures, fabrics, etc. Composites with other materials, agricultural materials, fishery materials, civil engineering. Building materials, stationery, medical supplies or other molded articles can be obtained by a conventionally known method.
In addition, these molded products include various housings, gears, gears, etc. It can be used for various applications such as electronic parts, building members, civil engineering members, agricultural materials, automobile parts (interior and exterior parts, etc.) and daily parts.

Specifically, notebook PC housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, CDs, DVDs, PDs, FDDs Recording medium drive housing and internal parts such as copier housing and internal parts, facsimile and other housing and internal parts, parabolic antennas, etc. Mention electronic components.
Furthermore, VTR housings and internal parts, TV housings and internal parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio. Examples include audio equipment parts such as laser disks (registered trademark) and compact disks, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, and home / office equipment parts.

  Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, motor cases, switches, capacitors, variable capacitor cases , Optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder , Transformer parts, coil bobbins and other electrical / electronic parts, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, Hot walls, adjusters, plastic restraints, ceiling fishing gear, stairs, doors, floors and other building components, fishing lines, fish nets, seaweed aquaculture nets, fishing bales, and other marine products, vegetation nets, vegetation mats, grass bags, Weedproof net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge, sludge dehydration bag, concrete formwork and other civil engineering parts, air flow meter, air pump, thermostat housing, engine mount, ignition Bobbin, ignition case, clutch bobbin, sensor housing, idle speed control valve, vacuum switching valve, ECU housing, vacuum pump case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base , ABS actuator case, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter, fuel cap, fuel strainer, distributor cap, vapor canister housing, air cleaner housing , Timing belt covers, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various paops and other automotive underhood parts, torque control levers, safety belt parts, register blades, washer levers , Window regulator handle, window regulator handle knob, pasig light lever, Automotive interior parts such as sun visor brackets, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Automotive exterior parts, wire harnesses, SMJ connectors, PCB connectors, door grommet connectors, and other automotive connectors, gears, screws, springs, bearings, levers, key systems, cams, ratchets, rollers, water supply parts, toy parts, fans, Machine parts such as teeth, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches, multi-films, tunnel films, bird protection sheets, vegetation protection nonwoven fabrics, seedling pots, Raw pile, seed string tape, germination sheet, house lining sheet, agricultural vinyl stopper, slow-release fertilizer, root-proof sheet, garden net, insect net, young tree net, print laminate, fertilizer bag, sandbag, Agricultural materials such as pest prevention nets, attracting cords, windproof nets, sanitary products such as disposable diapers, sanitary wrapping materials, cotton swabs, towels, toilet seat wipes, medical non-woven fabrics (stitching reinforcements, adhesion prevention films, artificial organ repair materials ), Wound dressings, wound tape bandages, adhesive base fabrics, surgical sutures, fracture reinforcements, medical supplies such as medical films, calendars, stationery, clothing, food packaging films, trays, blisters, Containers such as knives, forks, spoons, plastic cans, pouches, containers, tanks, baskets. Tableware, hot fill containers, microwave cooking containers, cosmetic containers, wraps, foam cushioning materials, paper laminates, shampoo bottles, beverage bottles, cups, candy packaging, shrink labels, lid materials, window wipes, envelopes, fruit bowls, Hand cut tape, easy peel packaging, egg pack, HDD packaging, compost bag, recording media packaging, shopping bag, electricity. Electronic parts wrapping film containers, packaging, natural fiber composite polo shirts, T-shirts, inners, uniforms, sweaters, socks, ties, etc., curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki Hot melt binders such as interior goods, carrier tape, print laminate, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, nonwoven fabric, etc. , Magnetic materials, zinc sulfide, electrode material binders, optical elements, conductive embossed tape, IC trays, golf tees, garbage bags, plastic bags, various nets, toothbrushes, stationery, draining nets, body towels, hand towels, tea Pack, drain filter, chestnut It can be used as a file, coating agent, adhesive, bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter, etc. .

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples.

1. Each value in the examples was determined by the following method.
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn):
It calculated | required by the comparison with the polystyrene standard sample by the gel permeation chromatography (GPC). The GPC measuring instrument is as follows.
Detector: Differential refractometer RID-6A manufactured by Shimadzu Corporation
Pump: LC-9A manufactured by Shimadzu Corporation
Column: Tosoh Corporation TSKgelG3000HXL, TSKgelG4000HXL, TSKgelG5000HXL and TSKguardcocumnHXL-L are connected in series, using chloroform eluent, flowing at a column temperature of 40 ° C, a flow rate of 1.0 ml / min, concentration of 1 mg / ml (containing 1% hexafluoroisopropanol) A 10 μl sample of chloroform) was injected.
(2) Melt stability (%):
The melt stability was evaluated by the retention rate (R) of the reduced viscosity after holding the sample at 260 ° C. for 10 minutes in a nitrogen atmosphere. The reduced viscosity retention rate (R ^m ) was calculated by the following equation.
R ^m = b / a × 100
a: Reduced viscosity of sample before heating b: Reduced viscosity after holding at 260 ° C. for 10 minutes Reduced viscosity retention rate (R ^m ) of 80% or more was accepted (OK), and less than 80% was rejected (NG) .
(3) Wet heat stability (%):
The sample was held at 80 ° C. and 90% RH for 11 hours, and the retention rate of reduced viscosity (η _sp / c) was measured to obtain wet heat stability (R ^h ).
R ^h (%) = c / a × 100
a: Reduced viscosity of the sample before heating c: Reduced viscosity after being held at 80 ° C. and 90% RH for 11 hours Wet heat stability (R ^h ) 80% or more passed (◯), 85% or more excellent (◎), Less than 80% was judged as rejected (NG).
(4) Reduced viscosity (η _sp / c):
1.2 mg of a sample was dissolved in 100 ml of [tetrachloroethane / phenol = (6/4) wt mixed solvent] and measured at 35 ° C. using an Ubbelohde viscosity tube.
(5) Stereoization degree (S):
As a differential scanning calorimeter (DSC), DCS7 manufactured by PerkinElmer Co., Ltd. was used. 10 mg sample, 1st RUN under nitrogen atmosphere at a rate of temperature increase of 20 ° C./min. From 30 ° C. to 250 ° C., heat of crystal melting of polylactic acid homophase (ΔHmh, J / g) and stereo complex poly The heat of crystal fusion (ΔHmsc, J / g) of the lactic acid phase was measured, and the stereogenicity (S) was determined from the following formula (1).
S (%) = [ΔHmsc / (ΔHmh + ΔHmsc)] × 100 (1)
(7) Haze Nippon Denshoku Co., Ltd. Hazemeter MDH2000 is used, in accordance with 6.4 of JIS K7105-1981, for molded products, 1 mm molded product plates are used, and for films and sheets, 100 μm is not used. Measurements were made on stretched samples.
For molded products, if the haze exceeds 10%, it is determined that the transparency is poor. When the haze is less than 10%, it can be used as a transparent molded product. About a film and a sheet | seat, when it was less than 3%, it can be used as a transparent film, and when it was 1% or less, it judged that it was the transparency which can be used as an optical film.
(6) Color difference b * value It put into the predetermined container using the chip | tip of 3-5 mm square, and b * value of the chip | tip was measured using color meter SD5000 by Nippon Denshoku Co., Ltd.
(7) Lactide content 1HNMR of a sample having a concentration of 5 mg / ml (deuterated chloroform containing 1% hexafluoroisopropanol) was measured using JEOL NMR. The signal derived from the methine proton was determined from the integration ratio of the methine proton derived from polylactic acid and the methine proton derived from lactide.
Lactide amount ppm = Lactide methine proton ratio / 2 × 144 / (Lactide methine proton ratio / 2 × 144 + polylactic acid methine proton ratio × 72) × 1000000

2. The raw materials used in the examples are as follows.
(1) Polylactic acid resin (B), (C)
B-1: D-polylactic acid (catalyst not deactivated, lactide reduced), weight average molecular weight 155,000, molecular weight dispersion = 1.7, optical purity 99%
B-2: D-polylactic acid (catalyst deactivation, lactide reduction), weight average molecular weight 155,000, molecular weight dispersion = 1.7, optical purity 99%
B-3: D-polylactic acid (catalyst not deactivated, lactide unreduced), weight average molecular weight 155,000, molecular weight dispersion = 1.7, optical purity 97.5%
C-1: L-polylactic acid (catalyst not deactivated, lactide reduced), weight average molecular weight 156,000, molecular weight dispersion = 1.8, optical purity 99%
C-2: D-polylactic acid (catalyst deactivation, lactide reduction), weight average molecular weight 156,000, molecular weight dispersion = 1.8, optical purity 99%
C-3: D-polylactic acid (catalyst not deactivated, lactide unreduced), weight average molecular weight 156,000, molecular weight dispersion = 1.8, optical purity 97.5%
(2) Carbodiimide (D)
D-1: Nisshinbo Carbodilite LA-1
D-2: Stabaxol (3) catalyst deactivator (E) manufactured by Rhein Chemie Japan
E-1: Rasa Soei Co., Ltd. Acid metaphosphate sodium E-2: Mitesima Chemical Co., Ltd. ultra sodium phosphate E-3: Reagent special grade 98% phosphoric acid E-4: Reagent special grade pyrophosphoric acid

<Examples 1-5, Comparative Examples 1-2>
(Composition)
1/50 parts by weight of polylactic acid (B) and polylactic acid (C) listed in Table 1 were uniformly mixed using a tumbler and dried at 110 ° C. for 5 hours. To the first supply port. Additives of the types and amounts shown in Table 1 (parts by weight per 100 parts by weight of polylactic acid) were supplied to the second supply port. Additives of the types and amounts shown in Table 1 (parts by weight per 100 parts by weight of polylactic acid) were supplied to the third supply port.
The temperature of the first to second kneading zones is 280 ° C., the temperature of the third to fourth kneading zones is 220 ° C., and nitrogen is supplied from the nitrogen gas supply line (8, 9, 10, 11) at a nitrogen pressure of 200 kPa. The mixture was pelletized while being deaerated from the vacuum pump (12) at a degree of vacuum of 10.3 kPa.
The obtained pellets were measured for weight average molecular weight, color difference b * value, stereogenicity (S), melt stability, wet heat stability, and lactide content. The results are shown in Table 1.

(Molding)
Moreover, after drying the obtained pellet at 110 degreeC for 5 hours, using an injection molding machine (Sumitomo Heavy Industries, Ltd. SG150U type | mold), cylinder temperature 190 degreeC, mold temperature 100 degreeC cooling time 2.5 minutes Under these conditions, a molded product for ASTM measurement having a thickness of 3 mm and a molded product having a thickness of 1 mm were prepared. The haze of the obtained molded product was measured. The results are shown in Table 1. As shown in Table 1, the molded article of the present invention is excellent in transparency (haze).

<Example 6>
The pellets obtained in Example 1 were passed through a 30 mm biaxial ruder (cylinder temperature 190 ° C.) and sent to a T die of a molding machine. The film was sandwiched or touched with a mirror surface cooling roll and a mirror surface roll, and melt-extruded into an edgeless new film having a thickness of 0.1 mm and a width of 500 mm. The sheet could be molded well. The MD / TD direction strength of the sheet was 145/128 Mpa, haze value 1, and the number of fish eyes visually determined in a randomly cut 100 mm square film was 8.

<Example 7>
The pellets obtained in Example 1 were spun at a spinning pack temperature of 220 ° C., 36 filaments, an oil for fiber mainly composed of fatty acid ester, and spun at 3000 m / min. The undrawn yarn was drawn 1.45 times at a temperature of 90 ° C., heat-set at 130 ° C. and wound. Both spinning and stretching could be carried out satisfactorily.
The physical properties of the obtained multifilament were 25 ° C., initial sample length 200 mm, tensile speed 200 mm / min, a weighted elongation curve was obtained in accordance with JIS L1013, the breaking strength was divided by the initial fineness, and the strength and elongation were obtained. . Also, the boiling water shrinkage is the initial load, 200 mm of the sample is measured with an initial load of 0.09 cN / dtex, the initial length L0 is measured, then the load is treated free of boiling water for 15 minutes, and after air drying, the initial load is 0.09 cN / dtex. Was determined by (L0−L1) × 100 / L0. As a result, the obtained multifilament was a good fiber having a strength of 4.1 cN / dtex, an elongation of 36%, and a boiling water shrinkage of 9%.

  The polylactic acid composition of the present invention is useful as a material for various molded articles such as fibers, films and sheets.

1 is a schematic diagram of an apparatus used in Examples.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resin compounding line 2 Simultaneous rotation type twin screw extruder 3 1st supply port 4 2nd supply port 5 3rd supply port 6 Feeder 7 Feeder 8 Nitrogen gas supply line 9 Nitrogen gas supply line 10 Nitrogen gas supply line 11 Nitrogen gas Supply line 12 To vacuum pump 13 Cooling bath 14 Strand cutter 15 First kneading zone 16 Second kneading zone 17 Third kneading zone 18 Fourth kneading zone

Claims (13)

A polylactic acid (B) containing a D-lactic acid unit as a main component and a copolymer unit other than D-lactic acid in an amount of 0 to 10 mol% and an L-lactic acid unit as a main component and a copolymer unit other than L-lactic acid as 0 to 10 Containing polylactic acid (C) containing mol%, and the weight ratio (B / C) of polylactic acid (B) to polylactic acid (C) is from 10/90 to 90/10,
A) Stereoization degree (S) is 80% or more,
B) Wet heat stability is 80% or more,
C) Color difference b * value is 15 or less,
D) Lactide content of 1000 ppm or less,
A polylactic acid composition.
{However, the degree of stereogenicity (S) is a value defined by the following formula (1).
S = [ΔHmsc / (ΔHmh + ΔHmsc)] × 100 (1)
ΔHmh represents the heat of crystal fusion (J / g) of the polylactic acid homophase in the differential scanning calorimeter (DSC) measurement. ΔHmsc represents the heat of crystal fusion (J / g) of the stereocomplex polylactic acid phase in the differential scanning calorimeter (DSC) measurement.
The wet heat stability (%) is the retention rate (%) of the reduced viscosity (η _sp / c) when the sample is held at 80 ° C. and 90% RH for 11 hours. } A) Stereoization degree is 90% or more,
B) Wet heat stability is 85% or more,
C) Color difference b * value is 10 or less,
D) Lactide content of 500 ppm or less,
The polylactic acid composition according to claim 1. A) Stereoization degree is 95% or more,
B) Wet heat stability is 85% or more,
C) Color difference b * value is 8 or less,
E) Lactide content of 100 ppm or less,
The polylactic acid composition according to claim 1. The polylactic acid composition according to any one of claims 1 to 3, wherein the haze is 7% or less. The polylactic acid composition according to any one of claims 1 to 3, wherein the haze is 5% or less. A polylactic acid (B) containing a D-lactic acid unit as a main component and a copolymer unit other than D-lactic acid in an amount of 0 to 10 mol% and an L-lactic acid unit as a main component and a copolymer unit other than L-lactic acid as 0 to 10 A method for producing a polylactic acid composition by melt kneading polylactic acid (C) containing mol%, wherein polylactic acid (B) and polylactic acid (C) contain an inactivated polymerization catalyst, and are melt kneaded. A method for producing a polylactic acid composition, comprising adding a catalyst deactivator and a carbodiimide compound in this order. The process according to claim 6, wherein the catalyst deactivator is a metaphosphoric acid compound or phosphoric acid. The production method according to claim 6, wherein the melt kneading is performed at 230 to 300 ° C. The production method according to claim 6, wherein the melt-kneading is performed at 240 to 280 ° C. The production method according to claim 6, wherein the lactide contents of polylactic acid (B) and polylactic acid (C) are each 80000 ppm or less. The production method according to claim 6, wherein melt kneading is performed while deaeration. A molded article comprising the polylactic acid composition according to any one of claims 1 to 5. The molded article according to claim 12, which is a film, a sheet, an injection molded article, a blow molded article, a fiber or a fiber structure.

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