JP2010111736A - Polylactic acid composition and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polylactic acid composition having excellent heat stability, especially excellent flame retardancy, to provide a method for manufacturing the composition, and to provide a molded product of the composition. <P>SOLUTION: The composition includes 100 pts.wt. polylactic acid (component A), 0.001 to 5 pts.wt. phosphono fatty acid ester (component B), 0.01 to 5 pts.wt. phosphate metal salt (component C), 1 to 100 pts.wt. at least one flame retardant (component D) selected from the group consisting of a phosphorus-based flame retardant (component D-1), a nitrogen-based flame retardant (component D-2), and a metal hydroxide compound-based flame retardant (component D-3), and 0.001 to 10 pts.wt. terminal blocking agent (component E). The method for manufacturing the composition and the molded product of the composition are also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polylactic acid composition. More specifically, the present invention relates to a polylactic acid composition excellent in heat stability, particularly wet heat stability, and a molded product thereof.

In recent years, for the purpose of protecting the global environment, biodegradable polymers that are decomposed in a natural environment have attracted attention and are being studied all over the world. As biodegradable polymers, aliphatic polyesters such as polylactic acid, polyhydroxybutyrate, and polycaprolactone are known. Since polylactic acid uses lactic acid obtained from a raw material derived from a living body or a derivative thereof as a raw material, it is a high-safety and environmentally friendly polymer material. Therefore, the use as a general-purpose polymer is examined, and the use as a stretched film, a fiber, an injection molded product, etc. is examined.
However, since polylactic acid has a low crystal melting temperature of about 155 ° C., its heat resistance is limited. In addition, the thermal stability, particularly wet heat stability is poor, and there is a drawback that it is easily decomposed by humidity.
On the other hand, a stereocomplex polylactic acid is formed by mixing poly L-lactic acid (PLLA) composed of L-lactic acid units and poly D-lactic acid (PDLA) composed of D-lactic acid units in a solution or in a molten state. It is known (Patent Literature 1 and Non-Patent Literature 1). It is known that this stereocomplex polylactic acid has a crystal melting temperature of 200 to 230 ° C., a higher melting point than PLLA and PDLA, and high crystallinity.

However, formation of stereocomplex polylactic acid is not easy, and the difficulty becomes even more remarkable when the weight average molecular weight of PLLA or PDLA exceeds 150,000 (Patent Document 1). That is, the stereocomplex polylactic acid usually does not show a single phase, but becomes a mixed phase composition of PLLA and PDLA phases (homophase) and a polylactic acid stereocomplex phase (complex phase). In this mixed composition, if the ratio of the complex phase is small, it is difficult to exhibit the heat resistance inherent in stereocomplex polylactic acid. In addition, stereocomplex polylactic acid, like polylactic acid homopolymer, has a defect that it is susceptible to hydrolysis due to humidity as a characteristic of aliphatic polyester.
Various studies have been made on improving the thermal stability of polylactic acid in order to overcome this situation. For example, Patent Document 2 proposes adding a phosphoric acid compound or a phosphorous acid compound as a catalyst deactivator to polylactic acid when the molecular weight reaches 50,000 or more. Patent Documents 3 and 4 teach that an acid phosphate ester or a chelating agent is added as a catalyst deactivator to improve the thermal stability of polylactic acid. However, adding a catalyst deactivator to polylactic acid having a low molecular weight as in Patent Document 2 means that the subsequent polymerization reaction is inhibited and a high molecular weight product cannot be obtained. On the other hand, the acidic phosphoric acid esters described in Patent Documents 3 and 4 cause the corrosion of the production facility or the wet heat stability of the resin due to its acidity. Further, the exemplified chelating agents are generally poor in heat resistance, and are scorched before capturing the metal catalyst, causing serious coloring and malodor.

Patent Document 5 proposes that by containing a phosphono fatty acid ester in polylactic acid, the residual catalyst in the polylactic acid can be effectively deactivated, and the thermal stability of polylactic acid is improved. However, no consideration has been given to wet heat stability, and sufficient measures have not been taken for the characteristic feature of aliphatic polyesters that they are easily hydrolyzed by humidity.
In addition to heat resistance and heat stability, especially wet heat stability, a commonly known drawback of polylactic acid is that it is easily combustible, so it can be used for automobile parts, electrical / electronic parts, and electrical equipment exterior parts. Further, the development to industrial applications requiring flame retardancy exemplified by OA exterior parts was insufficient.
In order to develop polylactic acid for industrial use, various proposals for imparting flame retardancy have been made. Patent Document 6 proposes using a hydroxide compound, a phosphorus compound, and a silica compound as a flame retardant. Patent Document 7 proposes that brominated flame retardants and chlorinated flame retardants are used as flame retardants, and phosphorous flame retardants, nitrogen compound flame retardants, silicone flame retardants and other inorganic flame retardants. . Patent Document 8 proposes to use a phosphorus-based flame retardant as a flame retardant for an alloy of polylactic acid and polycarbonate. Patent Document 9 proposes using a flame retardant for polylactic acid and polybutylene terephthalate. However, these proposals focus only on imparting flame retardancy, do not take into account residual catalyst deactivation in polylactic acid, and thermal stability sufficient for deployment to industrial applications is ensured. It is difficult to say, and the current situation has not yet reached a level that satisfies the high-level characteristics that are excellent in both heat resistance and heat stability, particularly wet heat stability and flame retardancy.
JP 63-24014 A Japanese Patent No. 2886071 Japanese Patent No. 3487388 Japanese Patent Laid-Open No. 10-36651 International Publication No. 2007/114459 Pamphlet JP 2003-192925 A JP 2004-190025 A JP-A-2005-48066 JP 2008-31296 A Macromolecules, 24, 5651 (1991).

  An object of the present invention is to provide a polylactic acid composition having excellent thermal stability, particularly wet heat stability, and excellent flame retardancy, and a molded product thereof. Another object of the present invention is to provide a method for producing a polylactic acid composition having excellent thermal stability, particularly wet heat stability, and excellent flame retardancy.

  The present inventors diligently studied to improve the thermal stability of polylactic acid, particularly wet heat stability, and also improve the flame retardancy. As a result, phosphono fatty acid ester (component B) is used as a deactivator for residual catalyst that is considered to reduce the thermal stability of polylactic acid, and phosphoric acid ester metal salt (component C) is used as a crystal nucleating agent. One or more flame retardants (D component) selected from phosphorus-based flame retardants (D-1 component), nitrogen-based flame retardants (D-2 component), and metal hydroxide compound-based flame retardants (D-3 component) are used. As a result, the thermal stability of the matrix resin was improved by the deactivation effect of the phosphono fatty acid ester (component B), and the adverse effects of the thermal decomposition products were removed by the improvement of the thermal stability. The present inventors have found that a polylactic acid composition excellent in heat resistance, heat stability, particularly wet heat stability, and flame retardancy can be obtained. Furthermore, it is necessary to reduce the foul odor derived from the end-capping agent and the mold contamination that seems to be caused by the foul odor-causing substances that cause deterioration of the working environment and use environment, and surprisingly, it is necessary to demonstrate a certain degree of wet heat stability. It has been found that the amount of the end-capping agent (E component) added can be reduced.

  In addition, the addition of phosphono fatty acid ester (component B) to polylactic acid is not only at the end of polymerization of polylactic acid but also when kneaded with other additive components to prepare a polylactic acid composition. By adding a fresh catalyst deactivator that has not been exposed to water, a highly efficient deactivation effect is obtained, and a polylactic acid composition having a further high level of thermal stability, in particular wet heat stability, is obtained. And one or more flame retardants (D component) selected from phosphorus-based flame retardants (D-1 component), nitrogen-based flame retardants (D-2 component), and metal hydroxide compound-based flame retardants (D-3 component). The present inventors have found that the effect of improving flame retardancy by addition is further increased, and the present invention has been completed.

That is, the present invention comprises 100 parts by weight of polylactic acid (component A),
0.001 to 5 parts by weight of a phosphono fatty acid ester (component B),
0.01-5 parts by weight of a phosphate metal salt (component C),
1 to 100 parts by weight of at least one selected from the group consisting of a phosphorus-based flame retardant (D-1 component), a nitrogen-based flame retardant (D-2 component) and a metal hydroxide compound-based flame retardant (D-3 component) Flame retardant (D component), and 0.001 to 10 parts by weight of end-capping agent (E component),
It is a composition containing this.

In addition, the present invention provides (i) compositions-1 and 100 containing 0.001 to 3 parts by weight of a phosphono fatty acid ester (component B) with respect to 100 parts by weight of poly-L lactic acid (component A-1). Composition-2 containing 0.001-3 parts by weight of phosphono fatty acid ester (component B) with respect to parts by weight of poly-D lactic acid (component A-2) was replaced by composition-1 and composition-2. A step of preparing a stereocomplex polylactic acid by melt-kneading in the presence of 0.01 to 5 parts by weight of a phosphoric acid ester metal salt (component C) with respect to a total of 100 parts by weight of
(ii) 100 parts by weight of the obtained stereocomplex polylactic acid, 0.001 to 2 parts by weight of a phosphono fatty acid ester (component B), 1 to 100 parts by weight of a phosphorus flame retardant (component D-1), nitrogen At least one flame retardant (D component) selected from the group consisting of a series flame retardant (D-2 component) and a metal hydroxide compound-based flame retardant (D-3 component), and 0.001 to 10 parts by weight of end-capping Melt kneading agent (E component),
It is a manufacturing method of the said composition which consists of.

  Moreover, this invention includes the molded article which consists of this composition.

  The polylactic acid composition of the present invention and the molded product thereof are excellent in heat stability, particularly wet heat stability, and excellent in flame retardancy. Moreover, according to the manufacturing method of this invention, the polylactic acid composition excellent in heat stability, especially wet heat stability, and excellent in a flame retardance can be provided.

<Polylactic acid: A component>
The polylactic acid (component A) is poly-L lactic acid (A-1 component) mainly composed of L-lactic acid units, poly-D lactic acid (A-2 component) mainly composed of D-lactic acid units, or a mixture thereof.
Poly-L lactic acid (component A-1) is mainly composed of L-lactic acid units represented by the following formula (4). The component A-1 is preferably composed of 90 to 100 mol% of L-lactic acid units and 0 to 10 mol% of copolymerized units other than L-lactic acid. Poly-D lactic acid (component A-2) is mainly composed of D-lactic acid units represented by the following formula (4). The A-2 component is preferably composed of 90 to 100 mol% of D-lactic acid units and 0 to 10 mol% of copolymerized units other than D-lactic acid.

The optical purity of poly-L lactic acid (component A-1) or poly-D lactic acid (component A-2) is preferably 90 to 100 mol%. If the optical purity is lower than this, the crystallinity and melting point of polylactic acid are lowered, and it is difficult to obtain high heat resistance. For this reason, the melting point of poly-L lactic acid (component A-1) or poly-D lactic acid (component A-2) is preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and even more preferably 175 ° C. or higher.
In this respect, the optical purity of lactic acid and lactide of the polymer raw material is preferably 96 to 100 mol%, more preferably 97.5 to 100 mol%, further preferably 98.5 to 100 mol%, and particularly preferably 99 to 99 mol%. The range is 100 mol%.

The copolymer unit is a D-lactic acid unit if poly-L lactic acid (A-1 component), an L-lactic acid unit if poly-D lactic acid (A-2 component), and includes units other than lactic acid. It is done. The copolymer unit other than the lactic acid unit is in the range of 0 to 10 mol%, preferably 0 to 5 mol%, more preferably 0 to 2 mol%, still more preferably 0 to 1 mol%.
Copolymerized units include units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like having functional groups capable of forming two or more ester bonds, and various polyesters, various polyethers, various types composed of these various components. Examples are units derived from polycarbonate and the like.

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

The weight average molecular weights of poly L-lactic acid (component A-1) and poly D-lactic acid (component A-2) are preferably 80,000 to 300,000 in order to achieve both mechanical properties and moldability of the composition of the present invention. More preferably, it is in the range of 100,000 to 250,000, and more preferably in the range of 1 to 230,000. The weight average molecular weight and number average molecular weight of polylactic acid are values measured by gel permeation chromatography (GPC) and converted to standard polystyrene.
The method for producing poly L-lactic acid (component A-1) and poly D-lactic acid (component A-2) is not particularly limited and can be produced by a conventionally known method, for example, L- or D-lactide. Examples thereof include a melt ring-opening polymerization method, a solid-phase polymerization method of low molecular weight polylactic acid, and a direct polymerization method in which lactic acid is subjected to dehydration condensation.

The polymerization reaction can be carried out in a conventionally known reaction apparatus. For example, a vertical reactor or a horizontal reactor equipped with a high-viscosity stirring blade such as a helical ribbon blade can be used alone or in parallel. Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.
In the solid-state polymerization method, it is preferable to crystallize the prepolymer in advance from the viewpoint of preventing fusion of pellets and production efficiency, and the container itself rotates like a fixed vertical or horizontal reaction vessel, or a tumbler or kiln. In a reaction vessel (such as a rotary kiln), the polymerization is carried out by raising the temperature gradually with the progress of the polymerization at a constant temperature in the temperature range from the glass transition temperature of the prepolymer to less than the melting point. For the purpose of efficiently removing generated water, a method of reducing the pressure inside the reaction vessels or circulating a heated inert gas stream is also preferably used.

  The composition of this invention contains the metal catalyst used when manufacturing polylactic acid. The metal catalyst is a compound containing at least one metal element selected from the group consisting of alkaline earth metals, rare earth metals, third-period transition metals, aluminum, germanium, tin, and antimony. Examples of the alkaline earth metal include magnesium, calcium, and strontium. Examples of rare earth elements include scandium, yttrium, lanthanum, and cerium. As the transition metal of the third period, iron, cobalt, nickel, and zinc can be cited. Metal catalysts are added to the composition, for example, as carboxylates, alkoxides, aryloxides or enolates of β-diketones of these metals. In view of polymerization activity and hue, tin octylate, titanium tetraisopropoxide, and aluminum triisopropoxide are particularly preferable.

The content of the metal catalyst is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.1 part by weight with respect to 100 parts by weight of polylactic acid. When the content of the metal catalyst is too small, the polymerization rate is remarkably lowered. On the contrary, if the amount is too large, coloring due to reaction heat, or open polymerization or transesterification reaction is accelerated, so that the hue and thermal stability of the resulting composition are deteriorated.
Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid. For example, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and the like can be suitably used.

<Stereo complex polylactic acid>
The polylactic acid preferably contains a stereocomplex crystal. Polylactic acid containing this stereocomplex crystal is called stereocomplex polylactic acid. The stereocomplex crystal is formed by mixing poly L-lactic acid (A-1 component) and poly D-lactic acid (A-2 component). In this case, the weight ratio of poly L-lactic acid (A-1 component) to poly D-lactic acid (A-2 component) is preferably 90:10 to 10:90, more preferably 75:25 to 25:75. More preferably, it is 60: 40-40: 60.
The polylactic acid (component A) contains poly-L lactic acid (component A-1) mainly composed of L-lactic acid units and poly-D lactic acid (component A-2) mainly composed of D-lactic acid units. It is preferable that the weight ratio of a component and A-2 component exists in the range of 10: 90-90: 10. In this case, poly-L lactic acid (component A-1) contains 90 mol% or more of L-lactic acid units, and poly-D lactic acid (component A-2) contains 90 mol% or more of D-lactic acid units. preferable.
Highly stereocomplexed stereocomplex polylactic acid has a ratio of 195 ° C. or higher in the melting peak in the temperature rising process of differential scanning calorimeter (DSC) measurement of 80% or higher.

The melting peak of stereocomplex polylactic acid is preferably 200 ° C. or higher, more preferably 205 ° C. or higher, and further preferably 210 ° C. or higher. When the melting peak of stereocomplex polylactic acid is lower than 195 ° C., heat resistance is insufficient due to its crystallinity and low melting point.
The ratio of 195 ° C. or higher of the melting peak of stereocomplex polylactic acid is preferably 80% or higher, more preferably 90% or higher, and most preferably 100%. If the ratio of the melting peak at 195 ° C. or higher is lower than 80%, the characteristics of the homocrystal derived from poly-L lactic acid or poly-D lactic acid appear, and the heat resistance becomes insufficient.

Such highly stereocomplex of stereo complex polylactic acid, poly L- lactic acid (A-1 component) and poly D- lactic acid (A-2 component), but by the presence in such an amount ratio, ¹³ C- The enantiomeric average chain length determined by NMR can be suitably in the range of 10 to 40, and only the crystal melting peak of the stereocomplex phase polylactic acid is observed without the crystal melting peak of the homophase polylactic acid. become.
Here, the enantiomeric average chain length (Li) determined by ¹³ C-NMR is the peak of the quadruple structure of CH carbon of polylactic acid. Chem. 191, 287 (1990), the area ratio (Iiii, Iisi, Isi, Iiis, Isis, Issi, Iiss, Iss) is a value defined by the following formula (IV). i represents isotactic (LL, DD), and s represents syndiotactic (LD, DL) linkage.
Li = (3Iiii + 2Iisi + 2Isi + 2Iii + Isis + Issi + Iiss) / (Iisi + Iis + Isi + 2Isis + 2Issi + 2Iiss + 3Isss) +1
(IV)
In the present invention, the enantiomeric average chain length (Li) is preferably in the range of 10 to 40. By satisfying such conditions, the heat resistance of the composition, in particular, suitable mold release properties can be achieved.
If the average enantiomeric chain length is less than 10, even if a stereocomplex phase polylactic acid is highly formed in the DSC measurement, the composition may be inferior in heat resistance. Lactic acid formation is inferior and heat resistance may be inferior. In addition to this viewpoint, from the viewpoint of mold releasability of the composition, the enantiomeric average chain length is preferably selected in the range of 15 to 40, more preferably 18 to 39.

<Phosphono fatty acid ester>
The composition of the present invention contains a phosphono fatty acid ester (component B) as a metal catalyst deactivator for polylactic acid (component A). A phosphono fatty acid ester (component B) is a compound in which a phosphonic acid diester moiety and a carboxylic acid ester moiety are bonded via an aliphatic hydrocarbon group, and is colorless and transparent and excellent in heat resistance, so that the resulting composition has a good hue. . Particularly preferred are phosphono fatty acid esters represented by the following general formula (1).

In the formula, R ^{1 to} R ³ are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group and a naphthalenyl group. R ^{1 to} R ³ may be the same or different from each other. N is an integer of 1 to 3.

  As the compound represented by the formula (1), ethyl diethylphosphonoacetate, di-n-propylphosphonoacetate ethyl, di-n-butylphosphonoacetate ethyl, di-n-hexylphosphonoacetate ethyl, di-n-octyl Ethyl phosphonoacetate, ethyl di-n-decylphosphonoacetate, ethyl di-n-dodecylphosphonoacetate, ethyl di-n-octadecylphosphonoacetate, ethyl diphenylphosphonoacetate, decyl diethylphosphonoacetate, dodecyl diethylphosphonoacetate , Octadecyl diethylphosphonoacetate, ethyl diethylphosphonopropionate, ethyl di-n-propylphosphonopropionate, ethyl di-n-butylphosphonopropionate, ethyl di-n-hexylphosphonopropionate, di-n -Ethyl octylphosphonopropionate, di-n-decylphosphono Ethyl lopionate, ethyl di-n-dodecylphosphonopropionate, ethyl di-n-octadecylphosphonopropionate, ethyl diphenylphosphonopropionate, decyl diethylphosphonopropionate, dodecyl diethylphosphonopropionate, diethylphosphono Octadecyl propionate, ethyl diethylphosphonobutyrate, ethyl di-n-propylphosphonobutyrate, ethyl di-n-butylphosphonobutyrate, ethyl di-n-hexylphosphonobutyrate, ethyl di-n-octylphosphonobutyrate, di- Ethyl n-decylphosphonobutyrate, ethyl di-n-dodecylphosphonobutyrate, ethyl di-n-octadecylphosphonobutyrate, ethyl diphenylphosphonobutyrate, decyl diethylphosphonobutyrate, dodecyl diethylphosphonobutyrate, octadecyl diethylphosphonobutyrate And the like. In view of efficacy and ease of handling, ethyl diethylphosphonoacetate, ethyl di-n-propylphosphonoacetate, ethyl di-n-butylphosphonoacetate, ethyl di-n-hexylphosphonoacetate, decyl diethylphosphonoacetate, Examples thereof include octadecyl diethylphosphonoacetate.

In the formula (1), when the carbon number of R ^{1 to} R ³ is 20 or less, the melting point becomes lower than the production temperature of polylactic acid or the composition, so that the mixture is sufficiently melted and mixed, and the metal catalyst is efficiently captured. can do. The phosphono fatty acid ester (component B) has an aliphatic hydrocarbon group between the phosphonic acid diester moiety and the carboxylic acid ester moiety. In order to efficiently supplement the metal catalyst in the polylactic acid, in the formula (1), n is preferably an integer of 1 to 3.

Content of phosphono fatty acid ester (B component) is 0.001-5 weight part with respect to 100 weight part of polylactic acid (A component), Preferably it is 0.005-2 weight part. If the content of the phosphono fatty acid ester is too small, the deactivation efficiency of the remaining metal catalyst is extremely poor and a sufficient effect cannot be obtained. On the other hand, when the amount is too large, contamination of the mold used at the time of molding processing becomes significant.
The phosphono fatty acid ester (B component) is usually added at the end of the polymerization, but the B component also has a deactivating effect on the phosphate ester metal salt (C component). When deterioration of thermal stability is remarkable, rather than adding all of the predetermined amount of B component at the end of polymerization, at the end of polymerization, and then when kneading with other components in each process of extrusion and molding It is preferable to add in portions.

  The amount of the phosphono fatty acid ester (component B) added in each process of extrusion and molding is 0. 0 with respect to a total of 100 parts by weight of poly L-lactic acid (A-1 component) and poly D-lactic acid (A-2 component). 001 to 2 parts by weight, preferably 0.005 to 1 part by weight. When there is too little addition amount of B component, the effect which deactivates a metal catalyst will not be acquired. Further, the contamination of the mold due to too much B component becomes significant.

<Phosphate metal salt: Component C>
Examples of the phosphoric ester metal salt (component C) include compounds represented by the following general formula (2) or (3).

In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, a propyl group, and a butyl group. R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, a propyl group, a butyl group, a hexyl group, and a decyl group. M ₁ is an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. Examples of the alkali metal atom include sodium and potassium. Examples of the alkaline earth metal atom include magnesium, calcium, and lithium. p is 1 or 2. q is 0 when M ₁ is an alkali metal atom, alkaline earth metal atom or zinc atom, and is 1 or 2 when M ₁ is an aluminum atom.

In the formula, R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, a propyl group, a butyl group, a hexyl group, and a decyl group. M ₂ is an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. Examples of the alkali metal atom include sodium and potassium. Examples of the alkaline earth metal atom include magnesium, calcium, and lithium. p is 1 or 2. q is 0 when M ₂ is an alkali metal atom, alkaline earth metal atom or zinc atom, and is 1 or 2 when M ₂ is an aluminum atom.

Examples of phosphoric acid ester metal salts (component C) include sodium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, aluminum bis (2,2′-methylenebis-4,6-di-). t-butylphenyl phosphate) and the like.
M ₁ and M ₂ of the phosphoric acid ester metal salt represented by the formula (2) or (3) are preferably Na, K, Al, Mg, Ca, Li, and particularly, among K, Na, Al, and Li. Li and Al can be most preferably used. Among them, trade names manufactured by ADEKA Co., Ltd., ADK STAB NA-10, NA-11, NA-21, NA-30, NA-35, NA-71 and the like are exemplified as suitable agents.
The content of the phosphoric acid ester metal salt (component C) is 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.01 to 100 parts by weight of polylactic acid (component A). -0.5 parts by weight, more preferably 0.02-0.3 parts by weight. When the amount is too small, the effect of improving the degree of stereoization is small, and when too large, the complex phase crystal melting point is lowered, which is not preferable.

<Flame retardant: D component>
The composition of the present invention contains a flame retardant (D component). Examples of the flame retardant (D component) include phosphorus-based flame retardant (D-1 component), nitrogen-based flame retardant (D-2 component), and metal hydroxide compound-based flame retardant (D-3 component). These three types may be used alone or in combination of two or more, and a single or more compounds may be used in each type. It is preferable to use it properly according to the purpose.

(Phosphorus flame retardant: D-1 component)
As phosphorus flame retardant (D-1 component), (1) phosphate ester flame retardant, (2) phosphonitrile flame retardant, (3) phosphonate flame retardant, (4) polyphosphate flame retardant, (5) A phosphinic acid salt type is mentioned.

(1) Phosphate ester flame retardant Specific examples of the phosphate ester flame retardant include one or more phosphate ester compounds represented by the following formula (5).

In the formula, X is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy It is a group derived from phenyl) sulfide. n is an integer of 0 to 5, or an average value of 0 to 5 in the case of a mixture of phosphate esters having different n numbers. R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol substituted or unsubstituted with one or more halogen atoms. It is a group.

More preferably, X in the formula is a group derived from hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, n is an integer of 1 to 3, or a blend of n different phosphate esters. In the case of R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each independently from phenol, cresol, or xylenol that is substituted or more preferably substituted with one or more halogen atoms. Those that are groups to be derived are mentioned.
Among such organic phosphate ester flame retardants, triphenyl phosphate is preferable as a phosphate compound, and resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable as phosphate oligomers because of their excellent hydrolysis resistance. Can be used. More preferred are resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) from the viewpoint of heat resistance. This is because they have good heat resistance and are free from adverse effects such as thermal deterioration and volatilization.

(2) Phosphononitrile-based flame retardant The phosphonitrile-based flame retardant used in the present invention is a phosphonitrile linear polymer and / or a cyclic polymer, and is an oligomer or polymer having a repeating unit represented by the following formula (6). The number average degree of polymerization is 3 or more. Although it may be either linear or cyclic, a cyclic trimer is particularly preferably used. Further, it may be a mixture in which a linear product and a cyclic product are mixed at an arbitrary ratio.

In formula (6), A and B each independently represent an O, N, or S atom. R ¹ and R ² are each independently an aryl group having 6 to 15 carbon atoms, an alkyl group having 6 to 15 carbon atoms, an aralkyl group having 6 to 15 carbon atoms, or a cycloalkyl group having 6 to 15 carbon atoms. R ¹ and ^{R 2} may be a cyclic structure linked. x and y are 0 or 1. n means the number average degree of polymerization and represents a value of 3 or more.
Such phosphonitrile linear polymers and / or cyclic polymers include hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, or poly (dichlorophosphazene) obtained by ring-opening polymerization of these cyclic oligomers and alcohol, phenol, amine, thiol, It can be synthesized by reacting with a nucleophilic reagent such as a Grignard reagent by a known method.

(3) Phosphonate flame retardant The phosphonate flame retardant is preferably represented by the following general formula (7).

In formula (7), each of R ¹ and R ² independently represents a branched or unbranched alkylene group having 1 to 24 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a group having 6 to 30 carbon atoms. A substituted or unsubstituted aralkylene group or a substituted or unsubstituted alkarylene group having 6 to 30 carbon atoms.
R ³ is a hydrogen atom, a branched or unbranched alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, Or it is a C6-C30 substituted or unsubstituted alkaryl group. x and y are each independently a number from 1 to 50.

(4) Polyphosphate flame retardant Examples of the polyphosphate flame retardant used in the present invention include ammonium polyphosphate and melamine polyphosphate.

(5) Phosphinate Flame Retardant Examples of the phosphinate flame retardant used in the present invention include salts represented by the following formula (8) or the following formula (9).

Each independently wherein _{R 11, R 12} is a straight-chain or branched alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 7 to 20 carbon atoms Is an aralkyl group. R ₁₃ represents a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylene arylene group having 7 to 20 carbon atoms or a cycloalkylene arylene group. It is a group. M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zn, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. x is 1 or 2. m is 2 or 3, and n is 1 or 3.

R ₁₂ and R ₁₃ appropriately maintain the phosphorus content in the component B, and preferably exhibit flame retardancy, and at the same time, preferably exhibit the crystallinity of the composition. A linear or branched alkyl group, cycloalkyl group, aryl group or aralkyl group in the range of is preferably selected. Of these, an alkyl group and an aryl group are preferably selected. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, or a phenyl group is preferably exemplified.
R ₁₃ appropriately retains the phosphorus content in the B component, and preferably exhibits flame retardancy, and at the same time, preferably exhibits the crystallinity of the composition. Therefore, R ₁₃ is a straight chain having 1 to 10 carbon atoms. Alternatively, a branched alkylene group, cycloalkylene group, arylene group, alkylene arylene group or cycloalkylene arylene group is preferably selected.

  Specifically, for example, methylene group, ethylene group, methylethane-1,3-diyl group, propane-1,3-diyl group, 2,2-dimethylpropane-1,3-diyl group, butane-1,4-diyl Group, octane-1,8-diyl group, phenylene group, naphthylene group, ethylphenylene group, tert-butylphenylene group, methylnaphthylene group, ethylnaphthylene group, phenylenemethylene group, phenyleneethylene group, phenylenepropylene group, phenylenebutylene group Etc. are exemplified.

M represents Mg, Ca, Al, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. When there are a plurality of M, each is independently selected. Examples of protonated nitrogen bases include amide groups, ammonium groups, alkylammonium groups, and melamine-derived groups. In order to improve the flame retardancy, crystallinity, moldability, etc. of the composition of the present invention, M is selected from the group of Mg, Ca, Al, Zn and groups derived from amide groups, ammonium groups, alkylammonium groups or melamines. The Of these, Al is most preferably selected. )
When the phosphinates represented by the formulas (8) and (9) are used in combination, the weight ratio of (8) / (9) is preferably selected from the range of 10/90 to 30/70.
(Nitrogen flame retardant: D-2 component)
The nitrogen-based flame retardant (D-2 component) used in the present invention is a nitrogen-based flame retardant containing a triazine skeleton, and is an agent that synergistically increases the flame retardancy of a phosphorus-based flame retardant. And at least one selected from the group consisting of (11).

In the formula, each of R _{14 to} R ₁₆ independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 16 carbon atoms, (these are not substituted, hydroxyl groups or 1 to 4), an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an acyl group, an acyloxy group, an aryl group having 6 to 12 carbon atoms, -O-RA , -N (RA) (RB) or a group represented by N-alicyclic or N-aromatic -N (RA) RB. Here, RA and RB are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a -cycloalkyl group having 5 to 16 carbon atoms (these are not substituted, a hydroxyl group or a hydroxyalkyl having 1 to 4 carbon atoms). Substituted with a functional group), an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an acyl group, an acyloxy group, or an aryl group having 6 to 12 carbon atoms.

However, all of R _{14 to} R ₁₆ are not simultaneously hydrogen atoms, and in the formula (10), all of R _{14 to} R ₁₆ are not simultaneously —NH ₂ . X is an acid capable of forming an adduct with the melamine or triazine compound (10), and s and t are each independently 1 or 2.
In Formula (10), when at least one of R _{14 to} R ₁₆ is an aryl group having 6 to 12 carbon atoms, the flame retardancy can be more effectively enhanced when blended with a phosphinate in a phosphorus flame retardant. In addition, the flame retardancy, crystallinity and moldability of the composition of the present invention can be improved more suitably.
In the formula (11), when all of R _{14 to} R ₁₆ are —N (RA) (RB), the flame retardancy can be more effectively increased, and the flame retardancy and crystal of the composition of the present invention can be increased. (10) and (11) are preferably exemplified by dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, melon polyphosphate, and the like. Is done.

  In the present invention, the flame retardancy of the composition of the present invention is improved by additionally using at least one compound represented by the following formulas (12) to (15) in addition to the nitrogen-based flame retardant having a triazine skeleton. Can be made.

In the formula, R _{7 to} R ₁₀ and R _{17 to} R ₂₂ are each preferably independently exemplified by the functional groups described as R _{14 to} R ₁₆ . For example, tris (hydroxyethyl) isocyanurate, allanin, glycoluril, urea. Cyanurate and the like are preferably exemplified. Such an agent is applied in the range of 10 to 50% by weight based on the nitrogen-based flame retardant containing a triazine skeleton.

(Metal hydroxide compound flame retardant: D-3 component)
The metal hydroxide compound-based flame retardant (D-3 component) of the present invention is aluminum hydroxide, magnesium hydroxide and calcium hydroxide, and preferably has high purity in order to improve the thermal stability of the composition. Particularly preferred are those having a purity of 99.5% or more. The purity of the metal hydroxide compound flame retardant can be measured by a known method. For example, the content of impurities contained in the metal hydroxide compound flame retardant is measured by a known method, and the purity of the metal hydroxide compound flame retardant is obtained by subtracting the impurity content from the total amount. be able to. More specifically, for example, in the case of aluminum hydroxide, examples of impurities include Fe ₂ O ₃ , SiO ₂ , T—Na ₂ O, S—Na ₂ O, and the like. The content of Fe ₂ O ₃ is determined by O-phenanthroline spectrophotometry (JIS H 1901) after melting in a sodium carbonate-boric acid solution. The content of SiO ₂ is determined by the molybdenum blue absorptiometry (JIS H 1901) after melting in sodium carbonate-boric acid solution. The content of T-Na ₂ O is determined by flame photometry after melting in sulfuric acid, and S-Na ₂ O is determined by flame photometry after extraction with hot water. The purity of the hydroxide can be obtained by reducing the content obtained as described above from the weight of aluminum hydroxide. Of course, it is needless to say that different types of metal hydroxide compound flame retardants can be used in combination.

  The shape of the metal hydroxide compound flame retardant used in the present invention is not particularly limited, but is preferably granular. As for the particle diameter, it is preferable that the average particle diameter calculated | required by the laser diffraction method is about 100 micrometers or less. In this case, the particle size distribution does not matter. From the viewpoint of injection moldability in the molding process and dispersibility at the time of kneading, the average particle diameter is preferably in the above range, and more preferably in the above range. Of course, in order to increase the filling rate of the composition, a plurality of kinds of metal hydroxide compound flame retardants having different average particle diameters can be used in combination.

Furthermore, it is preferable to use particles having a BET specific surface area of about 5.0 m ² / g or less determined by a nitrogen gas adsorption method. Of course, in order to increase the filling rate into the composition, a plurality of types of metal hydroxide compound flame retardants having different BET specific surface areas can be used in combination. From the viewpoint of moldability, the BET specific surface area is preferably in the above range, and a smaller one is more preferable in the above range.
Containing one or more flame retardants (component D) selected from phosphorus-based flame retardants (component D-1), nitrogen-based flame retardants (component D-2), and metal hydroxide compound-based flame retardants (component D-3) The amount is 1 to 100 parts by weight, more preferably 3 to 90 parts by weight, and still more preferably 5 to 80 parts by weight with respect to 100 parts by weight of polylactic acid (component A). If the content is less than 1 part by weight, the amount of the flame retardant added is too small and flame retardancy cannot be obtained. If the content exceeds 100 parts by weight, the heat resistance is deteriorated and the releasability is lowered.

<End blocker: E component>
The composition of this invention contains terminal blocker (E component). The terminal blocking agent (component E) is preferably at least one selected from the group consisting of carbodiimide compounds, epoxy compounds, oxazoline compounds and oxazine compounds.

(Carbodiimide compound)
Examples of the carbodiimide compound include the following compounds. For example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, octyldecylcarbodiimide, di-t-butylcarbodiimide, dibenzylcarbodiimide, diphenylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'- Phenylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, bis (p-aminophenyl) carbodiimide, bis (p-chlorophenyl) carbodiimide, bis (o-chlorophenyl) Carbodiimide, bis (o-ethylphenyl) carbodiimide, bis (p-ethylphenyl) carbodiimide bis (o-isopropylphenol) Lu) carbodiimide, bis (p-isopropylphenyl) carbodiimide, bis (o-isobutylphenyl) carbodiimide, bis (p-isobutylphenyl) carbodiimide, bis (2,5-dichlorophenyl) carbodiimide, bis (2,6-dimethylphenyl) Carbodiimide, bis (2,6-diethylphenyl) carbodiimide, bis (2-ethyl-6-isopropylphenyl) carbodiimide, bis (2-butyl-6-isopropylphenyl) carbodiimide, bis (2,6-diisopropylphenyl) carbodiimide, Bis (2,6-di-t-butylphenyl) carbodiimide, bis (2,4,6-trimethylphenyl) carbodiimide, bis (2,4,6-triisopropylphenyl) carbodiimide, bis (2,4,6- Ributylphenyl) carbodiimide, di-β-naphthylcarbosiimide, N-tolyl-N′-cyclohexylcarbosiimide, N-tolyl-N′-phenylcarbosiimide, p-phenylenebis (o-toluylcarbodiimide), p- Phenylenebis (cyclohexylcarbodiimide, p-phenylenenebis (p-chlorophenylcarbodiimide), 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, hexamethylenebis (cyclohexylcarbodiimide), ethylenebis (phenylcarbodiimide), ethylenebis Examples thereof include mono- or polycarbodiimide compounds such as (cyclohexylcarbodiimide).
Of these, bis (2,6-diisopropylphenyl) carbodiimide and 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide are preferred from the viewpoints of reactivity and stability.

  Of these, industrially available dicyclohexylcarbodiimide and bis (2,6-diisopropylphenyl) carbodiimide can be suitably used. Furthermore, a commercially available polycarbodiimide compound as the polycarbodiimide compound can be suitably used without the need for synthesis. Examples of such commercially available polycarbodiimide compounds include Carbodilite LA-1 and HMV-8CA sold under the trade name of Carbodilite sold by Nisshinbo Co., Ltd. A carbodiimide compound is preferred because of its influence on the color tone, thermal decomposability, hydrolysis resistance and the like of the composition of the present invention.

(Epoxy compound)
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 blending such an agent, a polylactic acid resin composition and a molded product excellent in mechanical properties, moldability, heat resistance, and durability can be obtained.

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

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

  Examples of the glycidylamine compound include tetraglycidylamine diphenylmethane, triglycidyl-p-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, triglycidyl isocyanurate, and the like.

  Examples of glycidyl imide and glycidyl amide compounds include, for example, N-glycidyl phthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3,6-dimethylphthalimide, N-glycidyl succinimide, N-glycidyl-1 , 2,3,4-tetrahydrophthalimide, N-glycidyl maleimide, N-glycidyl benzamide, N-glycidyl stearyl amide and the like. Of these, N-glycidylphthalimide is preferable.

  Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexyl-3,4-cyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4,5- Examples thereof include epoxycyclohexane-1,2-dicarboxylic imide, N-phenyl-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.

(Oxazoline compound)
Examples of the oxazoline compound include 2-methoxy-2-oxazoline, 2-butoxy-2-oxazoline, 2-stearyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-benzyl Oxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2- Phenyl-2-oxazoline, 2-o-ethylphenyl-2-oxazoline, 2-o-propylphenyl-2-oxazoline, 2-p-phenylphenyl-2-oxazoline, 2,2′-bis (2-oxazoline) 2,2′-bis (4-methyl-2-oxazo ), 2,2'-bis (4-butyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-) Oxazoline), 2,2′-p-phenylenebis (4,4′-methyl-2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline) ), 2,2′-hexamethylenebis (2-oxazoline), 2,2′-ethylenebis (4-methyl-2-oxazoline), 2,2′-tetramethylenebis (4,4′-dimethyl-2) -Oxazoline), 2,2'-cyclohexylenebis (2-oxazoline), 2,2'-diphenylenebis (4-methyl-2-oxazoline) and the like. Furthermore, the polyoxazoline compound etc. which contain the said compound as a monomer unit are mentioned.

(Oxazine compound)
Examples of the oxazine compound include 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-hexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-decyloxy-5,6- Dihydro-4H-1,3-oxazine, 2-cyclohexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-allyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy -5,6-dihydro-4H-1,3-oxazine and the like.

Further, 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′- Ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylene Bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-P, P′-diphenylenebis (5,6-dihydro-4H-1,3-oxazine) and the like can be mentioned. Furthermore, the polyoxazine compound etc. which contain the above-mentioned compound as a monomer unit are mentioned.
Among the oxazoline compounds and oxazine compounds, 2,2′-m-phenylenebis (2-oxazoline) and 2,2′-p-phenylenebis (2-oxazoline) are preferably selected.

  The content of the end-capping agent (component E) is preferably 0.001 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and still more preferably 0, per 100 parts by weight of polylactic acid (component A). 0.1 to 3 parts by weight. If the content is less than 0.001 part, the amount of the end-capping agent added to the carboxyl terminal is too small, and sufficient hydrolysis resistance cannot be obtained. If the content exceeds 10 parts by weight, gelation occurs and the fluidity is remarkably high. Not only does this decrease, but the bad odor derived from the end-capping agent and the mold contamination that seems to be derived from the odor-causing substance become severe, which is not preferable.

<Inorganic filler: F component>
The composition of the present invention may contain an inorganic filler (F component). A composition excellent in mechanical properties, heat resistance and moldability can be obtained by the inorganic filler. As the inorganic filler used in the present invention, a fibrous, plate-like, or powder-like material used for reinforcing ordinary thermoplastic resins can be used.

  Specifically, for example, carbon nanotube, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, imogolite, sepiolite, Asbestos, slag fiber, zonolite, gypsum fiber, silica fiber, silica. 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 particulate inorganic fillers such as carbon nanoparticles such as titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite, and white clay fullerene.

  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.

Among these inorganic fillers, fibrous or plate-like inorganic fillers are preferable, and glass fiber, wollastonite, aluminum borate whisker, potassium titanate whisker, mica, and kaolin, a cation-exchanged layered silicate. Is preferred. The aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.
Such a filler may be coated or converged with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane. May be.

  The content of the inorganic filler (component F) is preferably 0.05 to 100 parts by weight, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 100 parts by weight of polylactic acid (component A). 50 parts by weight, particularly preferably 1 to 30 parts by weight, most preferably 1 to 20 parts by weight. When the blending amount is less than 0.05 parts by weight, the reinforcing effect is not sufficient, and when it exceeds 100 parts by weight, the appearance of the molded product is deteriorated or the strand breaks at the time of extrudability.

<Anti-dripping agent>
The composition of the present invention may contain an anti-dripping agent. The anti-dripping agent is at least one selected from a fluorine-containing polymer having fibril forming ability and polyphenylene ether.

(Fluoropolymer with fibril-forming ability)
Examples of the fluorinated polymer having fibril-forming ability include polytetrafluoroethylene, tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers, etc.), as shown in US Pat. No. 4,379,910. Examples thereof include a partially fluorinated polymer and a polycarbonate resin produced from a fluorinated diphenol. Polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.
Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability has a very high molecular weight, and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise.

Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.
Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of fibrillated PTFE include: Fluon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers, Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui A representative example is Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd.

As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and coprecipitated to obtain a coaggregated mixture (Japanese Patent Laid-Open No. Sho 60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing a monomer that forms an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583)), and (5) After uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A-11-29679, etc.) can be used. Commercial products of these mixed forms of fibrillated PTFE include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals, and “Product of Pacific Interchem Corporation” “POLY TS AD001” (product name) is exemplified. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, in 100% by weight of the mixture. When the ratio of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved.
The content of the fluorinated polymer having fibril-forming ability is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, still more preferably based on 100 parts by weight of polylactic acid (component A). 0.05 to 1.5 parts by weight.

(Polyphenylene ether)
The polyphenylene ether is a phenol polymer or copolymer having a phenylene ether structure (hereinafter sometimes simply referred to as a PPE polymer).
Specific examples of PPE polymers include poly (oxy-1,4-phenylene), poly (oxy-2,6-dimethylphenylene-1,4-diyl), and poly (oxy-2-methyl-6-ethylphenylene). -1,4-diyl), poly (oxy-2,6-diethylphenylene-1,4-diyl), poly (oxy-2-ethyl-6-n-propylphenylene-1,4-diyl), poly ( Oxy-2,6-di (n-propyl) phenylene-1,4-diyl), poly (oxy-2-methyl-6-n-butylphenylene-1,4-diyl), poly (oxy-2-ethyl) -6-isopropylphenylene-1,4-diyl), poly (oxy-2-methyl-6-hydroxyethylphenylene-1,4-diyl), poly (oxy-2-methyl-6-chloroethylphenylene) , 4-diyl), and the like. Of these, poly (oxy-2,6-dimethylphenylene-1,4-diyl) is particularly preferred.

Examples of the copolymer having a phenylene ether structure include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2, Examples include a copolymer of 6-dimethylphenol, 2,3,6-trimethylphenol and o-cresol.
The method for producing the PPE polymer is not particularly limited, and can be produced by oxidative coupling polymerization according to, for example, the method described in US Pat. No. 4,788,277.

The molecular weight of polyphenylene ether is, for example, preferably as a molecular weight parameter (0.5 g / dl chloroform solution, 30 ° C.), with a reduced viscosity in the range of 0.05 to 0.70 dl / g, preferably 0.10 to 0.55 dl / g. The range of g is more preferable.
Further, the polyphenylene ether may contain various phenylene ether units as partial structures as long as it does not contradict the gist of the present invention.
As such a structure, for example, oxy-2- (N, N-dialkylaminomethyl) -6-methylphenylene-1 described in JP-A Nos. 63-12698 and 63-301222 is disclosed. , 4-diyl unit, oxy-2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene-1,4-diyl unit, and the like. Also included are those in which a small amount of diphenoquinone or the like is bonded to the main chain of polyphenylene ether.

The PPE polymer may also contain polyphenylene ether modified with an ethylenically unsaturated compound such as the following α, β-unsaturated carboxylic acid or anhydride thereof. When such a modified polyphenylene ether is used, it is possible to provide a molded article having excellent mixing properties with a vinyl compound polymer and free from phase separation.
Examples of α, β-unsaturated carboxylic acids or anhydrides thereof include maleic anhydride, phthalic acid, itaconic anhydride, and glutaconic anhydride described in JP-B-49-2343 and JP-B-3-52486. Citraconic anhydride, aconitic anhydride, hymic anhydride, 5-norbornene-2-methyl-2-carboxylic acid, or maleic acid, fumaric acid, etc., but are not limited thereto, maleic anhydride Is particularly preferred.
PPE can be modified with the ethylenically unsaturated compound by heating to a temperature equal to or higher than the glass transition temperature of PPE in the presence or absence of an organic peroxide.

In the present invention, a PPE resin previously modified with the ethylenically unsaturated compound may be used. Moreover, it can also be made to react with a polyphenylene ether polymer by adding the said ethylenically unsaturated compound simultaneously when manufacturing this invention composition.
The content of polyphenylene ether is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 25 parts by weight, and further preferably 1 to 20 parts by weight per 100 parts by weight of polylactic acid (component A).
In addition, according to use and the objective, you may use combining the fluorine-containing polymer which has the said fibril formation ability, and polyphenylene ether.

<Antioxidant>
The composition of the present invention may contain an antioxidant. Examples of the antioxidant include at least one selected from the group consisting of phosphite compounds, phosphonite compounds, hindered phenol compounds, and thioether compounds. It is particularly preferable that the antioxidant is composed of two kinds of phosphite compounds and hindered phenol compounds from the viewpoint of further reducing the mold blockage derived from the end-capping agent and the odor-causing odor-derived substance.

(Phosphite compounds)
As phosphite compounds, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl Phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) Phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaeri Ritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

Furthermore, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, and the like.
Suitable phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methyl). Phenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

(Phosphonite compounds)
Examples of phosphonite compounds include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylene diphospho. Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, bis ( 2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4- Examples thereof include phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite. Tetrakis (di-tert-butylphenyl) -biphenylene diphosphonite, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylene diphospho Knight and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  The phosphonite compound is preferably tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, and stabilizers based on the phosphonite are Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos P. -It is commercially available as EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and any of them can be used.

(Hindered phenolic compounds)
As the hindered phenol compound, various compounds usually blended in a resin can be used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl. -6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) Phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6) -Tert-butylphenol), 4,4'-methylenebis (2,6-di-t) rt-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2′-ethylidene -Bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) ), Triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl-5) Methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3-methyl-6- tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodiethylenebi -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino ) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl- 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate , Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl -4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3 -Tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2- {3- 3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [methylene-3 -(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy-5-methyl Examples include benzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

  Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The said hindered phenol type compound can be used individually or in combination of 2 or more types.

(Thioether compounds)
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.

The content of the antioxidant is preferably 0.001 to 2 parts by weight, more preferably 0.005 to 1 part by weight, and particularly preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of polylactic acid (component A). 0.5 parts by weight.
Further, it is particularly preferable to use the phosphite compound and the hindered phenol compound in combination. By using a combination of a phosphite compound and a hindered phenol compound, a synergistic effect as an antioxidant is exhibited, and deterioration of the thermal stability of the composition can be further suppressed.

<Light stabilizer>
The composition of the present invention may contain a light stabilizer. Specific examples of the light stabilizer include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, hindered amine compounds, and the like.
Examples of the benzophenone compounds include benzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′. -Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy -2'-carbo Shi 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-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) -Tolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl -4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- “2- {3- (3,5-di-t-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.

  The content of the stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of polylactic acid (component A).

<Crystal Accelerator>
The composition of the present invention may contain a crystallization accelerator. By containing a crystallization accelerator, the action of the phosphate ester metal salt (component C) can be further enhanced, and a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
That is, by applying a crystallization accelerator, the moldability and crystallinity of polylactic acid (component A) are improved, and a molded product that is sufficiently crystallized even in normal injection molding and has excellent heat resistance and moist heat resistance is obtained. Can do. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.
As the crystallization accelerator, either an inorganic crystallization nucleating agent or an organic crystallization nucleating agent can be used.

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

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

In addition, stearic acid amide, ethylene bislauric acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide) and other organic carboxylic acid amides, low density polyethylene, high density polyethylene, polyiso Propylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid copolymer, sodium of styrene-maleic anhydride copolymer Examples thereof include salts (so-called ionomers), benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.
Among these, at least one selected from talc and organic carboxylic acid metal salts is preferably used. Only one type of crystallization nucleating agent may be used in the present invention, or two or more types may be used in combination.
The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight per 100 parts by weight of polylactic acid (component A).

<Organic filler>
The composition of the present invention may contain an organic filler. By containing the organic filler, 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, cellulose fibers processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, Angola, cashmere, camel, etc., synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers , Paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like. From the viewpoint of moldability, powdery materials such as paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, and starch are preferred. Powder, bamboo powder, cellulose powder and kenaf powder are preferred. Paper powder and wood powder are more preferable. Paper dust is particularly preferable.

These organic fillers may be collected directly from natural products, but may be recycled recycled waste paper such as waste paper, waste wood and old clothes. The wood is preferably a softwood material such as pine, cedar, oak or fir, or a hardwood material such as beech, shii or eucalyptus.
Paper powder is an adhesive from the viewpoint of moldability, especially emulsion-based adhesives such as vinyl acetate resin-based emulsions and acrylic resin-based emulsions when processing paper, polyvinyl alcohol-based adhesives, polyamide-based adhesives, etc. Preferred examples include those containing a hot melt adhesive.

  In the present invention, the content of the organic filler is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, and still more preferably 100 parts by weight of polylactic acid (component A) from the viewpoint of moldability and heat resistance. Is 10 to 150 parts by weight, particularly preferably 15 to 100 parts by weight.

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

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

Examples of the oxy fatty acid include 1,2-oxysteric acid. Paraffin having 18 or more carbon atoms is preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like.
As the low molecular weight polyolefin, for example, those having a molecular weight of 5000 or less are preferable, and specific examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidized type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Fatty acid amides having 6 or more carbon atoms are preferred, and specific examples include oleic acid amide, erucic acid amide, and behenic acid amide.
The alkylene bis fatty acid amide is preferably one having 6 or more carbon atoms, and specifically includes methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2-hydroxyethyl) stearic acid amide and the like. As the aliphatic ketone, those having 6 or more carbon atoms are preferable, and examples thereof include higher aliphatic ketones.

Examples of the fatty acid partial saponified ester include a montanic acid partial saponified ester. Examples of the fatty acid lower alcohol ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidonic acid ester, montanic acid ester, isostearic acid ester and the like.
Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol Examples include tall stearate, pentaerythritol adipate stearate, and sorbitan monobehenate. Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters and polypropylene glycol fatty acid esters.

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

<Antistatic agent>
The composition of the present invention may contain an antistatic agent. Examples of the antistatic agent include (β-lauramidopropionyl) trimethylammonium sulfate, quaternary ammonium salts such as sodium dodecylbenzenesulfonate, sulfonate compounds, and alkyl phosphate compounds.
One type of antistatic agent may be used, or two or more types may be used in combination. The content of the antistatic agent is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of polylactic acid (component A).

<Plasticizer>
The composition of the present invention may contain a plasticizer. Examples of the plasticizer include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.

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

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

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

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

<Others>
Moreover, in this invention, you may contain thermosetting resins, such as a phenol resin, a melamine resin, a thermosetting polyester resin, a silicone resin, an epoxy resin, in the range which is not contrary to the meaning of this invention. 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.

<Method for producing composition>
The composition of the present invention comprises (i) composition-1 containing 0.001 to 3 parts by weight of a phosphono fatty acid ester (component B) with respect to 100 parts by weight of poly-L lactic acid (component A-1). And composition-2 containing 0.001 to 3 parts by weight of phosphono fatty acid ester (component B) with respect to 100 parts by weight of poly-D lactic acid (component A-2), composition-1 and composition -2 for a total of 100 parts by weight, a step of preparing stereocomplex polylactic acid by melt-kneading in the presence of 0.01 to 5 parts by weight of a phosphoric acid ester metal salt (component C), and
(ii) 100 parts by weight of the obtained stereocomplex polylactic acid, 0.001 to 2 parts by weight of a phosphono fatty acid ester (component B), 1 to 100 parts by weight of a phosphorus flame retardant (component D-1), nitrogen At least one flame retardant (D component) selected from the group consisting of a series flame retardant (D-2 component) and a metal hydroxide compound-based flame retardant (D-3 component), and 0.001 to 10 parts by weight of end-capping Melt kneading agent (E component),
Can be manufactured.

  The production method of the present invention is characterized by a phosphono fatty acid ester (as a deactivator of a metal polymerization catalyst of polylactic acid at the end of polymerization of poly-L lactic acid (A-1 component) and poly-D lactic acid (A-2 component). B component), and then selected from the group consisting of phosphorus flame retardant (D-1 component), nitrogen flame retardant (D-2 component), and metal hydroxide compound flame retardant (D-3 component). The phosphono fatty acid ester (component B) is also added when melt kneading with at least one flame retardant (component D). By adding the phosphono fatty acid ester (component B) to the final stage of preparing the composition, the easily volatile phosphono fatty acid ester (component B) can always coexist with the remaining metal polymerization catalyst. The live effect can be maintained. As a result, a polylactic acid composition excellent in thermal stability and flame retardancy can be obtained.

In step (i), composition-1 is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of poly-L lactic acid (component A-1). Phosphono fatty acid ester (component B). Composition-2 is preferably 0.05 to 2 parts by weight, more preferably 0.01 to 1 part by weight of phosphono fatty acid ester (B) with respect to 100 parts by weight of poly-L lactic acid (component A-1). Component).
In step (ii), the addition amount of the phosphono fatty acid ester (component B) is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the stereocomplex polylactic acid. is there. One or more flame retardants (D component) selected from phosphorus-based flame retardants (D-1 component), nitrogen-based flame retardants (D-2 component), and metal hydroxide compound-based flame retardants (D-3 component) Is preferably 3 to 90 parts by weight, more preferably 5 to 80 parts by weight with respect to 100 parts by weight of the stereocomplex polylactic acid.

As melt kneading in the step of producing stereocomplex polylactic acid, the melting temperature is preferably 250 to 300 ° C, more preferably 250 to 290 ° C. If it exceeds 300 ° C., it is not preferable because it is difficult to suppress the decomposition reaction, and if it is less than 240 ° C., uniform mixing by heat treatment does not proceed, and it is difficult to efficiently produce a stereocomplex. The melting time is not particularly limited, but is 0.2 to 60 minutes, preferably 1 to 20 minutes. As the atmosphere during melting, either an inert atmosphere at normal pressure or a reduced pressure can be applied.
For melt kneading, a tumbler, V-type blender, super mixer, nauter mixer, Banbury mixer, kneading roll, 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 polylactic acid composition of the present invention is preferably in the form of pellets. The pellets are cut into strands or plate-like polylactic acid compositions in the air or water after the resin is completely solidified or not completely solidified and still in the molten state Such methods are conventionally known, but any of them can be suitably applied in the present invention.
The shape of the pellet may be any shape such as a spherical shape, a die shape, a linear shape, a curved shape, and a cross-sectional shape such as a circle, an ellipse, a flat shape, a triangle, a polygon having a square shape or more, and a star shape. However, it is preferable to have a shape suitable for further molding the pellets by various molding methods. Specifically, the pellet length is preferably 1 to 7 mm, the major axis is 3 to 5 mm, and the minor axis is 1 to 4 mm. Further, it is preferable that the shape does not vary.

<Physical properties of the composition>
The tensile strength retention (T) of the composition of the present invention is 50% or more, preferably 60% or more, more preferably 70% or more, and further preferably 80% to 100%. Tensile strength retention (T) is expressed by the following formula: T (%) = t ¹ / t ⁰ × 100 (%)
It is represented by
However, t ⁰ is the initial tensile strength, and t ¹ is the tensile strength after 100 hours in an atmosphere of 80 ° C. and 95% RH. Although the test piece for measuring the tensile strength is not particularly limited, a test piece having a length of 150 mm, a width of 20 mm, and a thickness of 4 mm conforming to ISO527 can be suitably exemplified. The tensile strength test conditions are not particularly limited, but a test speed of 5 mm / min can be suitably exemplified. In addition, examples of the tensile strength include yield strength and breaking strength. The tensile strength of the present invention indicates one of the higher strengths, that is, the maximum tensile strength measured in a so-called tensile test.
The enantiomeric average chain length determined by ¹³ C-NMR of the composition of the present invention is preferably 10 to 40, more preferably 15 to 40, and still more preferably 18 to 39.

<Molding>
The molded product made of the composition of the present invention is preferably molded by injection molding, extrusion molding, thermoforming, blow molding or foam molding.
Conventionally known molding methods can be applied to the injection molded product without any limitation. From the viewpoint of increasing the crystallization of the molded product and the molding cycle during injection molding, the mold temperature is preferably 30 ° C. or higher, more preferably 60 ° C. As mentioned above, More preferably, it is 70 degreeC or more. However, in order to prevent deformation of the molded product, the mold temperature is preferably 140 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower. Examples of these molded products include automobile parts, electrical / electronic parts, electrical equipment exterior parts, OA exterior parts, and the like.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.

1. Production of polylactic acid Polylactic acid was produced by the method shown in the production examples below. Moreover, each value in a manufacture example was calculated | required with the following method.
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer:
It was measured by gel permeation chromatography (GPC) and converted to standard polystyrene. The GPC measurement instrument used a differential refractometer Shimadzu RID-6A as a detector and Toso-TSKgel G3000HXL as a column. The measurement was performed by injecting 10 μl of a sample having a concentration of 1 mg / ml (chloroform containing 1% hexafluoroisopropanol) at a temperature of 40 ° C. and a flow rate of 1.0 ml / min using chloroform as an eluent.
(2) Carboxyl group concentration The sample was dissolved in purified o-cresol under a nitrogen stream, and then titrated with 0.05 N potassium hydroxide in ethanol using bromocresol blue as an indicator.
(3) Measurement with a differential scanning calorimeter (DSC) In the first heating process of the sample using DSC (TA-2920, manufactured by TA Instrument Co., Ltd.), a melting peak at 190 ° C. or higher was used as a melting peak derived from stereo crystals. The melting temperature was Tms and the melting enthalpy was Hms. In addition, the melting peak at 190 ° C. or less was defined as a homocrystalline melting peak, the melting temperature was Tmh, and the melting enthalpy was Hmh.
Stereogenicity = ΔHms / (ΔHms + ΔHmh) × 100
(4) Enantiomeric average chain length The sample was dissolved in HFIP / chloroform = 1/1 mixed solvent and then reprecipitated with methanol. This reprecipitation polymer component was ultrasonically washed with methanol, and centrifugation was repeated 10 times to remove impurities and solvent components, followed by drying with a vacuum dryer for 1 day to extract a polylactic acid component that could be a measurement sample.
Using the sample thus extracted, the average enantiomeric chain length was measured as follows.
¹³ C-NMR apparatus: BURKER ARX-500 manufactured by Nippon Bruker
Sample: 50mg / 0.7ml
Measurement solvent: 10% HFIP-containing deuterated chloroform Internal standard: Tetramethylsilane (TMS) 1% (v / v)
Measurement temperature: 27 ° C (300K)
Measurement frequency: 125 MHz
The ¹³ C-NMR measurement, out of carbon peaks attributed to carbonyl carbon (C = O), a peak (a) (170.1-170.3MHz around) the homo sequence (LLLLLL or DDDDDD), peaks ( b) (around 170.0-169.8 MHz) belongs to the racemic chain (LLLDDD...), and the average chain length was calculated from the integrated value of these peaks by the following formula.
v = Integral value of peak (a) / Integral value of peak (b) In the examples and comparative examples of the present invention, the following materials were used.

[Reference Example: Synthesis of ethyl di-n-hexylphosphonoacetate (DHPA)]
100 parts by weight of trihexyl phosphite and 100 parts by weight of ethyl bromoacetate were placed in a reaction vessel, and the interior was purged with nitrogen. Subsequently, the reaction vessel was heated to 170 ° C., and the reaction was carried out for 3 hours while heating to reflux. After excess ethyl bromoacetate was distilled off at 80 ° C. under reduced pressure, the reaction mixture was distilled under reduced pressure at 190 ° C. to obtain a colorless transparent liquid (yield 84%, boiling point 146 ° C./0.5 mmHg).

[A-1 component: production of poly L-lactic acid (PLLA)]
[Production Example 1]
100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%) and 0.15 part by weight of stearyl alcohol are charged from a raw material charging port of a polymerization reaction vessel equipped with a cooling distillation pipe under a nitrogen stream. It is. Subsequently, the inside of the reaction vessel was purged with nitrogen five times, and L-lactide was melted at 190 ° C. When L-lactide was completely melted, 0.005 part by weight of a toluene 500 μL solution of tin octylate was added and polymerized at 190 ° C. for 1 hour. After completion of the polymerization, 0.082 parts by weight of ethyl di-n-hexylphosphonoacetate was added from the raw material charging port and kneaded for 15 minutes. Lastly, excess L-lactide was devolatilized, and the polymer was discharged from the reaction vessel to form chips to obtain poly-L lactic acid (PLLA).
The resulting poly L-lactic acid resin has a weight average molecular weight of 151,000, a glass transition point (Tg) of 55 ° C., a melting peak temperature (Tmh) of 177 ° C., a carboxyl group content of 15 eq / ton, and an enantiomer average chain length. The syndiotactic connecting part could not be measured and could not be calculated.

[Component A-2: Production of poly-D-lactic acid (PDLA)]
[Production Example 2]
Poly D-lactic acid (PDLA) was prepared in the same manner as in Production Example 1 except that D-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%) was used instead of L-lactide in Production Example 1. Obtained. The resulting poly-D-lactic acid resin has a weight average molecular weight of 152,000, a glass transition point (Tg) of 55 ° C., a melting peak temperature (Tmh) of 177 ° C., a carboxyl group content of 14 eq / ton, and an enantiomer average chain length. The syndiotactic connecting part could not be measured and could not be calculated. Met.

[Component A-3-1: Production of stereocomplex polylactic acid-1 (scPLA-1)]
[Production Example 3-1]
100 parts by weight of polylactic acid resin composed of 50 parts by weight of PLLA and PDLA obtained in Production Examples 1 and 2 and sodium 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate (Adekastab) (NA-11: manufactured by ADEKA Co., Ltd.) 0.1 parts by weight was mixed with a blender, dried at 110 ° C. for 5 hours, and supplied to a vent type twin-screw extruder having a diameter of 30 mmφ [TEX30XSST manufactured by Nippon Steel Works, Ltd.] Then, it was melt-extruded and pelletized at a cylinder temperature of 250 ° C., a screw rotation speed of 250 rpm, a discharge rate of 9 kg / h, and a vent vacuum of 3 kPa to obtain stereocomplex polylactic acid-1. The resulting stereocomplex polylactic acid-1 had a weight average molecular weight of 130,000, a glass transition point (Tg) of 58 ° C., a complex phase polylactic acid crystal melting peak temperature (Tms) of 220 ° C., and a carboxyl group content of 17 eq / ton, The average enantiomeric chain length was 28, and the ratio of melting peaks at 195 ° C. or higher was 100% among the melting peaks in the temperature rising process of differential scanning calorimetry (DSC) measurement. The amount of NA-11 added is part by weight per 100 parts by weight of PLLA1 and PDLA1 in total.

[Component A-3-2: Production of stereocomplex polylactic acid-2 (scPLA-2)]
[Production Example 3-2]
The PLLA and PDLA obtained by the same method as in Production Examples 1 and 2 except that 0.082 parts by weight of ethyl di-n-hexylphosphonoacetate used in Production Examples 1 and 2 were changed to 1 part by weight. The stereocomplex polylactic acid-2 was produced in the same manner as in Production Example 3-1. The resulting stereocomplex polylactic acid-2 had a weight average molecular weight of 125,000, a glass transition point (Tg) of 58 ° C., a complex phase polylactic acid crystal melting peak temperature (Tms) of 222 ° C., and a carboxyl group content of 45 eq / The average chain length of ton and enantiomer was 27, and the ratio of the melting peak at 195 ° C. or higher among the melting peaks in the temperature rising process of differential scanning calorimetry (DSC) was 100%. The amount of NA-11 added is part by weight per 100 parts by weight of PLLA1 and PDLA1 in total.

[Component A-3-3: Production of stereocomplex polylactic acid-3 (scPLA-3)]
[Production Example 3-3]
Using PLLA and PDLA obtained by the same method as in Production Examples 1 and 2, except that 0.082 parts by weight of ethyl di-n-hexylphosphonoacetate used in Production Examples 1 and 2 was not added at all. Stereocomplex polylactic acid-3 was produced in the same manner as in Production Example 3-1. The resulting stereocomplex polylactic acid-3 had a weight average molecular weight of 1270, a glass transition point (Tg) of 58 ° C., a complex phase polylactic acid crystal melting peak temperature (Tms) of 221 ° C., and a carboxyl group content of 28 eq / The average chain length of ton and enantiomer was 28, and the ratio of the melting peak at 195 ° C. or higher among the melting peaks in the temperature rising process of differential scanning calorimetry (DSC) measurement was 100%. The amount of NA-11 added is part by weight per 100 parts by weight of PLLA1 and PDLA1 in total.
The results are summarized in Table 1.

2. Production and Evaluation of Composition Pellet Composition pellets were produced by the methods shown in the following Examples and Comparative Examples. Moreover, each value in an Example was calculated | required with the following method.

(1) Enantiomeric average chain length The composition was injected using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 230 ° C. and a mold temperature of 120 ° C., a length of 130 mm, a width of 13 mm, A molded piece having a thickness of 1.5 mm was formed. The enantiomeric average chain length of the molded piece thus obtained was calculated by the method described above.

(2) Release property The composition was molded using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 230 ° C, a mold temperature of 120 ° C, and a molding cycle of 100 seconds. The releasability of a molded piece having a thickness of 130 mm, a width of 13 mm, and a thickness of 1.5 mm was determined according to the following criteria. The molding cycle T referred to here is the total of the injection time, pressure holding time, and cooling time.
○: There is no deformation of the molded piece, and there is no problem of releasability.
Δ: Although some deformation is observed in the molded piece, the mold is released.
X: The molded piece is deformed and does not release.

(3) Flame retardancy The composition was molded using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 230 ° C, a mold temperature of 120 ° C, and a molding cycle of 100 seconds. A molded piece having a thickness of 130 mm, a width of 13 mm, and a thickness of 2.0 mm was molded, and the flame retardancy at a test piece thickness of 2.0 mm was evaluated by a method (UL94) defined by US Underwriter Laboratory.

(4) Tensile strength retention after wet heat treatment (ΔTYratio-1)
Test the composition according to the ISO standard with a thickness of 4 mm using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 230 ° C., a mold temperature of 120 ° C. and a molding cycle of 100 seconds. A piece was molded. The test piece was left to stand for 100 hours in a constant temperature and humidity tester having a temperature of 80 ° C. and a relative humidity of 95%, and then left for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50% (after wet heat treatment). And the tensile strength measured using a test piece (test piece before wet heat treatment) left for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The tensile strength retention (ΔTYratio-1) after the wet heat treatment was calculated.
ΔTYratio-1 = 100 × (tensile strength of test piece after wet heat treatment) / (tensile strength of test piece before wet heat treatment)
In addition, the tensile strength said here points out the intensity | strength with the higher intensity | strength among tensile breaking strength and tensile yield strength.

(5) Tensile strength retention after retention molding (ΔTYratio-2)
The composition was molded using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 230 ° C., a mold temperature of 120 ° C., and a molding cycle of 100 seconds. After forming the test piece (normally formed test piece) in a molding cycle of 100 seconds, the molding machine was stopped for 10 minutes while maintaining the temperature, and the molding was performed again in a molding cycle of 100 seconds. The test piece (residual molding test piece) was allowed to stand for 24 hours in an environment at a temperature of 23 ° C. and a relative humidity of 50%, and then subjected to a tensile test, and the measured tensile strength was calculated according to the following formula. The tensile strength retention ratio (ΔTYratio-2) of was calculated.
ΔTYratio-2 = 100 × (tensile strength of stay-molded test piece) / (tensile strength of normal-molded test piece)
In addition, the tensile strength said here points out the intensity | strength with the higher intensity | strength among tensile breaking strength and tensile yield strength.

(6) Evaluation of mold contamination 130 mm in length at a cylinder temperature of 230 ° C., a mold temperature of 120 ° C., and a molding cycle of 100 seconds using an injection molding machine (manufactured by Toshiba Machine Co., Ltd .: IS-150EN). Then, 500 shots of a molded piece having a width of 13 mm and a thickness of 1.5 mm were molded, and the state of the mold surface before and after the molding was visually observed and evaluated as follows.
○: No change before and after the continuous molding test △: There is a considerable amount of deposit after the continuous molding test ×: Very much deposit after the continuous molding test As the A component, A-1, A-2, A described above As 3-1 to 3 and B component, DHPA (B-1 component) described in Reference Example and ammonium hypophosphite [reagent] (B-2 component) for comparison, and as C component, Production Example 3-1 The NA-11 described was used, and the following materials were used as other raw materials.

(D component)
(D-1 component: phosphorus flame retardant)
D-1-1: Phosphate ester flame retardant PX-200 [resorcinol bis (di-2,6-xylyl phosphate)] manufactured by Daihachi Chemical Industry Co., Ltd.
D-1-2: Phosphonate flame retardant FP-100 manufactured by Fushimi Pharmaceutical Co., Ltd. [phenoxyphosphazene oligomer]
D-1-3: Polyphosphate flame retardant AP462 manufactured by Clariant Japan Co., Ltd. [ammonium polyphosphate]
D-1-4: Phosphinate flame retardant EXOLIT1240 [Aluminum diethylphosphinate] manufactured by Clariant Japan Co., Ltd.

(D-2 component: nitrogen-based flame retardant)
D-2-1: Melamine phosphate MELAPUR 200 from Chiba,
D-2-2: Melamine isocyanurate MC610 manufactured by Nissan Chemical Co., Ltd.

(D-3: Metal hydroxide compound)
D-3: Al (OH) 3 reagent [purity 95%]

(E component: terminal blocking agent)
E-1: Aliphatic polycarbodiimide (Carbodilite LA-1 (trade name) manufactured by Nisshinbo Co., Ltd.)
E-2: Epoxy group-containing acrylic-styrene copolymer (ADR-4368CS (trade name) manufactured by BASF Japan K.K.)
E-3: Oxazoline group-containing acrylic-styrene copolymer (Epocross RPS-1005 (trade name) manufactured by Nippon Shokubai)

(F component: inorganic filler)
F-1: Talc (Nippon Talc Co., Ltd. product P-3 [average particle diameter of 5 μm] (trade name))
F-2: Glass fiber (3PE-937S manufactured by Nittobo Co., Ltd. [chopped strand having an average diameter of 13 μm and a cut length of 3 mm] (trade name))

<Examples 1-13, Comparative Examples 1-9>
Using polylactic acid A-1, A-2, A-3-1 to A-3-3 components produced in Production Examples 1, 2, 3-1 to 3-3 as polylactic acid, Tables 2-3 After the composition excluding F-2 in the composition is uniformly premixed by dry blending, the premix is supplied from the first supply port, the F-2 component is supplied from the second supply port, melt-extruded and pelletized. Turned into. Here, the first supply port is a base supply port, and the second supply port is a supply port provided to the side screw. In addition, when F-2 component is not contained in a composition, it cannot be overemphasized that it becomes supply only from a 1st supply port.
In dry blending, all of the examples and comparative examples were prepared by adding 100% by weight of polylactic acid MPA FA500 (trade name) of Daikin Chemical Industries, Ltd., which is a fluorine-containing polymer having the ability to form fibrils as a drip inhibitor. In contrast, 0.1 part by weight, 3 parts by weight of SA120 (trade name) manufactured by Sabic IP, which is a polyphenylene ether as a dripping inhibitor, is 100 parts by weight of polylactic acid, and is a phosphite antioxidant. ADEKA ADK STAB PEP24G (trade name) is 0.05 parts by weight with respect to 100 parts by weight of polylactic acid, and hindered phenol antioxidant Irganox 1076 (trade name) is 100 parts by weight of polylactic acid. 1 part by weight was added.

The melt extrusion was carried out using a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] with a diameter of 30 mmφ equipped with a side screw. The extrusion temperature is C1 / C2-C5 / C6 / C7-C11 / D = 10 ° C./240° C./230° C./220° C./220° C., the main screw rotation speed is 150 rpm, the side screw rotation speed is 50 rpm, The discharge rate was 20 kg / h, and the vent pressure reduction was 3 kPa.
The obtained pellets were dried with a hot air circulation dryer at 100 ° C. for 5 hours and molded with an injection molding machine (manufactured by Toshiba Machine Co., Ltd .: IS-150EN), molding cycle, cracks in molded product, uneven color. The bending elastic modulus, the deflection temperature under load, and the flame retardance were evaluated.

<Examples 1-5>
The composition containing the components A to E within the range described in the present invention has excellent properties such as flame retardancy, small deterioration in physical properties during wet heat treatment and retention molding. In addition, Examples 3-5 whose enantiomer chain length is in the range of 10-40 showed high releasability. Example 3 in which component B was added in step (ii) had a higher physical property retention rate and less mold contamination than Examples 4 and 5 in which component B was added in step (i). It was a good composition with no bad odor during work.

<Comparative Examples 1 and 2>
Comparative Examples 1 and 2 in which the amount of component B added is outside the scope of claims are not preferable, as compared with Example 3, because the flame retardancy and physical property deterioration during wet heat treatment and retention molding are large. In particular, since Comparative Example 2 contains the B-1 component beyond the scope of claims, the flame retardancy is low, the mold contamination is severe, and the bad odor in the working environment is conspicuous.

<Comparative Examples 3 and 4>
In Comparative Example 3 using a B component other than the specific compound, the flame retardancy, the physical property deterioration at the time of wet heat treatment or at the time of residence molding are larger than those of Example 3, and Comparative Example 4 containing no C component is separated. It is inferior in moldability and is not practically preferable.

<Comparative Example 5>
Comparative Example 5 containing no C component is inferior in releasability and is not preferable for practical use.

<Comparative Example 6>
Since the comparative example 6 in which D component is not mix | blended is inferior to a flame retardance compared with Example 3, it is unpreferable.

<Comparative Example 7>
Comparative Example 7 in which the D component is blended beyond the claimed range is inferior in flame retardancy and releasability as compared with Example 3, and is not practically preferable.

<Comparative Examples 8 and 9>
Comparative Examples 8 and 9 in which the amount of component E added is out of the scope of claims are not preferable because, compared with Example 3, the physical properties are greatly reduced during wet heat treatment and during residence molding. In particular, since Comparative Example 9 contains the E component beyond the scope of claims, the mold contamination was severe and the bad odor during the working environment was conspicuous.

<Examples 6 to 8>
Examples 6 to 8 containing the components A to E have flame retardancy, a decrease in physical properties at the time of wet heat treatment and retention molding, and have clearly superior characteristics as compared with the comparative example 6 in which the component D is not blended. .

<Examples 9 and 10>
Examples 9 and 10 are a combination of the E-1 component and the E-2 component, which are excellent in flame retardancy, physical property retention during wet heat treatment and retention molding, and exhibit good properties, but the enantiomeric chain length is 40. In Example 10, exceeding the range, the releasability is slightly inferior to that in Example 9.

<Example 11>
Example 11 is obtained by changing the E-1 component of Example 3 to the E-3 component. Compared to Example 3, although the physical property deterioration at the time of wet heat treatment and retention molding is slightly large, the E component is It is far superior to Comparative Example 8 that is not contained, and industrial utility is recognized.

<Example 12>
Example 12 contains no F component and is slightly inferior in releasability, but has excellent physical property retention during wet heat treatment and retention molding as compared with the comparative example, and industrial utility is recognized. .

<Example 13>
Example 13 containing the F-2 component is slightly superior to the physical property retention at the time of stay molding as compared with Example 3, and the industrial utility value is recognized.

  The polylactic acid composition of the present invention is useful as a material for automobile parts, electrical / electronic parts, electrical equipment exterior parts, OA exterior parts, and the like.

Claims (16)

100 parts by weight of polylactic acid (component A),
0.001 to 5 parts by weight of a phosphono fatty acid ester (component B),
0.01-5 parts by weight of a phosphate metal salt (component C),
1 to 100 parts by weight of at least one selected from the group consisting of a phosphorus-based flame retardant (D-1 component), a nitrogen-based flame retardant (D-2 component) and a metal hydroxide compound-based flame retardant (D-3 component) Flame retardant (D component), and 0.001 to 10 parts by weight of end-capping agent (E component),
A composition containing The polylactic acid (component A) contains poly-L lactic acid (component A-1) mainly composed of L-lactic acid units and poly-D lactic acid (component A-2) mainly composed of D-lactic acid units. The composition according to claim 1, wherein the weight ratio of the component to the component A-2 is in the range of 10:90 to 90:10. The poly-L lactic acid (component A-1) contains 90 mol% or more of L-lactic acid units, and the poly-D lactic acid (component A-2) contains 90 mol% or more of D-lactic acid units. Composition. 4. The composition according to claim 2, wherein the polylactic acid (component A) has a ratio of 195 ° C. or higher of the melting peak in the temperature rising process of differential scanning calorimeter (DSC) measurement of 80% or higher. The composition according to any one of claims 1 to 4, wherein the phosphono fatty acid ester (component B) is represented by the following general formula (1).

(Wherein R ^{1 to} R ³ are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and n is an integer of 1 to 3). The composition according to any one of claims 1 to 5, wherein the phosphate metal salt (component C) is represented by the following formula (2) or (3).

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

Wherein R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₂ is an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. 1 or 2 q is 0 when M ₂ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₂ is an aluminum atom. The phosphorous flame retardant (D-1 component) is at least one selected from the group consisting of a phosphate ester, a phosphonitrile, a phosphonate, a polyphosphate, and a phosphinate. A composition according to claim 1. The nitrogen-based flame retardant (component D-2) is at least one selected from the group consisting of melamine compounds, reaction products of melamine compounds and polyphosphoric acid, and reaction products of melamine condensates and polyphosphoric acid. The composition according to any one of claims 1 to 7. The composition according to any one of claims 1 to 8, wherein the terminal blocking agent (component E) is at least one selected from the group consisting of a carbodiimide compound, an epoxy compound, an oxazoline compound, and an oxazine compound. The composition as described in any one of Claims 1-9 which contains 0.05-100 weight part inorganic filler (F component) with respect to 100 weight part of polylactic acid (A component). The composition as described in any one of Claims 1-10 whose tensile strength retention (T) represented by a following formula is 50% or more.
T (%) = t ¹ / t ⁰ × 100
(Where t ⁰ is the initial tensile strength, and t ¹ is the tensile strength after 100 hours in an atmosphere of 80 ° C. and 95% RH). The composition according to any one of claims 1 to 11, wherein the enantiomeric average chain length determined by ¹³ C-NMR of the polylactic acid (component A) is 10 to 40. (i) Composition-1 containing 0.001 to 3 parts by weight of a phosphono fatty acid ester (component B) and 100 parts by weight of poly-L lactic acid (A-1 component) Composition-2 containing 0.001 to 3 parts by weight of phosphono fatty acid ester (component B) with respect to D-lactic acid (component A-2) is 100 parts by weight in total of composition-1 and composition-2. In contrast, a step of preparing stereocomplex polylactic acid by melt-kneading in the presence of 0.01 to 5 parts by weight of a phosphoric acid ester metal salt (component C), and
(ii) 100 parts by weight of the obtained stereocomplex polylactic acid, 0.001 to 2 parts by weight of a phosphono fatty acid ester (B component), 1 to 100 parts by weight of a phosphorus flame retardant (D-1 component), At least one flame retardant (D component) selected from the group consisting of a nitrogen-based flame retardant (D-2 component) and a metal hydroxide compound-based flame retardant (D-3 component), and 0.001 to 10 parts by weight of terminals A step of melt-kneading the sequestering agent (component E),
The method for producing a composition according to claim 1, comprising: The molded article which consists of a composition as described in any one of Claims 1-12. The molded article according to claim 14, which is molded by injection molding, extrusion molding, thermoforming, blow molding or foam molding. The molded article according to claim 14, which is an automobile part, an electrical / electronic part, an electrical equipment exterior part, or an OA exterior part.