JP5155075B2 - Polylactic acid-containing composition and method for producing the same - Google Patents

Description

  The present invention relates to a method for producing a polylactic acid-containing composition. More specifically, the present invention relates to a method for producing a polylactic acid-containing composition having a good hue.

  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 the biodegradable polymer, polyhydroxybutyrate, polycaprolactone, aliphatic polyester, polylactic acid and the like are known.

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

  Therefore, the use as a general-purpose polymer is also examined, and application to the casing of electronic parts such as relays and connectors as well as stretched films and fibers as well as injection-molded products is being studied.

  As a method for producing such polylactic acid, many methods such as direct polymerization by dehydration of lactic acid, melt ring-opening polymerization of lactide, or solid phase polymerization of low molecular weight oligomers produced by these methods have been proposed, and reviews have been published. (See Non-Patent Document 1).

  Among these, melt ring-opening polymerization of lactide, particularly a method using a metal catalyst, is expected as a promising method from the viewpoint of production cost and quality of polylactic acid to be produced.

However polylactic acid by melt ring-opening polymerization method using a slave come known catalyst is a strong yellowness of the polymer, applied to thermal degradation in the polyester include polylactic acid for example a phosphite as a stabilizer In which the melt flow rate (hereinafter sometimes abbreviated as MFR) is stabilized has been proposed (for example, see Patent Document 1).

  However, this proposal uses this phosphite ester as a general polyester stabilizer, and there is no description or suggestion that phosphite ester is used as a catalyst component in the melt ring-opening polymerization of polylactic acid. .

  In addition, there are also proposals for improving the hue and stability of compositions by applying stabilizers such as various sterically hindered phenolic compounds, phosphite ester compounds and other thioether compounds to polylactic acid (see Patent Document 2). Although it was made and the hue of polylactic acid was mentioned, this proposal is also a proposal in the category of stabilizers as in the above-mentioned proposal, and no suggestion is made as to its effectiveness as a catalyst component.

  The practically important point that the present inventors have focused on is that even if a stabilizer is added to the obtained polylactic acid, if the original polylactic acid has a poor hue, an improvement in hue cannot be achieved.

  Generally, in melt ring-opening polymerization of lactide using a metal catalyst, high-purity lactide with less acidic substances as the raw material lactide (acid amount is less than 0.05% by weight) in order to efficiently increase the average molecular weight of polylactic acid. Otherwise, the catalytic activity of the metal catalyst decreases rapidly, and on the other hand, there is little decrease in the activity of the coloring side reaction, so there is a problem that the polymerization time is greatly prolonged and the rapid deterioration of the polylactic acid hue becomes remarkable. In many cases, purification operations such as distillation and recrystallization are required, and as a result, there has been a problem that an increase in product cost is unavoidable.

JP 2002-138188 A JP 2003-321601 A Highly functional biodegradable plastics and their applications for the removal of petroleum materials, 2003 NTS Publishing Co., Ltd.

  An object of the present invention is to provide a method for producing a polylactic acid-containing composition having a good hue by solving the problems that could not be achieved by the above prior art.

  A further object of the present invention is to provide a polylactic acid-containing composition obtained by the above production method and a melt-molded product comprising the same.

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

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

（式中、Ｒ^７は単結合または炭素数１〜８のアルキレン基を示し、＊は酸素原子側に結合していることを示す。）で示される２価の残基を示し、Ｙ、Ｚはいずれか一方がヒドロキシル基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシル基または炭素数７〜１２のアラルキルオキシ基を示し、他の一方が水素原子または炭素数１〜８のアルキル基を示す。〕 As a result of intensive studies to solve the above problems, the present inventor has arrived at the present invention. That is, the object of the present invention is to
1. Presence of content of the acidic impurities phosphite compound represented by La Kuchido and the following formula in the range of 0.01 wt% to 0.3 wt% (1), tin, aluminum, zinc, calcium Polylactic acid that uses a metal compound containing at least one metal selected from titanium, germanium, manganese, magnesium, and rare earth elements as a catalyst, and is subjected to melt ring-opening polymerization under the following conditions (a) to (c) The manufacturing method of a containing composition.
(A) A total of 0.001 to 0.1 mmol of the above metal compound per mole of lactide.
(B) A total of 0.01 to 10 mmol of the above phosphite compound per mole of lactide.
(C) The molar ratio of the total amount of the phosphorous acid compound and the total amount of the metal compound is in the range of 0.01 to 1000.

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

(Wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents 2 to 8 carbon atoms. An alkylene group of formula (I-2)

(In the formula, R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond to the oxygen atom side.) Y, Z Is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or 1 to 8 carbon atoms. Represents an alkyl group. ]

３．金属化合物がオクチル酸スズ（ＩＩ）、スズメトキシド（ＩＩ）、スズアルコキシド（ＩＩ）、スズイソプロポキシド（ＩＩ）からなる群から選ばれる、上記１または２に記載の製造方法。
４．ラクチドが、Ｌ−ラクチド、Ｄ−ラクチドまたはメソラクチドである、上記１から３のいずれかに記載の製造方法。
５．酸性不純物が乳酸、乳酸オリゴマーおよびピルビン酸から選ばれる上記１に記載の製造方法。
６．上記１から５のいずれか記載の方法で製造されたポリ乳酸含有組成物。
７．下記要件を満たす、上記６に記載のポリ乳酸含有組成物。
（ｄ）チップとして測定したカラーｂ値が１５未満であること。
８．上記６から７のいずれかに記載のポリ乳酸含有組成物よりなる溶融成形品。
９．溶融成形品がフィルム、シート、繊維、繊維構造体、射出成形品より選択される形状を有する、上記８に記載の溶融成形品。
１０．上記６に記載のポリ乳酸含有組成物に、更に、熱可塑性樹脂、安定剤、結晶化促進剤、充填剤、離型剤、帯電防止剤、末端末端封止剤、可塑剤および耐衝撃性安定剤からなる群より選ばれる少なくとも一種を含有する、ポリ乳酸含有組成物。
１１．上記１０に記載のポリ乳酸含有組成物よりなる溶融成形品。
１２．溶融成形品がフィルム、シート、繊維、繊維構造体、射出成形品より選択される形状を有する、上記１１記載の溶融成形品。 Further, the present invention includes the following matters.
2. 2. The production method according to 1 above, comprising a divalent tin compound as the metal compound and a phosphite ester represented by the following formula (2) as the phosphite compound.

3. 3. The production method according to 1 or 2 above, wherein the metal compound is selected from the group consisting of tin (II) octylate, tin methoxide (II), tin alkoxide (II), and tin isopropoxide (II).
4). 4. The production method according to any one of 1 to 3 above, wherein the lactide is L-lactide, D-lactide, or meso lactide.
5. 2. The production method according to 1 above, wherein the acidic impurity is selected from lactic acid, a lactic acid oligomer and pyruvic acid.
6). A polylactic acid-containing composition produced by the method according to any one of 1 to 5 above.
7). 7. The polylactic acid-containing composition according to 6 above that satisfies the following requirements.
(D) The color b value measured as a chip is less than 15.
8). A melt-molded article comprising the polylactic acid-containing composition according to any one of 6 to 7 above.
9. 9. The melt molded product according to 8 above, wherein the melt molded product has a shape selected from a film, a sheet, a fiber, a fiber structure, and an injection molded product.
10. In addition to the polylactic acid-containing composition described in 6 above, a thermoplastic resin, a stabilizer, a crystallization accelerator, a filler, a mold release agent, an antistatic agent, a terminal end-capping agent, a plasticizer, and a stable impact resistance A polylactic acid-containing composition containing at least one selected from the group consisting of agents.
11. A melt-molded article comprising the polylactic acid-containing composition as described in 10 above.
12 12. The melt-formed product according to 11 above, wherein the melt-formed product has a shape selected from a film, a sheet, a fiber, a fiber structure, and an injection- molded product.

  According to the production method of the present invention, it is possible to economically and advantageously produce a polylactic acid-containing composition that can greatly shorten the polymerization time of polylactic acid and has a good hue. Furthermore, according to the polylactic acid-containing composition of the present invention, it is possible to obtain a molded article having a good hue.

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

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

（式中、Ｒ^７は単結合または炭素数１〜８のアルキレン基を示し、＊は酸素原子側に結合していることを示す。）で示される２価の残基を示し、Ｙ、Ｚはいずれか一方がヒドロキシル基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシル基または炭素数７〜１２のアラルキルオキシ基を示し、他の一方が水素原子または炭素数１〜８のアルキル基を示す。〕 Hereinafter, the present invention will be described in detail.
In the present invention, the coexistence of a phosphite compound represented by the content is in the range of 0.01 wt% to 0.3 wt% La Kuchido and the following formula of acidic impurities (1), tin, Using a metal compound containing at least one kind of metal selected from aluminum, zinc, calcium, titanium, germanium, manganese, magnesium and rare earth elements as a catalyst, it is melt-opened under the conditions of the following requirements (a) to (c). Ring polymerize.

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

(Wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents 2 to 8 carbon atoms. An alkylene group of formula (I-2)

(In the formula, R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond to the oxygen atom side.) Y, Z Is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or 1 to 8 carbon atoms. Represents an alkyl group. ]

  First, the starting lactide is L-lactide, D-lactide, or meso lactide. These have no particular disadvantage in the polymerization ability of the catalyst of the present invention and the hue of the polylactic acid-containing composition even when the optical purity is low, but the hue of the resulting polylactic acid-containing composition, From the viewpoint of crystallinity and the like, the optical purity is suitably selected in the range of 90% or more, more preferably 95% or more, and still more preferably 97% or more.

In the present invention, it is essential that the lactide and the phosphite compound represented by the general formula (1) coexist.
Conventionally, the purity of the raw material lactides had to be extremely high. That is, apart from optical purity, when the content of acidic impurities in lactides exceeds 0.05% by weight, the catalytic activity of the metal catalyst decreases rapidly, but on the other hand, the decrease in the activity of the colored side reaction is small. Significantly prolonged time and rapid deterioration of polylactic acid hue.

  However, when the lactide and the phosphite ester represented by the general formula (1) coexist as described above and then subjected to a melt ring-opening polymerization reaction using a metal compound described later, the acid amount of the starting lactide is as follows: Naturally, a smaller amount is better, but from the viewpoints of polymerization time and polylactic acid hue, it can be seen that there is a remarkable effect that the acid impurity content of lactides is allowed to be up to about 0.3% by weight. It was. It was also found that the polymerization time was greatly shortened and the hue was improved even when the content of acidic impurities in the lactides was less than 0.05% by weight.

  In general, lactides are extremely hydrolytically resistant compounds, decomposed by slight moisture during storage and storage, and often increase the content of acidic impurities to more than 0.05% by weight. Lactides having an increased impurity content could not be used unless they were purified by distillation or the like.

  However, when the content of acidic impurities exceeds 0.3% by weight, it is rare under normal storage conditions, and it can be used in a polymerization reaction as it is without purification by distillation or the like, so that the economic effect is extremely large.

  In general, lactide melt ring-opening polymerization catalysts have conventionally been alkali metal, alkaline earth metal, rare earth, transition metals, fatty acid salts such as aluminum, germanium, tin, antimony, carbonates, sulfates, phosphates, oxides. Hydroxides, halides, alcoholates and the like have been used.

  However, in the present invention, it is essential to employ a compound containing at least one metal selected from tin, aluminum, zinc, calcium, titanium, germanium, manganese, magnesium, and rare earth elements.

  Specifically, stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, tin myristate, tin octylate, tin stearate, tetraphenyltin, tin methoxide, Tin ethoxide, tin propoxide, tin butoxide, aluminum oxide, aluminum acetylacetonate, aluminum isopropoxide, aluminum-imine complex titanium tetrachloride, ethyl titanate, butyl titanate, glycol titanate, titanium tetrabutoxide, zinc chloride, oxidation Examples include zinc, diethyl zinc, antimony trioxide, antimony tribromide, antimony acetate, calcium oxide, germanium oxide, manganese oxide, manganese carbonate, manganese acetate, magnesium oxide, yttrium alkoxide and the like.

  Considering the catalytic activity and few side reactions, stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, stannous myristate, stannous octoate, stannous stearate Preferred are tin-containing compounds such as tetraphenyltin, tin methoxide, tin ethoxide, tin propoxide and tin butoxide, and aluminum-containing compounds such as aluminum acetylacetonate, aluminum butoxide and aluminum-imine complexes. More preferably, diethoxytin, dinonyloxytin, tin myristate, tin octylate, tin stearate, tin chloride, tin methoxide, tin ethoxide, tin propoxide, tin butoxide, aluminum acetylacetonate, aluminum isopropoxide and the like are exemplified. The

  Of these, II-valent tin compounds, particularly alkoxides of 4 to 22 carbon atoms of II-valent tin and salts of fatty acids are exemplified as suitable examples.

  Among these, tin (II) octylate is exemplified as the most preferable one in terms of safety and catalytic activity.

  The polylactic acid-containing composition of the present invention comprises poly-L-lactic acid, poly-D-lactic acid obtained by melt ring-opening polymerization of L-lactide, D-lactide and / or meso-lactide and / or random or block copolymerized polylactic acid of these components. is there.

  In poly L-lactic acid and poly D-lactic acid, the main repeating unit is preferably substantially composed of an L-lactic acid unit and a D-lactic acid unit.

  The poly-L-lactic acid is preferably composed of 90 to 100 mol%, more preferably 97 to 100 mol%, and more preferably 99 to 100 mol% L-lactic acid units to achieve a higher melting point. .

  Examples of units other than L-lactic acid include D-lactic acid units and copolymerized units other than lactic acid. The content of D-lactic acid units and copolymer units other than lactic acid is preferably selected in the range of 0 to 10 mol%, more preferably 0 to 3 mol%, and still more preferably 0 to 1 mol%.

  The poly-D-lactic acid is preferably 90 to 100 mol%, more preferably 97 to 100 mol%, and more preferably 99 to 100 mol% L-lactic acid units to achieve a higher melting point. .

  Examples of units other than D-lactic acid include L-lactic acid units and copolymerized units other than lactic acid. The L-lactic acid unit and the copolymer unit other than lactic acid are selected in the range of 0 to 10 mol%, preferably 0 to 3 mol%, 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. Polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol, Examples thereof include aliphatic polyhydric alcohols such as sugar alcohols, and aromatic polyhydric alcohols obtained by adding ethylene oxide to bisphenol. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid. Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like. In the present invention, in order to obtain polylactic acid having a good hue, the above metal compound is used in an amount of 0.001 to 0.1 mmol and a phosphorous acid compound in the range of 0.01 to 10 mmol per mol of lactide, In addition, it is essential that the molar ratio of the total amount of the phosphorous acid compound and the total amount of the metal is in the range of 0.1 to 1000.

  In this aspect, the metal compound is preferably used in an amount of 0.001 to 0.1 mmol per mol of lactide, a phosphorous acid compound in the range of 0.01 to 10 mmol, and the total amount (mol) of the metal. More preferably, the ratio of the total amount of the phosphite compound is 0.1 to 1000, and the amount of the specific metal catalyst used is 0.002 to 0.05 mmol per mol of lactide, and the specific phosphite compound is 0.1. It is used in the range of 02 to 5 mmol, and the total amount of the specific metal (mole) and the total amount of the specific phosphite compound is in the range of 0.5 to 500, particularly preferably, the amount of the specific metal catalyst used is lactide 1 0.003 to 0.02 mmol per mole, the specific phosphite compound used in the range of 0.03 to 2 mmol, and the total amount of the specific metal and the total amount of the specific phosphite compound There range 1 350 is selected.

In the specific phosphorous acid compound represented by the formula (I) used in the present invention, R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 5 carbon atoms. A -12 alicyclic group, a C7-12 aralkyl group or an aromatic group is shown.

  Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, t- A pentyl group, i-octyl group, t-octyl group, 2-ethylhexyl group and the like can be mentioned.

  Examples of the alicyclic group having 5 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-methylcyclopentyl group, a 1-methylcyclohexyl group, and a 1-methyl-4-i-propylcyclohexyl group. Group and the like.

  Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group and the like.

  Examples of the aromatic group having 7 to 12 carbon atoms include phenyl group, naphthyl group, 2-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, and 2,6-dimethylphenyl group. .

R ¹ , R ² , and R ⁴ are preferably an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 5 to 12 carbon atoms, and the like.

R ¹ and R ⁴ are more preferably a t-alkyl group such as a t-butyl group, a t-pentyl group or a t-octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group.

R ² is preferably an alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group and t-pentyl group. , Methyl group, t-butyl group, t-pentyl group and the like are more preferable. R5 is a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, t-pentyl group, etc. ~ 5 alkyl groups are preferred.

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

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

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

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

R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms. Examples of the alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, and a hexamethylene group. Group, octamethylene group, 2,2-dimethyl-1,3-propylene group and the like. Such R7 is preferably a single bond, an ethylene group or the like.

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

  Y and Z are Y is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and Z is a hydrogen atom or 1 to 8 carbon atoms. Z may be a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and Y may be a hydrogen atom or It may be an alkyl group having 1 to 8 carbon atoms.

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

Examples of the phosphorous acid compound (I) include 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo. [d, f] [1,3,2] dioxaphosphepin [ "Sumiraiza chromatography (registered trademark) G P" (commercially available as Sumitomo chemical Co., Ltd.). 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] dibenzo [D, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -12H Dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di -T-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8 , 10-Tetra-t-butyl-6- (3,5-di-t-butyl-4- Roxybenzoyloxy) -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t -Butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,10 -Diethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3 2] Dioxaphosphocin, 2,4,8,10-tetra-t-butyl Ru-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphine Etc.

  Among them, the compound represented by the formula (2) is particularly exemplified as a compound that can be most suitably used because of its activity and the existence of a commercially available product with relatively high purity and low cost.

  Such phosphorous acid compound (I) can be produced, for example, by the method described in JP-A-9-149270.

  In the present invention, melt polymerization of polylactic acid is preferably performed under the specific polymerization atmosphere described below.

  That is, in the present invention, melt ring-opening polymerization is performed in an inert gas atmosphere at a pressure of 13.33 kPa (100 Torr) to 0.3 MPa (3 atm). At this time, the oxygen-containing concentration of the inert gas is 1 to 500 v / A range of vppm is preferably employed. Although various literatures have shown that the oxygen gas concentration affects the polymer hue, the relationship with the activity of the melt ring-opening polymerization catalyst has not yet been established.

  From this point of view, the oxygen content concentration in the present invention is preferably selected in the range of preferably 2 to 300 v / vppm, more preferably 3 to 200 v / vppm.

  Conventionally, when polymerizing using only a metal catalyst, the polymerization temperature is polymerized at a temperature in the vicinity of 180 ° C. when the conversion rate of lactide is about 70 to 80%, but the catalytic activity decreases as the degree of polymerization increases. Therefore, it is a usual method to gradually raise the polymerization temperature after this, and finally carry out the polymerization at 200 to 210 ° C.

  However, when polymerizing at such a high temperature for a long time, it is essentially difficult to suppress side reactions of polylactic acid, and coloring of polylactic acid is an unavoidable problem.

  In contrast, the reaction system of the present invention possesses sufficiently high activity from the initial stage to the late stage of polymerization, so that it is possible to perform polymerization efficiently in a temperature range in which mechanical stirring and removal are not difficult. In addition, it is possible to obtain polylactic acid with good quality.

  Therefore, in the present invention, it is possible to efficiently proceed from the initial stage to the final stage of the polymerization reaction at a temperature in the vicinity of 170 to 210 ° C., and obtain polylactic acid with good quality.

  In the present invention, alcohol may be used as a polymerization initiator. Such alcohols are preferably non-volatile without inhibiting the polymerization of polylactic acid. For example, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, and polyhydric alcohols include ethylene glycol, propylene glycol, butane. Diol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol, aliphatic polyhydric alcohols such as sugar alcohol, etc. or bisphenol Aromatic polyhydric alcohols such as those obtained by adding ethylene oxide to can be suitably used. Moreover, molecular weight can be adjusted with addition amount. In melt ring-opening polymerization, it can be produced by a conventionally known method.

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

  The polymerization reaction can be carried out in a conventionally known reaction vessel. For example, a vertical reactor or a horizontal reactor equipped with a stirring blade for high viscosity, such as a helical ribbon blade, can be used alone or in parallel. Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.

  In the solid phase polymerization method, a relatively low molecular weight lactic acid polylactic acid obtained by the above-described ring-opening polymerization method is used as a prepolymer. It can be said that the prepolymer is preferably crystallized in advance in the temperature range of the glass transition temperature (Tg) or higher and lower than the melting point (Tm) from the viewpoint of preventing fusion. The crystallized prepolymer is filled in a fixed vertical or horizontal reaction vessel, or a reaction vessel (rotary kiln, etc.) where the vessel itself rotates like a tumbler or kiln, and the prepolymer glass transition temperature (Tg) or higher. Heated to a temperature range below the melting point (Tm).

  There is no problem even if the polymerization temperature is raised stepwise as the polymerization proceeds. In addition, for the purpose of efficiently removing water generated during solid phase polymerization, a method of reducing the pressure inside the reaction vessels or circulating a heated inert gas stream is also preferably used.

For polylactic acid, it is preferable to inactivate the metal-containing catalyst used during polymerization with a deactivator. Examples of such a deactivator include an organic ligand comprising a group of chelate ligands having an imino group and capable of coordinating to a polymerized metal catalyst, dihydridooxoline (I) acid, dihydridotetraoxodilin (II, II ) Acid, hydridotrioxoline (III) acid, dihydridopentaoxodiphosphorus (III) acid, hydridopentaoxodi (II, IV) acid, dodecaoxohexaphosphorus (III) III, hydridooctaoxotriphosphate (III, IV) , IV) acid, octaoxotriphosphoric acid (IV, III, IV), hydridohexaoxodiphosphoric acid (III, V), hexaoxodiphosphoric acid (IV), decaoxotetraphosphoric acid (IV), ) Low oxidation number phosphoric acid having an acid number of 5 or less, such as acid or eneoxooxo triphosphoric acid (V, IV, IV), represented by the formula xH ₂ O · yP ₂ O ₅ Orthophosphoric acid of x / y = 3, 2> x / y> 1, and polyphosphoric acid called a diphosphoric acid, triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid and the like based on the degree of condensation, and a mixture thereof, Metaphosphoric acid represented by x / y = 1, especially trimetaphosphoric acid, tetrametaphosphoric acid, ultraphosphoric acid represented by 1> x / y> 0 and having a network structure with a part of the phosphorus pentoxide structure (These may be collectively referred to as metaphosphate compounds), and acid salts of these acids, monovalent and polyhydric alcohols, partial esters of polyalkylene glycols, fully ether, phosphono-substituted lower Examples thereof include aliphatic carboxylic acid derivatives.

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

  The metaphosphoric acid compound used in the present invention is a cyclic metaphosphoric acid in which about 3 to 200 phosphoric acid units are condensed, an ultra-regional metaphosphoric acid having a three-dimensional network structure, or an alkali metal salt or an alkaline earth metal salt thereof. Onium salts).

  Among them, cyclic sodium metaphosphate, ultra-region sodium metaphosphate, phosphono-substituted lower aliphatic carboxylic acid derivative dihexylphosphonoethyl acetate (hereinafter sometimes abbreviated as DHPA) and the like are preferably used.

  Under such polymerization atmosphere and polymerization conditions, the weight average molecular weight of the polylactic acid of the present invention obtained has a sufficiently high heat resistance, for example, a high heat distortion temperature and crystallinity, in terms of both moldability and physical properties of the molded product. The polylactic acid preferably has a weight average molecular weight in the range of 100,000 to 500,000. If the weight average molecular weight is less than 100,000, the mechanical strength and toughness of the molded product are low, which is not preferable. Further, if the weight average molecular weight exceeds 500,000, the melt viscosity is high, and melt molding becomes difficult.

  Further, the hue of the polylactic acid-containing composition has a color b value of less than 10, more preferably 8 or less, still more preferably less than 6, and particularly preferably 5 or less.

  Such a polylactic acid-containing composition having a good hue can be suitably used for apparel applications with severe taste and preference and optical applications that require strict transparency.

  Furthermore, in the present invention, polylactic acid has a crystal melting peak (Tmh) between 150 and 190 ° C. as measured by differential scanning calorimetry (DSC), and the heat of crystal melting (ΔHmsc) is 10 J / g or more. Preferably there is.

  This is because the heat resistance is preferably enhanced by satisfying the range of the crystal melting point and the crystal melting heat.

  The lactide content in the polylactic acid-containing composition of the present invention is suitably selected in the range of 0 to 700 ppm. More preferably, a range of 0 to 500 ppm, more preferably 0 to 200 ppm, particularly preferably 0 to 100 ppm is selected. The melt ring-opening polymerized poly L- and / or poly D-lactic acid usually contains 1% by weight or more of lactide, but a conventionally known lactide removal method, that is, a vacuum devolatilization method using a single or multi-screw extruder, or The amount can be reduced according to high vacuum treatment in the polymerization apparatus. The smaller the lactide content, the better the melt stability and wet heat stability of the resin, but there is also an effect of lowering the melt viscosity, and it is rational and economical to adjust the content to meet the desired purpose.

  By having a lactide content in such a range, the polylactic acid-containing composition improves the stability of the resin composition of the present invention at the time of melting, the advantage that the production of the molded product can be efficiently performed in a high cycle and the resistance of the molded product. It is because hydrolysis stability and low gas property can be improved.

  Melt stability is a parameter of resin stability at the time of melting, and is evaluated by a retention rate of molecular weight after being held at 260 ° C. for 10 minutes. If the melt stability is 80% or more, normal injection molding and extrusion molding can be performed by appropriately setting the conditions. Therefore, the range of melt stability is preferably 80% or more, more preferably 85% to 99%, and still more preferably 90% to 98%.

Hydrolysis stability is a stability parameter when a sample is exposed to wet heat conditions in a solid state, and is expressed as a molecular weight retention rate when the sample is held at 120 ° C. and 100% RH for 10 hours. The If the parameter is 80% or more, it is judged that the molded product made of the composition of the present invention can be used as a guideline for maintaining various physical properties under wet heat conditions. Hydrolytic stability is more preferably 8 5% to 99%, more preferably 90% to 98%.

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

  If desired, the composition of the present invention may contain a thermoplastic resin other than polylactic acid. The thermoplastic resin is not particularly limited, and is not limited to polyester resin other than polylactic acid, polyamide resin, polyacetal resin, polyolefin resin such as polyethylene resin and polypropylene resin, polystyrene resin, acrylic resin, polyurethane resin, chlorinated polyethylene. Resin, chlorinated polypropylene resin, aromatic and aliphatic polyketone resin, fluorine resin, polyphenylene sulfide resin, polyetherketone resin, polyimide resin, thermoplastic starch resin, AS resin, ABS resin, AES resin, ACS resin, polychlorination Vinyl resin, polyvinylidene chloride resin, vinyl ester resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene Kisaido resin, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, and thermoplastic resins such as polyvinyl alcohol resins.

  Among them, polyester resin other than polyacetal resin and polylactic acid resin, for example, selected from polyester resins such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyamide resin. It is preferable to blend at least one kind.

  By blending these resins, a molded product having superior surface properties, moldability, mechanical properties, durability, toughness and the like can be obtained from the composition of the present invention.

  The content of the thermoplastic resin other than polylactic acid is preferably 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, still more preferably 3 to 70 parts by weight, even more preferably, per 100 parts by weight of polylactic acid. Is 5 to 50 parts by weight. By blending these resins, a composition and a molded product having excellent characteristics can be obtained.

  The composition of the present invention preferably contains a stabilizer. As a stabilizer, what is used for the stabilizer of a normal thermoplastic resin can be used. For example, an antioxidant, a light stabilizer, etc. can be mentioned. By blending these agents, it is possible to obtain a composition and a molded article excellent in the mechanical properties, moldability, heat resistance and durability of the composition organism.

  Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphite compounds, thioether compounds, and the like.

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

  As a hindered amine compound, N, N′-bis-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis [3- (3′-Methyl-5′-t-butyl-4′-hydroxyphenyl) propionyl] diamine, N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionyl ] Hydrazine, N-salicyloyl-N'-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N'-bis [2- {3- (3,5-di -T-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide and the like. Preferably, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate] and tetrakis [methylene-3- (3 ′, 5′-di-t-butyl) -4-hydroxyphenyl) propionate] methane and the like.

  As the phosphite compound, those in which at least one P—O bond is bonded to an aromatic group are preferable. Specifically, tris (2,6-di-t-butylphenyl) phosphite, tetrakis ( 2,6-di-t-butylphenyl) 4,4′-biphenylene phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-t-butylphenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris ( Nirufeniru) phosphite, 4,4'-isopropylidene-bis (phenyl - dialkyl phosphite), and the like.

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

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

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

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

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

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

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

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

  Examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2, 6,6-tetramethylpiperidine, 4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarba Yloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethylpi-4-peridyl) adipate, bis (2,2,6,6-tetramethylpi-4-peridyl) terephthalate, 1,2-bis (2,2,6,6-tetramethylpi-4-peridylo) Cis) -ethane, α, α′-bis (2,2,6,6-tetramethylpi-4-peridyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) -tolylene -2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4 -Piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- "2 -{3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid and 1 , 2,2,6,6 A condensate of pentamethyl-4-piperidinol with β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethanol, etc. Can be mentioned. In the present invention, these components may be used alone or in combination of two or more.

  As the stabilizer component, a hindered phenol compound and / or a benzotriazole compound are preferable. The content of the stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of polylactic acid.

  The polylactic acid-containing composition of the present invention can contain an organic or inorganic crystallization accelerator. By containing the crystallization accelerator, the action of the phosphate ester metal salt can be further enhanced, and a composition excellent in mechanical properties, heat resistance, and moldability can be obtained.

  Composition containing polylactic acid, polycarbodiimide, metaphosphoric acid compound and phosphoric acid ester metal salt containing a crystallization accelerator improves the crystallinity of the composition and has excellent moldability and heat resistance. Thus, a molded product that is sufficiently crystallized and excellent in heat resistance can be obtained even in ordinary injection molding. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.

  As the crystallization nucleating agent used in the present invention, those generally used as a polymer nucleating agent can be used, and any of an inorganic crystal nucleating agent and an organic crystal nucleating agent can be used.

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

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

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

  Among these, at least one selected from talc and organic carboxylic acid metal salts is preferably used. Only one type of crystal nucleating agent may be used in the present invention, or two or more types may be used in combination.

  The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight per 100 parts by weight of polylactic acid.

  In the present invention, an organic or inorganic filler can be contained. By containing the filler component, a composition excellent in mechanical properties, heat resistance, and moldability can be obtained.

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

  These organic fillers may be those directly collected from natural products, but may also be those obtained by recycling waste materials such as waste paper, waste wood and old clothes. Waste paper is newspaper, magazines, other recycled pulp, or paperboard such as cardboard, cardboard, paper tube, etc. Any one may be used as long as it is processed from plant fiber. From the viewpoint of formability, pulverized products of paperboard such as newspaper, cardboard, cardboard and paper tube are preferred. The wood is preferably a softwood material such as pine, cedar, oak or fir, or a hardwood material such as beech, shii or eucalyptus.

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

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

  As paper powder, chemicals generally used as a papermaking raw material from the viewpoint of formability, for example, sizing agents such as rosin, alkyl ketene dimer, alkenyl succinic anhydride, paper strength enhancer such as polyacrylamide, polyethyleneimine Yield improver such as, polymer flocculant, filterability improver, deinking agent such as nonionic surfactant, slime control agent such as organic halogen, pitch control agent such as organic or enzyme, peroxide Detergents such as hydrogen, defoaming agents, pigment dispersants, lubricants, and other organic substances, aluminum sulfate used as a fixing agent for sizing agents, and other sodium hydroxide and magnesium hydroxide used as raw materials for papermaking Inorganic substances such as sodium sulfate, sodium silicate, aluminum chloride and sodium chlorate are preferably included.

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

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

  Specifically, for example, glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, imogolite, sepiolite, slag fiber, zonolite, elestite, Fibrous inorganic fillers such as gypsum fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, layered silicate, layered silicate exchanged with organic onium ions, glass flakes, Non-swelling mica, graphite, metal foil, ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, powdered silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate Arm, barium sulfate, oxide Karushikumu, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, include plate-like or granular inorganic fillers such as dawsonite and white clay.

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

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

  Examples of the cation and organic onium ion to be exchanged include ammonium ion, phosphonium ion, and sulfonium ion. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred because of their high ion exchange properties. The ammonium ion may be any of primary to quaternary ammonium ions.

  Those having a reactive functional group and those having high affinity are preferred, and ammonium ions derived from 12-aminododecanoic acid, polyalkylene glycol having an amino group at the terminal, and the like are also preferred.

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

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

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

  The amount of the inorganic filler is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 50 parts by weight, particularly preferably 1 to 100 parts by weight of polylactic acid. -30 parts by weight, most preferably 1-20 parts by weight.

  In this invention, it is preferable to mix | blend a mold release agent. As the release component used in the present invention, those used for ordinary thermoplastic resins can be used.

  Specific examples of mold release components 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 resin composition and a molded product excellent in mechanical properties, moldability, and heat resistance can be obtained.

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

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

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

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

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

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

  Examples of the modified silicone include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.

  Of these, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferred. Of these, montanic acid ester, montanic acid partial saponified ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferred, and particularly, montanic acid partial saponified ester and ethylene bisstearic acid amide are preferred. preferable.

  A mold release agent may be used by 1 type and may be used in combination of 2 or more type. The content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight with respect to 100 parts by weight of polylactic acid.

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

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

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

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

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

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

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

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

Furthermore, a commercially available polycarbodiimide compound as the polycarbodiimide compound can be suitably used without the need for synthesis. Such commercial polycarbodiimide compounds are commercially available from e.g. Nisshinbo Industries, Inc. "Karubojirai bets (registered trademark)" "Karubojirai bets (registered trademark)" sold under the trade name of LA-1 or HMV-8 CA, Etc. can be illustrated.

  In the present invention, a carboxyl group-reactive end-capping agent is preferably contained. Any agent that can seal the carboxyl terminal group of polylactic acid can be used without particular limitation.

  In the present invention, the carboxyl group-reactive terminal blocking agent not only seals the terminal carboxyl group of the polylactic acid resin, but also includes a carboxyl group generated by the decomposition reaction of the polylactic acid resin and various additives, lactic acid, formic acid and the like. The carboxyl group of a low molecular compound can be sealed. Moreover, it is preferable that the said sealing agent is a compound which can seal | block the hydroxyl group terminal which an acidic low molecular weight compound produces | generates not only by a carboxyl group but by thermal decomposition, or the water | moisture content which penetrate | invades into a resin composition.

  As the terminal blocking agent, it is preferable to use at least one compound selected from an epoxy compound, an oxazoline compound, an oxazine compound, an isocyanate compound, and a lactam compound, and among them, an epoxy compound, an oxazoline compound, and an isocyanate compound are preferable.

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

  As glycidyl ether compounds, butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol di Glycidyl ether, polypropylene glycol diglycidyl ether, neopentylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglyci Bisphenol A diester obtained by condensation reaction of bisphenols such as ether, other 2,2-bis- (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone and the like with epichlorohydrin Examples thereof include glycidyl ether type epoxy resins, bisphenol F diglycidyl ether type epoxy resins, and bisphenol S diglycidyl ether type epoxy resins. Of these, bisphenol A diglycidyl ether type epoxy resin and polyacrylate-polyglycidyl acrylate copolymer are preferable.

  As the glycidyl ester compound, benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, oleic acid glycidyl ester, linol Acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, methyl terephthalic acid glycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthal Acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester , Adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedioic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, etc. . Of these, glycidyl benzoate and glycidyl versatate are preferred.

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

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

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

  As other epoxy compounds, epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and the like can be used.

As the oxazoline compound, 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propyloxy-2-oxazoline, 2-butoxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-octyloxy 2-oxazoline, 2-decyloxy-2-oxazoline, 2-dodecyloxy-2-oxazoline, 2-stearyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2- methallyl-2-oxazoline, 2-Kurochiruoki sheet 2 - oxazoline, 2-phenoxy-2-oxazoline, 2-benzyloxy-2-oxazoline, 2-cresyloxy-2-oxazoline, 2-o-ethylphenoxy -2 -Oxazoline, 2- o-propylphenoxy-2-oxazoline, 2-o-phenylphenoxy-2-oxazoline, 2-m-ethylphenoxy-2-oxazoline, 2-m-propylphenoxy-2-oxazoline, 2-p-phenylphenoxy-2 -Oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-nonyl-2-oxazoline 2-decyl-2-oxazoline, 2-tridecyl-2-oxazoline, 2-myristyl-2-oxazoline, 2-oleyl-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyl-2-oxazoline, 2 -Methallyl-2-oxazoline, 2-crotyl-2-oxazo 2-phenyl-2-oxazoline, 2-benzyl-2-oxazoline, 2-o-ethylphenyl-2-oxazoline, 2-o-propylphenyl-2-oxazoline, 2-o-phenylphenyl-2-oxazoline 2-m-ethylphenyl-2-oxazoline, 2-m-propylphenyl-2-oxazoline, 2-p-phenylphenyl-2-oxazoline 2-p-ethylphenyl-2-oxazoline, 2-p-propylphenyl -2-oxazoline, 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2′-bis (4,4′-dimethyl-2-oxazoline) ), 2,2′-bis (4-ethyl-2-oxazoline), 2,2′-bis (4,4′-diethyl-2-oxazoline), 2,2′-bis (4- Propyl-2-oxazoline), 2,2′-bis (4-butyl-2-oxazoline), 2,2′-bis (4-hexyl-2-oxazoline), 2,2′-bis (4-phenyl-) 2-oxazoline), 2,2′-bis (4-cyclohexyl-2-oxazoline), 2,2′-bis (4-benzyl-2-oxazoline), 2,2′-p-phenylenebis (2-oxazoline) ), 2,2′-m-phenylenebis (2-oxazoline), 2,2′-o-phenylenebis (2-oxazoline), 2,2′-p-phenylenebis (4-methyl-2-oxazoline) 2,2′-p-phenylenebis (4,4′-methyl-2-oxazoline), 2,2′-m-phenylenebis (4,4′-methyl-2-oxazoline), 2,2′-ethylene Bis (2-oxazoline), 2,2'-te Ramethylene bis (2-oxazoline), 2,2′-hexamethylene bis (2-oxazoline), 2,2′-octamethylene bis (2-oxazoline), 2,2′-decamethylene bis (2-oxazoline), 2 , 2′-ethylenebis (4-methyl-2-oxazoline), 2,2′-tetramethylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-9,9′-diphenoxyethane Bis (2-oxazoline), 2,2′-cyclohexylenebis (2-oxazoline), 2,2′-diphenylenebis (4-methyl-2-oxazoline) and the like can be mentioned.

Furthermore, the polyoxazoline compound etc. which contain the said compound as a monomer unit are mentioned.
As the oxazine compound, 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-ethoxy-5,6-dihydro-4H-1,3-oxazine, 2-propyloxy-5,6-dihydro -4H-1,3-oxazine 2-butoxy-5,6-dihydro-4H-1,3-oxazine, 2-pentyloxy-5,6-dihydro-4H-1,3-oxazine, 2-hexyloxy- 5,6-dihydro-4H-1,3-oxazine, 2-heptyloxy-5,6-dihydro-4H-1,3-oxazine, 2-octyloxy-5,6-dihydro-4H-1,3- Oxazine, 2-nonyloxy-5,6-dihydro-4H-1,3-oxazine, 2-decyloxy-5,6-dihydro-4H-1,3-oxazine, 2-cyclopentyloxy- , 6-dihydro-4H-1,3-oxazine, 2-cyclohexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-allyloxy-5,6-dihydro-4H-1,3-oxazine, Examples include 2-methallyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy-5,6-dihydro-4H-1,3-oxazine, and the like.

2,2'-bis (5,6-Jihido b -4 H-1,3-oxazine), 2,2'-methylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2 '-Ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-propylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-butylenebis ( 5,6-dihydro-4H-1,3-oxazine), 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylenebis (5 , 6-dihydro-4H-1,3-oxazine), 2,2′-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-naphthylene (5,6- Dihydro-4H-1,3-oxazine), 2,2′-P, P′-diphenylenebi (5,6-dihydro-4H-1,3-oxazine), and the like. Furthermore, the polyoxazine compound etc. which contain the above-mentioned compound as a monomer unit are mentioned.

  Among the oxazoline compounds and oxazine compounds, 2,2'-m-phenylenebis (2-oxazoline) and 2,2'-p-phenylenebis (2-oxazoline) are preferably selected.

  As the isocyanate compound, aromatic, aliphatic, and alicyclic isocyanate compounds and mixtures thereof can be used.

  Examples of the monoisocyanate compound include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.

  As the diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate) mixture, hexamethylene diisocyanate, cyclohexane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane -4,4'-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylpheny 1,4-diisocyanate, and the like.

  Of these isocyanate compounds, aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate and phenyl isocyanate are preferred.

  As a lactam compound, 1,1-carbonylbiscaprolactam, N, N′-terephthaloylbis-ε-caprolactam, N, N′-isophthaloylbis-ε-caprolactam, N, N′-adipoylbis-ε-caprolactam Etc. are preferably used.

As the terminal blocking agent, one or more compounds can be appropriately selected and used. The composition of the present invention may be sealed with a carboxyl group terminal or an acidic low molecular compound depending on the use used as a molded product. Specifically, the carboxyl group terminal or acidic low molecular compound is sealed. From the viewpoint of hydrolysis resistance, the acid value of the composition is preferably 20 equivalents / 10 ⁶ g or less, more preferably 10 equivalents / 10 ⁶ g or less, and 5 equivalents / 10 ⁶ g or less. It is particularly preferred. The acid value of the composition can be determined by dissolving the resin composition in a suitable solvent and titrating with an alkaline solution having a known concentration.

  The content of the terminal blocking agent is preferably 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, per 100 parts by weight of polylactic acid.

  When using terminal blocker in this invention, you may use the reaction catalyst of terminal blocker. The end capping agent reaction catalyst is a compound that has the effect of accelerating the reaction between the end capping agent and the polymer end, or the carboxyl group of an acidic low molecular weight compound, and has the ability to promote the reaction with a small amount of addition. Is preferred. Examples of such compounds include alkali metal compounds, alkaline earth metal compounds, tertiary amines, imidazole compounds, quaternary ammonium salts, phosphine compounds, phosphonium compounds, phosphate esters, organic acids, Lewis acids, and the like. .

  These can be used alone or in combination of two or more. It is preferable to use an alkali metal compound, an alkaline earth metal compound, or a phosphate ester, and among them, an alkali metal salt or an alkaline earth metal acid salt is preferable. Particularly preferred are sodium stearate, potassium stearate, calcium stearate, magnesium stearate, sodium benzoate, sodium acetate, potassium acetate, calcium acetate and magnesium acetate.

  The added amount of the end capping agent reaction catalyst is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, still more preferably 0.01 per 100 parts by weight of the polylactic acid composition. -0.1 parts by weight.

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

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

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

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

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

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

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

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol-bis (2-ethylbutyrate), and fatty acids such as stearamide. Examples thereof include fatty acid esters such as amide and butyl oleate, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.

  As the plasticizer, at least one selected from polyester plasticizers and polyalkylene plasticizers can be preferably used. These components may be used alone or in combination of two or more.

  The content of the plasticizer is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, and still more preferably 0.1 to 10 parts by weight per 100 parts by weight of polylactic acid. In the present invention, each of the crystal nucleating agent and the plasticizer may be used alone, or more preferably used in combination.

  The impact resistance improver used in the present invention can be used to improve the impact resistance of thermoplastic resins, and is not particularly limited. For example, at least one selected from the following impact resistance improvers can be used.

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

  In addition, those having various cross-linking degrees, various micro structures such as those having a cis structure, a trans structure, etc., a core layer and one or more shell layers covering the core layer, and adjacent layers are composed of heterogeneous polymers. A so-called core-shell type multi-layered polymer can also be used.

  Further, the various (co) polymers mentioned in the above specific examples may be any of randomand copolymers, block copolymers, block copolymers and the like, and can be used as the impact resistance improver of the present invention.

  In producing these (co) polymers, it is also possible to copolymerize monomers such as other olefins, dienes, aromatic vinyl compounds, (meth) acrylic acid, (meth) acrylic acid esters and the like. is there.

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

  The impact resistance improver is preferably a multilayer polymer called a so-called core shell, which is composed of a core layer and one or more shell layers covering the core layer, and the adjacent layer is composed of different polymers. It is more preferred that the polymer is a multilayer structure polymer containing methyl acrylate units in the shell layer.

  Such a multilayer structure polymer preferably contains a (meth) acryl unit, or a unit having an acid anhydride group and / or a glycidyl group. As a suitable example of the (meth) acryl unit, methacrylic acid Examples thereof include a methyl unit, an ethyl acrylate unit, and a methyl acrylate unit. Preferred examples of the unit having an acid anhydride group or a glycidyl group include a maleic anhydride unit and a glycidyl methacrylate unit.

  In particular, the shell layer contains at least one selected from (meth) acrylmethyl units, maleic anhydride units and glycidyl methacrylate groups, and selected from butyl acrylate units, ethylhexyl acrylate units, styrene units and butadiene units. A multilayer structure containing at least one of the above in the core layer can be preferably used. The glass transition temperature of the impact modifier is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.

  The impact resistance improver is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, and still more preferably 10 to 20 parts by weight with respect to 100 parts by weight of polylactic acid.

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

  A composition containing these additives can be prepared by mixing the respective components. For the mixing, a tumbler, a V-type blender, a super mixer, a nauter mixer, a Banbury mixer, a kneading roll, a monoaxial or biaxial extruder can be used. The resulting composition can be molded as it is or after being once pelletized with a melt extruder.

  The shape of the pellet preferably has a shape suitable for molding the pellet by various molding methods. Specifically, the pellet length is preferably 1 to 7 mm, the major axis is 3 to 5 mm, and the minor axis is 1 to 4 mm. Further, it is preferable that the shape does not vary.

  The composition of the present invention can be processed into a molded product by a method such as injection molding or extrusion molding. The mold temperature is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and further preferably 70 ° C. or higher from the viewpoint of increasing the crystallization of the molded product and the molding cycle during injection molding. However, in order to prevent deformation of the molded product, the mold temperature is preferably 140 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.

  Molded articles comprising the composition of the present invention include injection molded articles, extruded molded articles, vacuum, compressed air molded articles, blow molded articles, etc., and films, sheets, sheet nonwoven fabrics, fibers, cloths, and composites with other materials. , Agricultural materials, fishery materials, civil engineering. Building materials, stationery, medical supplies or other molded articles can be obtained by a conventionally known method.

  In addition, these molded products can be used for various applications such as various housings, electric / electronic parts such as gears and gears, building members, civil engineering members, agricultural materials, automobile parts (interior parts, exterior parts, etc.), and daily parts.

  Specifically, notebook PC housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, CDs, DVDs, PDs, FDDs Recording medium drive housing and internal parts such as copier housing and internal parts, facsimile and other housing and internal parts, parabolic antennas, etc. Mention electronic components.

  In addition, VTR housing and internal parts, TV housing and internal parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs (registered trademark), compact discs and other audio equipment parts, lighting parts And household / office equipment parts represented by refrigerator parts, air conditioner parts, typewriter parts, word processor parts and the like.

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

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

1. Measuring method (1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of polymer:
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were converted to standard polystyrene by gel permeation chromatography (GPC).
GPC measurement equipment
Detector: Differential refractometer RID-6A manufactured by Shimadzu Corporation
Column: Tosoh Corporation TSKgelG3000HXL, TSKgelG4000HXL, TSKgelG5000HXL and TSKguardc ol mnHXL-L connected in series, or Tosoh Corporation TSKgelG2000HXL, TSKgelG3000HXL and TSKgel GXLHXL did. Chloroform was used as an eluent, flowed at a temperature of 40 ° C. and a flow rate of 1.0 ml / min, and 10 μl of a sample having a concentration of 1 mg / ml (chloroform) was injected and measured.

(2) Hue:
The color b value was measured with an SD-5000 color difference meter manufactured by Nippon Denshoku Industries Co., Ltd. using the polylactic acid-containing composition as a chip. A larger color b value indicates a worse hue.

(3) Measurement of crystal melting point and melting enthalpy:
It measured using the Shimadzu Corporation DSC-60 differential scanning calorimeter DSC.
A 10 mg sample was heated from room temperature to 250 ° C. under a nitrogen atmosphere at a rate of temperature increase of 20 ° C./min. The crystal melting temperature (Tm) and the heat of crystal melting (ΔHmh) of the complex phase crystal were determined.

(4) Hydrolysis stability:
The sample (3 mm square pellet) is represented by the retention rate of molecular weight when held at 120 ° C. in an atmosphere of 100% RH for 10 hours. If the parameter is 80% or more, it is judged that the molded product made of the composition of the present invention can be used as a guideline for maintaining various physical properties under wet heat conditions.
The hydrolysis resistance is more preferably 85% to 99%, more preferably 9%.
0% to 98%.

(5) Carboxy end group concentration:
The sample was dissolved in purified chloroform / ethanol (1: 1), dissolved in a nitrogen stream, and used as a BTB indicator, and titrated with an ethanol solution of 0.05 N potassium hydroxide.

(6) Light transmittance of the sheet:
Measurements were performed according to ASTM D1003.

(7) Number of fish eyes in the sheet:
The film was observed under polarized light for the number of fish eyes in a 100 mm square sheet that had been randomly extracted from the sample and cut, and those having foreign particles in the polarized light were measured as fish eyes.

(8) Multifilament strength and elongation:
Measurement was performed with a “Tensilon” tensile tester manufactured by Orientec Co., Ltd. under the conditions of a sample length of 25 cm and a tensile speed of 30 cm / min.

[Example 1]
Polymerization was carried out using a vertical stirring tank (40 L) equipped with a vacuum pipe, a nitrogen gas pipe, a catalyst, a lactide solution addition pipe, an alcohol initiator addition pipe, and a vertical raking blade.
After nitrogen substitution in the system, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo as a phosphite compound [D, f] [1, 3, 2] dioxaphosphine (hereinafter abbreviated as “PES1”) 0.3 kg, optical purity 99.5% or more, acidic impurity content 0.065 wt% 60 kg of L-lactide and 0.2 kg of stearyl alcohol were charged, and the temperature was raised to 150 ° C. in an atmosphere with a nitrogen pressure of 106.4 kPa and an oxygen concentration of 10 ppm.
When the contents are melted, 3.6 g of tin octylate is added, stirring is started, the internal temperature is further increased to 190 ° C., and the reaction is continued for 1 hour while maintaining the internal temperature from 185 ° C. to 190 ° C. The stirring was stopped, the internal pressure was increased to 0.2 MPa with nitrogen pressure, and the obtained polymer was removed with a biaxial stirring devolatilizer under high vacuum of 133.32 Pa (1 mmHg), and then a chip cutter. A polylactic acid-containing composition having an extruded weight average molecular weight (Mw) of 175,000, a molecular weight dispersion (Mw / Mn) of 1.8, and a lactide content of 0.01% by weight was obtained. The chip color b value of this polylactic acid-containing composition was 3.3.

[Example 2]
In Example 1, the same operation was performed except that L-lactide had a purity of 99.5% or more, an acidic impurity content of 0.15% by weight, stearyl alcohol 0.1 kg, and the reaction time was 3 hours. It was. The resulting polylactic acid-containing composition had a weight average molecular weight (Mw) of 172,000, a molecular weight dispersion (Mw / Mn) of 1.8, a lactide content of 0.015% by weight, and a chip color b value of 4. .7.

[Comparative Example 1]
The same operation was performed except that PES1 was not used in Example 1. A polymerization reaction of 5 hours was required to reach the highest molecular weight.
The resulting polylactic acid-containing composition had a weight average molecular weight (Mw) of 67,000, a molecular weight dispersion (Mw / Mn) of 1.7, a lactide content of 0.009% by weight, and a chip color b value of 24. Met.

[Comparative Example 2]
The same operation was performed except that PES1 was not used in Example 2. A 6 hour polymerization reaction was required to reach the highest molecular weight.
The resulting polylactic acid-containing composition has a weight average molecular weight (Mw) of 121,000, a molecular weight dispersion (Mw / Mn) of 1.5, a lactide content of 0.011% by weight, and a chip color b value. Was 19.

[Example 3]
In Example 1, the same operation was performed except that L-lactide was changed to D-lactide having an optical purity of 99.5% or more and an acid impurity content of 0.065% by weight. The resulting polylactic acid-containing composition had a weight average molecular weight (Mw) of 165,000, a molecular weight dispersion (Mw / Mn) of 1.8, a lactide content of 0.013% by weight, and a chip color b value of 4. .5.

[Example 4]
In Example 1, except that L-lactide was changed to D-lactide having an optical purity of 99.5% or more and an acidic impurity content of 0.15 wt%, stearyl alcohol 0.1 kg, and reaction time 3 hours. Performed the same operation. The resulting polylactic acid-containing composition had a weight average molecular weight (Mw) of 15.9 million, a molecular weight dispersion (Mw / Mn) of 1.8, a lactide content of 0.017% by weight, and a chip color b value of 5 .4.

[Comparative Example 3]
In Example 3, the same operation was performed except that PES1 was not used. A 4 hour polymerization reaction was required to reach the highest molecular weight.
The resulting polylactic acid-containing composition had a weight average molecular weight (Mw) of 110,000, a molecular weight dispersion (Mw / Mn) of 1.7, a lactide content of 0.012% by weight, and a chip color b value of 18.

[Comparative Example 4]
In Example 4, the same operation was performed except that PES1 was not used. A 7 hour polymerization reaction was required to reach the highest molecular weight.
The resulting polylactic acid-containing composition had a weight average molecular weight (Mw) of 73,000, a molecular weight dispersion (Mw / Mn) of 1.5, a lactide content of 0.014% by weight, and a chip color b value of 17. It was.
From the above results, it is apparent that according to the production method of the present invention, not only a high molecular weight polylactic acid-containing composition can be obtained in a short time but also a polylactic acid-containing composition having a good hue can be obtained.
Furthermore, it is clear that the production method of the present invention can efficiently produce polylactic acid having a high molecular weight and a good hue even when the content of acidic impurities in lactide is high and the acid value is high.

[Examples 5 to 8]
In Example 1, the same operation was performed except that the addition amount of PES1 was changed as shown in Table 1. The results are shown in Table 1.

[Example 9]
In Example 1, L-lactide having a purity of 99.5% or more, an acidic impurity content of 0.01% by weight, stearyl alcohol of 0.3 kg, a maximum molecular weight of 30 minutes, and a reaction time of 1 hour The same operation was performed except that. The resulting polylactic acid-containing composition had a weight average molecular weight (Mw) of 178,000, a molecular weight dispersion (Mw / Mn) of 1.8, a lactide content of 0.013% by weight, and a chip color b value of 4. .6.

[Reference Example 1]
In Example 9, the same operation was performed except that PES1 was not used. A polymerization reaction of 1 hour was required to reach the highest molecular weight.
The resulting polylactic acid-containing composition had a weight average molecular weight (Mw) of 173,000, a molecular weight dispersion (Mw / Mn) of 1.7, a lactide content of 0.013% by weight, and a chip color b value of 9.8. It was .

[Example 10]
And a port re L- acid pellets 100 parts by weight obtained in the procedure of Example 1 was dried for 5 hours at 110 ° C., 30 mm? Vented twin-screw extruder first of (manufactured by Kobe Steel KTX-30, Ltd.) the supply port, Nisshinbo Industries, Ltd., "Karubojirai bets (registered trademark)" LA-1 were supplied from a 0.01 part by weight second supply port, a cylinder temperature of 200 ° C., the residence time of 3 minutes, 1.33 kPa The mixture was kneaded while deaerated at a vacuum of (10 mmHg), extruded into cold water from a nozzle, and pelletized.
The color b value of the chip was 9.4, the carboxyl end group concentration was 0.1 equivalent / ton, and the heat and humidity resistance was 95%.
This pellet was dried at 110 ° C. for 5 hours, and measured using an injection molding machine (SG150U model manufactured by Sumitomo Heavy Industries, Ltd.) with a cylinder temperature of 210 ° C. and a mold temperature of 100 ° C., and an ASTM measurement with a thickness of 3 mm. A molded piece was prepared. The hue of this molded product was good.

[Example 11]
100 parts by weight of the polylactic acid-containing composition obtained by the operation of Example 1 and 1 part by weight of talc (P-3 manufactured by Nippon Talc Co., Ltd.) per 100 parts by weight of polylactic acid were uniformly mixed using a tumbler. than the first supply port and dried 5 hours at 110 ° C., Nisshinbo Industries, Ltd., the "Karubojirai bets (registered trademark)" LA-1 on the same basis as above, 1 part by weight is supplied from the second supply port Using a twin screw extruder with a 0.30 mmφ vent (KTX-30 manufactured by Kobe Steel, Ltd.), kneading while degassing at a cylinder temperature of 200 ° C., a residence time of 3 minutes, and a vacuum of 1.33 kPa (10 mmHg), from a nozzle Extruded into cold water and pelletized.
The pellets were dried at 110 ° C. for 5 hours and then used for an ASTM measurement with a thickness of 3 mm using an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 100 ° C. A molded piece was created. This molded product had a good hue.

[Example 12]
Using the polymilk-containing composition obtained by the operation of Example 3, in Example 10, the talc was changed to calcium silicate manufactured by Nacalai Tesque Co., Ltd. A molded piece could be created.

[Example 13]
The pellets obtained by the operation of Example 1 were passed through a 30 mmφ biaxial ruder (cylinder temperature 190 ° C.) and sent to a T die of a molding machine. The sheet was sandwiched or touched on one side with a mirror surface cooling roll and a mirror surface roll, and melt extruded as an unstretched sheet having a thickness of 0.1 mm and a width of 500 mm. The sheet could be molded well. The light transmittance was 94%, and the number of fish eyes visually determined in a 100 mm square sheet cut at random was 5.

[Example 14]
The pellets obtained in Example 1 were spun at a spinning pack temperature of 200 ° C., a hole number of 36, and an oil for fiber mainly composed of fatty acid ester, and spun at a spinning speed of 1000 m / min. The undrawn yarn was drawn 1.45 times at a temperature of 90 ° C., heat-set at 130 ° C. and wound to obtain a multifilament. Both spinning and stretching could be carried out satisfactorily.
The obtained multifilament was a good fiber having a strength of 4.0 cN / dtex and an elongation of 38%.

According to the present invention, a good hue polylactic acid-containing composition, even especially have use as high lactide starting acid value contains more acidic impurities, it is possible to produce a good hue of the polylactic acid efficiently its significance is large. It is possible to produce a good quality molded articles from polylactic acid obtained by the method of manufacturing a present invention.

Claims (12)

In the coexistence of lactide having a content of acidic impurities in the range of 0.01 wt% to 0.3 wt% and a phosphorous acid compound represented by the following general formula (1), tin, aluminum, zinc, calcium, Polylactic acid containing melt ring-opening polymerization using a metal compound containing at least one metal selected from titanium, germanium, manganese, magnesium and rare earth elements as a catalyst under conditions (a) to (c) below A method for producing the composition.
(A) A total of 0.001 to 0.1 mmol of the above metal compound per mole of lactide.
(B) A total of 0.01 to 10 mmol of the above phosphite compound per mole of lactide.
(C) The molar ratio of the total amount of the phosphorous acid compound and the total amount of the metal compound is in the range of 0.01 to 1000.

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

(Wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents 2 to 8 carbon atoms. An alkylene group of formula (I-2)

(In the formula, R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond to the oxygen atom side.) Y, Z Is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or 1 to 8 carbon atoms. Represents an alkyl group. ] The production method according to claim 1, comprising a divalent tin compound as the metal compound and a phosphite ester represented by the following formula (2) as the phosphite compound.

  The production method according to claim 1 or 2, wherein the metal compound is selected from the group consisting of tin (II) octylate, tin methoxide (II), tin alkoxide (II), and tin isopropoxide (II).   The manufacturing method in any one of Claim 1 to 3 whose lactide is L-lactide, D-lactide, or meso lactide.   The production method according to claim 1, wherein the acidic impurity is selected from lactic acid, a lactic acid oligomer, and pyruvic acid.   A polylactic acid-containing composition produced by the method according to claim 1. The polylactic acid-containing composition according to claim 6, which satisfies the following requirements.
(D) The color b value measured as a chip is less than 15. Melt molded article made of polylactic acid-containing composition according to any one of claims 6 or al 7.   The melt-formed product according to claim 8, wherein the melt-formed product has a shape selected from a film, a sheet, a fiber, a fiber structure, and an injection-molded product. The polylactic acid-containing composition according to claim 6 , further comprising a thermoplastic resin, a stabilizer, a crystallization accelerator, a filler, a release agent, an antistatic agent, a terminal end-capping agent, a plasticizer, and impact resistance. A polylactic acid-containing composition containing at least one selected from the group consisting of stabilizers.   A melt-molded article comprising the polylactic acid-containing composition according to claim 10. The melt-formed product according to claim 11, wherein the melt-formed product has a shape selected from a film, a sheet, a fiber, a fiber structure, and an injection- molded product.