JP2008120878A - Polylactide granule and composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide polylactide granules in which additives can uniformly be dispersed and which is suitably used for master powder, and to provide a composition excellent in the dispersibility of additives containing the same. <P>SOLUTION: The granules having an average granule diameter of 0.1 to 4 mm and comprising polylactide having a crystallization enthalpy of 5 to 20 J/g by a differential scanning calorimeter. The composition contains the same. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polylactide powder suitable for producing a masterbatch. The present invention also provides a composition (X) in which the polylactide particles and additives such as a deactivator and a higher aliphatic carboxylic acid derivative are uniformly dispersed, and the metering stability when blended with other resins is good. About. The present invention further relates to a composition (Y) containing the composition (X) and a thermoplastic resin. Moreover, this invention relates to the method of using a composition (Y) for manufacture of a polylactide stereocomplex.

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, polylactide and the like are well known.
Polylactide is a polymer material that has high biological safety and is friendly to the environment because it uses lactide obtained from a raw material derived from a living body. Polylactide is processed as a so-called general-purpose polymer into uniaxially, biaxially stretched films, fibers, injection-molded products, etc., and is considered for use in medical applications such as surgical sutures, sustained-release capsules, and reinforcing materials for fractures. ing.
However, D- or L-polylactide is highly transparent and tough, but since the melting point is 170 ° C., the heat resistance may not be sufficient for use as a general-purpose polymer.

On the other hand, a polylactide stereocomplex obtained by mixing D- and L-polylactide in a solution or in a molten state has biodegradability and biocompatibility, has higher heat resistance and stability than polylactide, and has a more severe environment. It is expected to be used in.
As for the production of polylactide, a direct melt polymerization method of lactic acid, a solid phase polymerization method, a melt ring-opening polymerization method of lactides and the like are well known. Among them, the method of melt ring-opening polymerization of lactide in the presence of a metal catalyst has a simple manufacturing process, has a high possibility of being able to suppress the manufacturing cost with high production efficiency, and the color tone of the resulting polylactide is good, and contains impurities. It is considered as a promising method for producing polylactide having a relatively small amount and excellent stability.

However, it is well known that polylactide subjected to melt ring-opening polymerization cannot be used as it is because if the metal catalyst remains in the resin, it causes decomposition and deterioration of the resin during molding. In order to remove such adverse effects of the metal catalyst, the use of various catalyst deactivators has been proposed, and the effect is sufficiently satisfactory, but regarding the method of adding such a deactivator into the resin, No industrially satisfactory method has yet been proposed.
That is, it is generally proposed that such a quenching agent is directly added to the polymerization tank at the end of the polymerization. In this method, however, the polymerization tank is contaminated with the quenching agent and further corroded. It is difficult to say that this method can be used industrially.

Alternatively, a method of adding and kneading a deactivator using an extruder in a melted state after polymerization or once solidified polylactide has also been proposed, but the amount of deactivator to be added is extremely small compared to the amount of resin. There are few, stable and quantitative additions that are difficult. In addition, the possibility of equipment corrosion has not yet been fully resolved.
Furthermore, polylactide and polylactide stereocomplex are rarely used alone, and in addition to a deactivator, a heat stabilizer, an antioxidant, a weathering (light) stabilizer, a release agent, and a lubricant based on the desired purpose. , Antistatic agents, plasticizers, pigments, dyes, fillers, reinforcing agents, flame retardants and the like may be used. Of these, quenchers, heat stabilizers such as sterically hindered phenol compounds, and mold release agents represented by higher aliphatic carboxylic acids are often used.

For example, the heat stabilizer is usually 1 × 10 ^{−4 to} 0.1 to 100 parts by weight of polylactide and polylactide stereocomplex so that the additive does not impair the original excellent physical properties of polylactide and polylactide stereocomplex. Often used in parts by weight and in small quantities. In addition, since a solid or liquid and an additive having a different state are often used in combination, selection of an additive supply means, quantitative supply, and uniform melt mixing are often difficult. Furthermore, even if the additives are of the same type, technical problems that must be added in various concentrations for each purpose are often seen.

In order to solve such a problem, a masterbatch method containing an additive in a concentrated manner has been considered. That is, a polylactide pellet or granular composition containing an additive in a high concentration, that is, a master batch is prepared in advance, and the composition is supplied in a fixed quantity by melting and kneading the composition with raw polylactide in an extruder. Attempts have been devised to solve the problems of stability, uniform dispersibility, and the problem of changing the additive concentration for each brand.
The method of extruding a pelletized masterbatch with a thermoplastic resin is called “master pellet method”, the pelletized composition is “master pellet”, and the method of extruding a master batch in powder form is The “powder method” and the granular composition may be abbreviated as “master powder”.
In the master pellet method, it is necessary to melt and knead and pelletize the additive and the raw material resin once in advance. For this reason, since the additive experiences a temperature of 180 to 250 ° C. or higher, which is the melt molding temperature of polylactide, prior to mixing with the thermoplastic resin, the resin is melted at least twice. The possibility of a part of the heat deterioration and denaturation is not negligible.

On the other hand, the master powder method, in which each additive is mixed with the polylactide powder using an appropriate mixing device, and a powder composition containing various additives at a high concentration is used, has such disadvantages. It is considered a preferred method without
However, the master powder containing the additive in a high concentration is deteriorated in fluidity, and when it is severe, the master powder may be condensed due to the additive and a situation where uniform dispersion of the agent cannot be realized may occur.

  An object of the present invention is to provide a polylactide granule suitable for use as a master powder, in which the additive can be uniformly dispersed. Another object of the present invention is to provide a powder composition (X) useful as a master powder in which additives are uniformly dispersed in the powder and are excellent in metering stability when kneaded with an extruder. There is to do. Furthermore, the objective of this invention is providing the composition (Y) containing this composition (X) and a thermoplastic resin. Another object of the present invention is to provide a method for using the composition (Y) in the production of a polylactide stereocomplex.

  This invention consists of a polylactide whose crystallization enthalpy by a differential scanning calorimeter is 5-20 J / g, and whose average particle diameter is 0.1-4 mm.

  The present invention is also characterized in that lactide is heat-treated at 60 to 140 ° C. for 0.5 to 10 hours after melt ring-opening polymerization in the presence of an initiator and a metal catalyst, before or after pulverization. It is a manufacturing method of a granular material.

Moreover, the present invention comprises (i) a polylactide having a crystallization enthalpy of 5 to 20 J / g measured by a differential scanning calorimeter, and 100 parts by weight of a granular material having an average particle size of 0.1 to 5 mm.
(ii) 0.01-5 parts by weight of phosphoric acid, metaphosphoric acid, phosphorous acid, pyrophosphoric acid, imine compound, phosphorus oxoacid, phosphorus oxoacid ester and the following formula (1)
R ⁵ -P (═O) _q (OH) _s (OR ⁴ ) _2-s (1)
(In formula (1), q is 0 or 1, s is 1 or 2, and R ⁴ and R ⁵ each independently represents a hydrocarbon group optionally having a substituent having 1 to 20 carbon atoms.)
A composition (X) containing at least one deactivator (component A) selected from the group consisting of organic phosphorus oxoacid compounds represented by the formula:

Furthermore, the present invention comprises (i) a polylactide having a crystallization enthalpy of 5 to 20 J / g by a differential scanning calorimeter, and 100 parts by weight of a granular material having an average particle size of 0.1 to 5 mm;
(ii) 0.01-5 parts by weight of phosphoric acid, metaphosphoric acid, imine compound, phosphorus oxo acid, phosphorus oxo acid ester and the following formula (1)
R ⁵ -P (═O) _q (OH) _s (OR ⁴ ) _2-s (1)
(In formula (1), q is 0 or 1, s is 1 or 2, and R ⁴ and R ⁵ each independently represents a hydrocarbon group optionally having a substituent having 1 to 20 carbon atoms.)
At least one deactivator (component A) selected from the group consisting of organic phosphorus oxoacid compounds represented by:
The composition (X) is produced by mixing in an atmosphere having a relative humidity of 0 to 60% and a cleanliness class of 100,000 or less.

  Moreover, this invention is a composition (Y) containing this composition (X) and a thermoplastic resin. Moreover, this invention is a manufacturing method of the composition (Y) characterized by melt-kneading this composition (X) and a thermoplastic resin.

  Furthermore, this invention includes the method of using this composition (Y) for manufacture of a polylactide stereocomplex composition, and the polylactide stereocomplex composition obtained by this method.

  The granular material of the present invention can uniformly disperse the additive. Therefore, it is excellent as a raw material for master powder. The composition (X) of the present invention can be suitably used as a master powder because the additives are uniformly dispersed. Moreover, it is excellent in measurement stability when kneading with an extruder. In the composition (Y) of the present invention, the deactivator is uniformly dispersed, the catalyst is sufficiently deactivated, and the thermal stability is excellent. Since the polylactide stereocomplex of the present invention is formed from the composition (Y), it has a high melting point and excellent thermal stability.

<Powder>
The granular material of this invention consists of a polylactide whose crystallization enthalpy by a differential scanning calorimeter is 5-20 J / g, and is an average particle diameter of 0.1-4 mm.
(Polylactide)
Polylactide mainly consists of L-lactic acid units or D-lactic acid units represented by the following formula.

Examples of polylactide include poly-L-lactide, poly-D-lactide, and poly-D / L-lactide.
The poly-L-lactide is preferably composed of 90 mol% or more, more preferably 95 mol% or more, and still more preferably 98 mol% or more of L-lactic acid units. Examples of other units include D-lactic acid units and units other than lactic acid. The D-lactic acid unit and the units other than lactic acid are preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 2 mol% or less.
The poly-D-lactide is preferably composed of 90 mol% or more, more preferably 95 mol% or more, and still more preferably 98 mol% or more of D-lactic acid units. Examples of other units include L-lactic acid units and units other than lactic acid. The L-lactic acid unit and the copolymer component unit other than lactic acid are preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 2 mol% or less.
Units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like having functional groups capable of forming two or more ester bonds as copolymerization component units in poly-L-lactide and poly-D-lactide Examples are units derived from various polyesters, various polyethers, various polycarbonates and the like comprising various constituent components.

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

  The weight average molecular weight (Mw) of the polylactide is preferably 100,000 to 300,000, more preferably 100,000 to 250,000, and still more preferably 110,000 to 200,000. In general, the Mw of polylactide used for molding applications is 100,000 or more. If the molecular weight is too high, the melt viscosity becomes high and the molding process becomes difficult. The lactide content of the polylactide is preferably 1000 ppm by weight or less, more preferably 800 ppm by weight or less, and even more preferably 500 ppm by weight or less. Mw / Mn of polylactide is preferably 1.4 to 2.4, more preferably 1.5 to 2.2, and still more preferably 1.6 to 2.1.

(Crystallization enthalpy)
Polylactide has a crystallization enthalpy by differential scanning calorimetry of 5 to 20 J / g, preferably 7 to 17 J / g. When the crystallization enthalpy is within this range, the fluidity of the composition (X) containing the powder and the additive can be suitably maintained, and the powdery composition in which the additive is uniformly dispersed Product (X) can be obtained. If the crystallization enthalpy is too small, the granular material may be modified by the additive to increase the tackiness, and a non-uniform composition (X) may be obtained. When the crystallization enthalpy is too large, coloring of the composition (Y) obtained when the composition (X) is melt-kneaded with a thermoplastic resin by, for example, a side feed method may become remarkable. In order to adjust the crystallization enthalpy to 5 to 20 J / g, the polylactide before or after pulverization may be heat-treated at 60 to 140 ° C. for 0.5 to 10 hours. For example, the heat treatment may be performed at 100 ° C. for 0.5 to 8 hours.

(Average particle size)
The average particle diameter of the granular material is 0.1 to 4 mm, preferably 0.20 to 3 mm. When the composition (X) containing powder and additives is melt-kneaded with a thermoplastic resin in an extruder, if the average particle size of the powder is less than 0.1 mm, a slip phenomenon occurs in the screw of the extruder. As a result, the biting property is deteriorated and the extrusion efficiency is lowered. Moreover, when larger than 5 mm, the dispersibility of the additive in composition (X) may be inferior. Granules with an average particle size of 0.1 to 4 mm can be obtained by combining polylactide with a normal pulverizer such as jaw crusher, hammer mill, ball mill, edge runner, integrator, pin mill and sieve classification. You can get a body. The average particle size is determined by screening powder particles using ASTM sieves 7, 14, 25, 35, 45, 60, 100, 140, and 200, and determining the cumulative particle size distribution according to the weight standard. % Is the particle size.

(Specific surface area (SSA))
The specific surface area (SSA) of the granular material is preferably 0.01 to ⁵ m ² / g.

<Production method of powder>
The granular material is produced by heat-treating lactide at 60 to 140 ° C. for 0.5 to 10 hours after melt ring-opening polymerization in the presence of an initiator and a metal catalyst, and before or after pulverization. Can do.

(Lactide)
Lactide is at least one selected from the group consisting of L-lactide, D-lactide, D / L-lactide, and meso-lactide. The optical purity of lactide is preferably 90 to 100%, more preferably 95 to 100%. D / L-lactide has a D / L ratio of 0/100 to 100/0.
That is, L-lactide preferably contains 90 mol% or more, more preferably 95 mol% or more, and further preferably 98 mol% or more of L-lactide. Examples of other components include components other than D-lactide and lactide. Components other than D-lactide and lactide are preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 2 mol% or less.
The D-lactide preferably contains 90 mol% or more, more preferably 95 mol% or more, and further preferably 98 mol% or more of D-lactide. Examples of other components include components other than L-lactide and lactide. Components other than L-lactide and lactide are preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 2 mol% or less.
As components other than lactide, units derived from dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid, lactone, etc. having functional groups capable of forming two or more ester bonds, and various polyesters, various polyethers composed of these various components, Examples are derived from various polycarbonates and the like.

Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples of polyhydric alcohols include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. Or aromatic polyhydric alcohol etc., such as what added ethylene oxide to bisphenol, etc. are mentioned. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid. Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.
Such lactide usually contains moisture and an acid component as impurities, but the acid value of lactide is preferably low. The acid value of lactide is preferably 5 to 20 eq / ton, more preferably 5 to 9 eq / ton, and further preferably 3 to 8 eq / ton. Water is undesirable because it causes ring-opening degradation of lactide. The water content in lactide is preferably 0.5% by weight or less, more preferably 0.1% by weight or less.

(Initiator)
The initiator is preferably at least one selected from the group consisting of alcohols represented by the following formula (2), formula (3) and formula (4).
R ¹ —OH (2)
In formula (2), R ¹ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms. As the monohydric alcohol represented by the formula (2), methanol, ethanol, n-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, pentyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, octyl alcohol, nonyl alcohol, 2 -Ethylhexyl alcohol, n-decyl alcohol, n-dodecyl alcohol, hexadecyl alcohol, lauryl alcohol, ethyl lactate, hexyl lactate and the like are exemplified.
R ^2- (OH) _n (3)
In formula (3), R ² represents an n-valent hydrocarbon group having 2 to 20 carbon atoms, and n represents an integer of 2 to 5.
Examples of the hydrocarbon group include an alkane-diyl group having 2 to 20 carbon atoms, an alkane-triyl group, and an alkane-tetrayl group. Examples of the polyhydric alcohol represented by the formula (3) include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, trimethylolpropane, and pentaerythritol. .
HO— (R ³ —O) _m —H (4)
In formula (4), R ³ represents an alkylene group having 2 to 5 carbon atoms, and m represents an integer of 2 to 100. Examples of the polyalkylene glycol represented by the formula (4) include diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, ethylene oxide adducts of other phenols, and ethylene glycol adducts of bisphenol.

From the viewpoint of reactivity and polylactide physical properties, stearyl alcohol, lauryl alcohol, ethylene glycol, propanediol, butanediol, hexanediol, polyethylene glycol, polypropylene glycol and the like are exemplified as preferable examples.
The amount of the initiator used is preferably 0.008 to 0.04 mol, more preferably 0.009 to 0.035 mol, and still more preferably 0.01 to 0.03 mol per kg of lactide.
As the initiator, those sufficiently dried and reduced are preferably used. The moisture content of the initiator is preferably 100 ppm or less, more preferably 50 ppm, and even more preferably 10 ppm or less.

(Metal catalyst)
As a metal catalyst, fatty acid salts such as alkali metals, alkaline earth metals, rare earths, transition metals, aluminum, germanium, tin, antimony, carbonates, sulfates, phosphates, oxides, hydroxides, halides, Examples include alcoholates.
The metal catalyst is preferably tin, aluminum, zinc, calcium, titanium, germanium, manganese, magnesium, a rare earth element fatty acid salt, carbonate, sulfate, phosphate, oxide, hydroxide, halide, Examples include alcoholates.
For example, as a tin compound, stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, tin myristate, tin octylate, tin stearate, tetraphenyltin, tin methoxide , Tin ethoxide, tin butoxide and the like.
Examples of the aluminum compound include aluminum oxide, aluminum acetylacetonate, aluminum isopropoxide, and an aluminum-imine complex.
Examples of the titanium compound include titanium tetrachloride, ethyl titanate, butyl titanate, glycol titanate, and titanium tetrabutoxide compound.

Further, zinc chloride, zinc oxide, 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 are exemplified.
In view of catalytic activity and few side reactions, a tin-containing catalyst, an aluminum-containing catalyst, and a titanium-containing catalyst are preferable.
In particular, tin-containing compounds such as stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, tin myristate, tin octylate, tin stearate, tetraphenyltin and the like Examples thereof include aluminum-containing compounds such as aluminum acetylacetonate, aluminum butoxide, and aluminum-imine complex.
Of these, an aliphatic alkoxide having 1 to 22 carbon atoms of tin, a fatty acid salt having 2 to 22 carbon atoms and tin chloride are preferable. Accordingly, diethoxytin, dinonyloxytin, tin myristate, tin octylate, tin stearate, tin chloride, aluminum acetylacetonate, aluminum isopropoxide and the like are preferable.

The amount of the catalyst used is preferably 0.42 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol, more preferably 0.8 × 10 ^{−4 to} 42.1 × 10 ⁻⁴ mol, and even more preferably, per kg of lactide. 1.1 × 10 ^{−4 to} 16.8 × 10 ⁻⁴ mol.
Therefore, it is preferable to use 0.002 to 0.04 mol of the initiator and 0.42 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol of the metal catalyst in terms of metal element with respect to 1 kg of lactide.
As the metal catalyst, those sufficiently dried and reduced are preferably used. The moisture content is 100 ppm or less, preferably 50 ppm, more preferably 10 ppm or less.

(Melting ring-opening polymerization)
The melt ring-opening polymerization is preferably performed in an inert gas atmosphere in order to prevent volatilization of the raw material lactide. The internal pressure is preferably 17.33 to 506.6 kPa, more preferably 111.5 to 202.7 kPa. The polymerization temperature is preferably 180 to 230 ° C, more preferably 185 to 220 ° C. When a plurality of polymerization tanks are used, it is preferable that the internal temperature of the polymerization tank on the downstream side is not lower than the internal temperature of the polymerization tank used on the upstream side. The polymerization time is preferably 0.1 to 10 hours, more preferably 0.3 to 8 hours, and further preferably 0.5 to 4 hours. The polymerization is preferably carried out while maintaining the reaction temperature at a relatively low temperature and suppressing side reactions of lactide.

(Pulverization)
A granular material having an average particle size of 0.1 to 4 mm can be obtained by combining polylactide with a normal pulverizer such as a jaw crusher, a hammer mill, a ball mill, an edge runner, an integrator, or a pin mill and sieve classification.

(Heat treatment)
In order to adjust the crystallization enthalpy to 5 to 20 J / g, the polylactide before or after pulverization may be heat-treated at 60 to 140 ° C. for 0.5 to 10 hours. The heat treatment is preferably performed at 80 to 1300 ° C. for 0.2 to 10 hours. For example, the heat treatment may be performed at 100 ° C. for 0.5 to 8 hours.

<Composition (X)>
The composition (X) is 0.01 to 5 parts by weight, preferably 0.02 to 3 parts by weight, more preferably 0.04 to 2 parts by weight of a deactivator (100 parts by weight). A component) is contained.

(A component)
The quenching agent (component A) is phosphoric acid, metaphosphoric acid, phosphorous acid, pyrophosphoric acid, imine compound, phosphoroxo acid, phosphoroxo acid ester and the following formula (1)
R ⁵ -P (═O) _q (OH) _s (OR ⁴ ) _2-s (1)
And at least one selected from the group consisting of organic phosphorus oxoacid compounds represented by:
In formula (1), q is 0 or 1, s is 1 or 2, and R ⁴ and R ⁵ each independently represents a hydrocarbon group which may have a substituent having 1 to 20 carbon atoms. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms. These quenchers may be used alone or in combination.
The content of the deactivator is preferably 0.3 to 20 equivalents, more preferably 0.5 to 10 equivalents per equivalent of the metal element of the metal catalyst.
As a deactivator, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, phenylphosphonic acid, benzylphosphinic acid, dibutyl phosphate, dinonyl phosphate, N′-bis (Salicylidene) ethylenediamine and N, N′-bis (salicylidene) propanediamine are exemplified, and phosphoric acid, phosphorous acid and pyrophosphoric acid are particularly preferable. These deactivators may be used singly or in some cases in combination.

  The imine compound is a phenotetradentate chelate ligand having an imino group in its structure and capable of coordinating with a metal catalyst. Since the imine compound is not a Bronsted acid or a base like conventional catalyst deactivators, it is possible to improve the thermal stability without deteriorating the hydrolysis resistance of polylactide. Such imine compounds include N, N′-bis (salicylidene) ethylenediamine, N, N′-bis (salicylidene) propanediamine, N, N-bis (salicylidene) -cis-cyclohexanediamine, N, N′-bis (salicylidene). ) -Trans-cyclohexanediamine, N, N′-bis (salicylidene) -o-phenylenediamine, N, N′-bis (salicylidene) -m-phenylenediamine, N, N′-bis (salicylidene) -p-phenylene Diamine, N, N′-bis (2-cyanobenzylidene) ethylenediamine, N, N′-bis (2-cyanobenzylidene) propanediamine, N, N′-bis (2-cyanobenzylidene) -cis-cyclohexanediamine, N N′-bis (2-cyanobenzylidene) -trans Rhohexanediamin NN'-bis (2-cyanobenzylidene) -o-phenylenediamine, N, N'-bis (2-cyanobenzylidene) -m-phenylenediamine, N, N'-bis (2-cyanobenzylidene) -p- Examples include phenylenediamine, N-methyliminomethylphenol, N-ethyliminomethylphenol, N-isopropyliminomethylphenol, and Nt-butyliminomethylphenol. Particularly preferred are N, N'-bis (salicylidene) ethylenediamine and N, N'-bis (salicylidene) propanediamine.

  Examples of the phosphorus oxoacid include dihydridooxoline (I) acid, dihydridotetraoxodiphosphorus (II, II) acid, hydridotrioxoline (III) acid, dihydridopentaoxodiphosphoric acid (III), and hydridopentaoxodioxy (II, IV) acid, dodecaoxohexaline (III) III, hydridooctaoxotriphosphate (III, IV, IV) acid, octaoxotriphosphate (IV, III, IV) acid, hydridohexaoxodiline (III, V) ) Low oxidation number phosphorus having an acid number of 5 or less, such as acid, hexaoxodiphosphorus (IV) acid, decaoxotetralin (IV) acid, hendecaoxotetralin (IV) acid, eneoxooxo triphosphoric acid (V, IV, IV) acid Examples include acids.

Also, the formula xH ₂ O. Polyphosphoric acid represented by yP ₂ O ₅ , x / y = 3 orthophosphoric acid, 2> x / y> 1, and referred to as diphosphoric acid, triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid or the like based on the degree of condensation Acids and mixtures thereof, metaphosphoric acid represented by x / y = 1, especially trimetaphosphoric acid, tetrametaphosphoric acid, and linear polyphosphoric acid and cyclic metaphosphoric acid called glassy phosphoric acid or icy phosphoric acid Mixture, ultraphosphoric acid represented by 1> x / y> 0 and having a network structure in which part of the phosphorus pentoxide structure is left, and monovalent, polyhydric alcohols, or polyalkylene glycols of these acids Examples of the partial ester and complete ester. From the catalyst deactivation ability, acids or acidic esters are preferably used.

  Although there is no restriction | limiting in particular regarding alcohol which forms ester of a phosphorus oxo acid, As C1-C22, as the monohydric alcohol, the alcohol represented by Formula (5) which may have a substituent is preferable.

Y-OH (5)
In formula (5), Y represents a hydrocarbon group having 1 to 22 carbon atoms, which may have a substituent. Y is preferably an alkyl group having 1 to 22 carbon atoms. Examples of the monohydric alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, 2-ethylhexyl alcohol, decanol, dodecanol, benzyl alcohol, cyclohexyl alcohol, hexyl alcohol, phenol, hexadecyl alcohol and the like.
Examples of the polyhydric alcohol include polyhydric alcohols and sugar alcohols represented by the formula (6) having 2 to 22 carbon atoms and optionally having a substituent.

X (—OH) _a (6)
In formula (6), X is a C2-C22 hydrocarbon group which may have a substituent, and a represents an integer of 2 to 6. X is preferably an alkane-diyl group, an alkane-triyl group, or an alkane-tetrayl group. Examples of the polyhydric alcohol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, pentaerythritol, trimethylolpropane, polyethylene glycol, polypropylene glycol, myo-inositol, D- , L-inositol, scyllo-inositol and other inositols, cyclitol and the like.

(B component)
The aliphatic carboxylic ester is used as a release agent, and specifically, an ester of an aliphatic carboxylic acid having 10 to 25 carbon atoms and an aliphatic polyhydric alcohol having 2 to 10 carbon atoms is preferable.
Aliphatic carboxylic acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isodecanoic acid, isotridecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachidic acid, isohexacic acid, oleic acid, linoleic acid 5,8,11,14-eicosatetraenoic acid, 4,7,10,13,16,19-docosahexaenoic acid and the like.

In addition, as aliphatic polyhydric alcohols, ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, 1,4-butenediol, sorbitol , Sorbitan, sucrose and the like.
The aliphatic carboxyl ester preferably has an HLB value of 3 to 7 and a melting point of 25 to 100 ° C, more preferably an HLB value of 3 to 6 and a melting point of 40 to 90 ° C. Aliphatic carboxylic esters having these conditions are preferred because they are easy to handle, have good releasability, and have little contamination of the molding die. The HLB value is an abbreviation of Hydrophile-Lipophile Balance, as described in, for example, [Surfactant; (Kodansha); Fumio Kitahara et al .; p24], and is a parameter representing a hydrophilicity / hydrophobicity balance.

Specific examples of esters satisfying such a balance include ethylene glycol monoisopalmitate, propylene glycol diolate, 1,4-butenediol diisostearate, 1,4-butenediol monostearate, glycerol monolaurate. Rate, glycerol monomyristate, glycerol monostearate, glycerol monobehenate, glycerol monoisomyristate, glycerol monoisostearate, glycerol monooleate, glycerol monolinoleate, glycerol dipalmitate, glycerol distearate, glycerol di Isostearate, glycerol diolate, glycerol stearate isopalmitate, glycerol trimyristate, glycerol tristearate, glyce Tribehenate, Glycerol triisostearate, Trimethylolpropane monostearate, Trimethylolpropane monobehenate, Trimethylolpropane monooleate, Trimethylolpropane dipalmitate, Trimethylolpropane diisostearate, Trimethylolpropane Tristearate, Trimethylolpropane trioleate, Pentaerythritol monopalmitate, Pentaerythritol diisopalmitate, Pentaerythritol trioleate, Pentaerythritol tetrastearate, Pentaerythritol tetraisopalmitate, Pentaerythritol dioleate distearate, etc. Examples include sorbitan monostearate and sucrose diisostearate. These aliphatic carboxylic acid esters (component B) may be used alone or in combination.
Since the amount of the aliphatic carboxylic acid ester used has a great influence on the dispersibility in the composition (X), it is 0.5 to 10 parts by weight, preferably 0.7 to 100 parts by weight with respect to 100 parts by weight of the granular material. 9 parts by weight, more preferably 1 to 8 parts by weight.

(C component)
The sterically hindered phenol compound (component C) is used as an antioxidant. As the sterically hindered phenol compound, those in which at least one of ortho positions of the phenolic hydroxyl group is substituted with a tertiary carbon atom are preferable.

  These sterically hindered phenol compounds include n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, tetrakis {methylene-3- (3 ′, 5′-di). -T-butyl-4-hydroxyphenyl) propionate} methane, triethylene glycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis { 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino)- 1,3,5-triazinepentaerythrityl-tetrakis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, , 2-thiodiethylenebis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, 2,2-thiobis (4-methyl-6-tert-butylphenol), N, N′- Hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, tris (3,5-di-t -Butyl-4-hydroxybenzyl) -isocyanurate isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,5,7,8-tetramethyl-2- (4 ' , 8 ′, 12′-trimethyltridecyl) chroman-6-ol, N, N′-bis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propioni Hydrazine} and the like. These C components may be used alone or in combination.

Since the usage-amount of C component has a big influence on the dispersibility in composition (X), Preferably it is 0.1-10 weight part with respect to 100 weight part of granular materials, More preferably, 0.2- 9 parts by weight, more preferably 0.5 to 8 parts by weight.
Therefore, (iii) 0.5 to 10 parts by weight of an aliphatic carboxylic acid ester (component B) and / or (iv) 0.1 to 10 parts by weight of a sterically hindered phenol compound with respect to 100 parts by weight of the granular material. It is preferable to further contain (C component).
Composition (X) is excellent in the dispersibility of an additive. It is preferable that 10 samples are collected from the composition (X), and the value obtained by dividing the standard deviation σ by the theoretical content is in the range of 0 to 10.

<Production Method of Composition (X)>
The A component, the B component, and the C component may each be mixed with the granular material alone, but it is more preferable from the viewpoint of dispersibility to add a homogeneous mixture obtained by melting and homogenizing several components.
The mixing of these additives and the granular material can be performed by a mixer such as a tumbler, a V-type blender, a nauta mixer, a Banbury mixer, a Henschel mixer, a super mixer, a turnbull mixer, a ribbon blender, or the like.
Mixing can be carried out effectively by a batch system or a continuous system. At the time of mixing, it is preferable to control the temperature of a granular material in the range of 10-100 degreeC. More preferably, it is preferable to control the temperature within the range of 20 to 70 ° C., more preferably 20 to 50 ° C., for uniform dispersion of the additive in the composition (X). If the temperature rises too much, the problem that the composition (X) aggregates and becomes non-uniform tends to occur. Furthermore, it is pointed out that the heat of friction between the mixing blade and the vessel wall is generated and the additive is denatured. Therefore, the temperature of the composition (X) is preferably as low as possible, and if there is a risk of heat generation, it is necessary to appropriately employ cooling means such as water cooling to suppress the temperature rise.

The mixing time and the stirring speed of the composition (X) are preferably performed while appropriately sampling and evaluating the dispersibility to determine whether or not the dispersibility of the additive has reached a good range. Usually, it can be uniformly dispersed by mixing for about 5 to 60 minutes.
When the amount of the additive is 1% by weight or less with respect to the granular material, it is preferable to apply a suitable inert solvent in order to improve the uniformity of the addition distribution in the composition (X). Such an inert solvent is not particularly limited as long as it does not adversely affect the physical properties of the composition (X). Examples of such solvents include water, lower alcohols such as methanol and ethanol, acetone, or a mixture thereof.

The atmosphere in which the mixing is performed preferably keeps the relative humidity low when the additive contains a highly hygroscopic material. That is, the relative humidity is preferably 0 to 60%, more preferably 0 to 45%, still more preferably 0 to 30%, and particularly preferably 0 to 20%. Further, it is an important condition that the humidity does not vary during batch production or between batches.
In addition, when the additive is easily oxidized, it is also preferable to carry out in an inert gas atmosphere such as nitrogen because the atmosphere is blocked from the outside.
Therefore, the composition (X) comprises (i) 100 parts by weight of a granular material and (ii) 0.01 to 5 parts by weight of a deactivator (component A) with a relative humidity of 0 to 60% and a cleanness. It can be produced by mixing in an atmosphere of class 100,000 or less.

Such a composition (X) is mixed with a thermoplastic resin and may be used for optical resin applications, and it is necessary to suppress contamination of foreign substances as much as possible. It is a necessary condition that the atmosphere gas supplied into the kneading apparatus and the atmosphere in which the kneading operation is performed are kept clean.
The atmosphere gas and atmosphere air have foreign substances filtered by a filter, and preferably have a cleanliness of class 100,000 or less, preferably class 10,000 or less, and more preferably class 1000 or less.

<Composition (Y)>
The composition (Y) contains the composition (X) and a thermoplastic resin. The composition (Y) is obtained by melt-kneading the composition (X) and a thermoplastic resin.
The amount of the composition (X) is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
In the melt-kneading of the composition (X) and the thermoplastic resin, kneading with an extruder when the thermoplastic resin is in a molten state after polymerization is not preferable, such as a decrease in hue and a decrease in molecular weight (Mw). This is preferable in that the side reaction can be suppressed to a low level. However, the solidified thermoplastic resin can be redissolved and kneaded with an extruder.

  Examples of the thermoplastic resin include polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, Resins such as amorphous polyarylate resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, epoxy resin, and polylactide Can be mentioned.

  The thermoplastic resin is preferably polylactide (2) obtained by melt ring-opening polymerization of lactide in the presence of an initiator and a metal catalyst. The optical purity of lactide is preferably 90 to 100%. In this case, the amount of the quenching agent in the composition (X) is preferably 0.3 to 20 equivalents, more preferably 0.5 to 10 per equivalent of the metal element in the metal catalyst in the polylactide (2). It is preferable to be equivalent.

(Other ingredients)
In addition to the components A to C, various known additives may be added to the composition (X) and the composition (Y) as long as they do not contradict the purpose of the present invention. These include, for example, plasticizers, stabilizers, antioxidants, weathering (light) stabilizers, mold release agents, lubricants, antistatic agents, plasticizers, pigments, dyes, fillers, reinforcing agents, flame retardants and the like. It is done. Moreover, you may further add another thermoplastic resin, a thermosetting resin, a soft thermoplastic resin, etc. to the composition (X) and the composition (Y) in the range which does not impair the objective of this invention.
In addition to the aliphatic carboxylic acid ester (component B) described above, examples of the release agent include hydrocarbon release agents, fatty acid release agents, fatty acid amide release agents, alcohol release agents, and the like.

  Examples of hydrocarbon release agents include natural and synthetic paraffin waxes, polyethylene waxes, fluorocarbons and the like. Examples of fatty acid release agents include higher fatty acids such as stearic acid and oxy fatty acids such as hydroxystearic acid. Examples of the fatty acid amide release agent include fatty acid amides such as ethylene bisstearyl amide and alkylene fatty acid amides such as erucic acid amide. Examples of the alcohol releasing agent include aliphatic alcohols such as stearyl alcohol and cetyl alcohol, and examples of the polyhydric alcohol include polyglycol, polyglycerol, and trimethylolpropane. Other polysiloxanes can also be used. These may be used singly or in combination of two or more.

  As stabilizers other than sterically hindered phenolic compounds (component C), thioether stabilizers such as dilauryl thiopropionate, dimyristyl-3,3′-thiodipropionate, pentaerythritol-tetrakis- (β-laurylthiopro) (Pionate).

  2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) as a weathering (light) stabilizer ) Benzotriazole, benzotriazole compounds such as 2- {2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) phenyl} benzotriazole, and benzophenones such as 2-hydroxy-4-octyloxybenzophenone Compounds, benzoate compounds such as 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, cyanoacrylate compounds such as 2-cyano-3,3-diphenyl acrylate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4-hydroxy-2, , 6,6-hindered amine compounds such as succinic acid polymers tetramethyl-1-piperidineethanol can be exemplified.

A known flame retardant may be used in combination with the composition (X) and the composition (Y) if desired. As flame retardants, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisophosphate Phosphate esters such as propenylphenyl, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate Compounds. If desired, polytetrafluoroethylene (Teflon) (registered trademark) or the like may be blended as an anti-drip agent.
In the composition (X) and the composition (Y), organic or inorganic colorants such as dyes and pigments may be used as desired.

As inorganic colorants, oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as bitumen, chromates such as zinc chromate, sulfates such as barium sulfate, Examples thereof include carbonates such as calcium carbonate, silicates such as ultramarine, phosphates such as manganese violet, carbon such as carbon black, and metal colorants such as bronze powder and aluminum powder.
Organic colorants include nitroso such as naphthol green B, nitro such as naphthol yellow S, azo such as naphthol red and chromophthal yellow, phthalocyanine such as phthalocyanine blue and fast sky blue, and condensation of indanthrone blue Examples include polycyclic colorants.

Various fillers can be contained in the composition (X) and the composition (Y) as desired. As the filler, an organic filler or an inorganic filler can be preferably used.
Examples of inorganic fillers include glass fiber, graphite fiber, carbon fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, sepiolite, zonolite, elestadite, gypsum fiber, silica fiber , Silica alumina fiber, zirconia fiber, silicon nitride fiber, boron fiber, glass flake, non-swellable mica, graphite, metal foil, talc, clay, mica, sericite, bentonite, kaolin, magnesium carbonate, magnesium sulfate, aluminum hydroxide , Acid value magnesium, hydrotalcite, magnesium hydroxide, gypsum, dosonite and the like.
Examples of the organic filler include natural fiber, para-type aramid fiber, polyazole fiber, polyarylate, polyoxybenzoic acid whisker, polyoxynaphthoic acid whisker, and cellulose whisker.

These fillers can be used in the form of fibers, plates, or needles. Among these fillers, fibrous inorganic fillers are preferable, and glass fibers are particularly preferable. The aspect ratio of the filler is preferably 5 or more, and more preferably 10 or more. Particularly preferred is 100 or more. The aspect ratio is a value obtained by dividing the fiber length by the fiber diameter in the case of a fibrous filler, and is a value obtained by dividing the length in the long period direction by the thickness in the case of a plate-like filler. The elastic modulus of the filler is preferably 50 GPa or more.
The filler is also preferably coated or focused with a thermoplastic resin or a thermosetting resin. For example, it may be treated with a coupling agent such as aminosilane or epoxysilane, or treated with various organic substances. The filler may be used alone or in combination of two or more.

The natural fiber has a strength as a single fiber of preferably 200 MPa or more, more preferably 300 MPa or more. This is because, within this range, sufficient mechanical properties can be exhibited as a composite, and the amount of the filler mixed can be reduced, so that the shape of the surface of the molded body can produce better results.
Natural fibers have a fiber diameter in the range of 0.1 μm to 1 mm, preferably in the range of 1 to 500 μm. The aspect ratio is preferably 50 or more. Such fibers can be well mixed with the resin and can be made into a composition having excellent physical properties by compounding. The aspect ratio is more preferably 100 to 500, still more preferably 100 to 3000.
Any natural fiber can be used effectively regardless of its type as long as it satisfies the above-mentioned conditions. Among these, plant fibers such as kenaf, bamboo, flax, hemp, wood pulp, and cotton can be preferably used. In particular, wood pulp obtained from waste materials, pulp obtained from waste paper, and fibers made from kenaf are very preferable because they have a low environmental load and high regeneration ability.

Any natural fiber produced by any method can be suitably used as long as its form and strength are maintained within an appropriate range. For example, (i) fiberization by chemical pulping, (ii) fiberization by biopulping, (iii) explosion, (iv) mechanical disintegration, etc. can be mentioned.
The surface of the natural fiber may be modified. This is even more desirable when the surface strength of the natural fiber is modified to increase the interfacial strength between the resin and the fiber, thereby increasing durability. Such modification methods include (i) a method of chemically introducing a functional group, (ii) a method of mechanically densifying the surface, or (iii) a method of smoothing (iv) a surface modifier. Examples thereof include a method of reacting by mechanical stimulation. The natural fiber may be a single fiber or a fiber assembly.

The weight ratio of polylactide and natural fiber in the composition (X) and the composition (Y) is from the former / the latter = 98/2 to 1/99. The former / the latter is preferably 85/15 to 40/60, more preferably 70/30 to 50/50.
The composition (X) or the composition (Y) containing the filler exhibits good biodegradability and sufficient strength, and both polylactide and natural fiber do not give a burden to the environment. It can be used suitably. In particular, it is suitable not only for structural members and building materials that require strength, but also for joinery materials and construction temporary materials. The biodegradable composite of the present invention has a heat distortion temperature of preferably 240 ° C. or lower, more preferably 200 ° C. or lower, more preferably 170 ° C. or lower. The composition of the present invention can be used for various applications as molded articles such as sheets and mats.

Using the composition (X) or the composition (Y) of the present invention, an injection molded product, an extrusion molded product, a vacuum / pressure molded product, a blow molded product, a film, a sheet, a sheet nonwoven fabric, a fiber, a cloth, and other materials Composites, agricultural materials, fishery materials, civil engineering. Building materials, stationery, medical supplies or other molded articles can be obtained by a conventionally known method.
<Polylactide stereo complex>
It is known that polylactide stereocomplexes can be obtained by mixing D- and L-polylactides in solution or in a molten state. The composition (Y) of the present invention can be used for production of a polylactide stereocomplex composition. The present invention also includes the resulting polylactide stereocomplex composition.

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples.
1. The physical properties measured in Examples and Comparative Examples were determined by the following methods.

(1) Weight average molecular weight (Mw) and number average molecular weight (Mn):
It calculated | required by the comparison with the polystyrene standard sample by the gel permeation chromatography (GPC). GPC measuring instrument
Detector: Differential refractometer RID-6A manufactured by Shimadzu Corporation
Pump: LC-9A manufactured by Shimadzu Corporation
Column: Tosoh Corporation TSKgelG3000HXL, TSKgelG4000HXL, TSKgelG5000HXL and TSKguardcocumHXL-L are connected in series.
Chloroform eluent was used. The column temperature was 40 ° C., the flow rate was 1.0 ml / min, and 10 μL of a sample having a concentration of 1 mg / ml (chloroform) was injected and measured.

(2) Crystallization enthalpy Using a DSC, measurement was performed at a heating rate of 20 ° C./min in a nitrogen atmosphere, and the crystallization point (Tc), melting point (Tm), crystallization enthalpy (ΔHc) and melting enthalpy (ΔHm) Asked.

(3) Dispersibility of additives (A component, B component, C component) in composition (X) or (Y) Dispersibility of A component (phosphorus deactivator):
1 g per sample was collected from 1 kg of the composition (X) or (Y), and a total of 10 samples were collected. About each sample, phosphorus atom content was measured in ICP-MS analysis, and the standard deviation (sigma) was calculated | required. Dispersibility was evaluated by calculating σ / Po by dividing this value by the theoretical content Po.
Dispersibility of component B (higher fatty acid derivative):
1 g per sample was collected from 1 kg of the composition (X) or (Y), and a total of 10 samples were collected. Each sample was dissolved in chloroform, and the content of higher fatty acid ester was quantified using high performance liquid chromatography at 20 ° C., and the standard deviation σ was determined. Dispersibility was evaluated by calculating σ / Ho by dividing this value by the theoretical content Ho.
Dispersibility of component C (sterically hindered phenol compound):
1 g per sample was collected from 1 kg of the composition (X) or (Y), and a total of 10 samples were collected. For each sample, the content of sterically hindered phenolic compounds was measured by the titanium coloring method, and the standard deviation σ was determined. Σ / Ko obtained by dividing this value by the theoretical content Ko was calculated to evaluate dispersibility.
A case where the dispersibility was 1 or less was judged good, and a case where the dispersibility was 1 or more was judged bad.

(4) Average particle size The ground polylactide was sieved using ASTM sieves 7, 14, 25, 35, 45, 60, 100, 140, and 200. The cumulative particle size distribution was determined by weight criteria, and the particle size at which the cumulative weight reached 50% by weight was defined as the average particle size.

(5) Thermal stability of composition (Y) The pellet of the composition (Y) dried at 100 degreeC for 5 hours was heat-processed at 260 degreeC for 1 hour in nitrogen atmosphere, and the weight loss was represented by -weight%.

(6) Metering stability The mechanism that vibrates the container while detecting the weight of the composition (X) from the second supply port and drops it to the lower supply ruder. The quality of the composition (X) is measured in the middle of the drop tube. Judgment was made based on the degree of adhesion of the granular material. The amount of adhesion after 1 hour operation was judged visually, and those with an acceptable amount of adhesion were judged as “good” and those with a large amount were judged as “bad”.

<Example 1 and Comparative Example 1>
(Manufacture of polylactide)
(apparatus)
The polymerization apparatus includes a charging tank, a first polymerization tank, a devolatilizer, and a pelletizer.
The charging tank is an anchor blade-equipped vertical stirring charging dissolution tank (capacity 250 L) equipped with a vacuum pipe, a nitrogen gas pipe and a heating / cooling device.
The first polymerization tank is a vertical stirring tank (120 L) equipped with a spiral blade equipped with a vacuum pipe, a nitrogen gas pipe, a catalyst / lactide solution addition pipe, an alcohol initiator addition pipe and a cooling device.
The devolatilization device is a tip feeding device using a hopper, a deactivator mixed liquid addition precision pump, a biaxial ruder equipped with a three-stage vacuum vent, or a monoaxial ruder equipped with a two-stage vacuum vent. A pelletizer was placed at the exit of the ruder.

(Operating conditions)
The charging tank was held at 140 ° C. and nitrogen gas at an internal pressure of 106.39 kPa, and 60 kg of lactide described in Table 1-1 (L-LD, D-LD, L-LD / D-LD) was dissolved and held.
Lactide is transferred from the charging tank to the first polymerization tank and polymerized at 180 to 210 ° C. in the presence of 0.45 × 10 ⁻² mol of tin octylate using 30 kg of lactide as a catalyst and 0.39 mol of stearyl alcohol as an initiator. I let you. The obtained polymer was pelletized to obtain a polymer chip.
To the polymer chip, 1.05 times moles of phosphoric acid with respect to the tin element of tin octylate was added as a quenching agent. After the addition, the mixture was degassed at 66.7 kPa for 20 minutes, and the resin extrusion rate was 5 kg / hour and the temperature was 220 with a 30 mm three-stage vented and three-stage inert gas supply port twin-screw extrusion devolatilizer (unit treatment zone number: 3). Nitrogen gas was supplied to each of the first, second and third treatment zones at a normal temperature of 100 ° C. and a rotation speed of 100 rpm, and kneading time was 6 seconds, and each vent pressure was 13.33 kPa, 2 kPa, and 0.67 kPa for a total of 18 seconds. After the treatment, it was pelletized with a chip cutter to obtain three types of polylactides PL1, PL2, and PL3.
The Mw of PL1 was 165,000, and the reaction rate was 94%. The Mw of PL2 was 164,000, and the Mw of PL3 was 165,000.

(Crushing, heat treatment)
The polylactide pellets PL1, PL2 and PL3 were each pulverized with a Willet crusher and sieved to obtain powder particles. The obtained granular material was heat-treated at 80 ° C. using a hot air dryer at varying times to obtain a granular material having the average particle diameter, crystallization enthalpy and specific surface area described in Table 1-2.

<Example 2 and Comparative Example 2>
(Composition (X))
Additives of the types and amounts listed in Table 2 with respect to 100 parts by weight of the granular material, with a dew point of −60 ° C. or less and a cleanness of class 100 in a dry nitrogen gas atmosphere, a stirring speed of 300 rpm with a Henschel mixer, a resin temperature of 20 to The mixture was stirred at 40 ° C. for 30 minutes to prepare Composition (X) MS1-1-5. The evaluation results of the dispersibility of the additive are shown in Table 2. The additive was diluted 10 times with acetone and added.

<Example 3 and Comparative Example 3>
The composition (X) containing the component of Table 3 was prepared using the granular material from which crystallization enthalpy differs like Example 2, and the dispersibility was evaluated. As apparent from Table 3, when the crystallization enthalpy of the granular material is out of the predetermined range, the dispersibility becomes poor.

<Example 4 and Comparative Example 4>
Composition (X) was prepared in the same manner as in Example 2 except that the kind and concentration of the additive were changed. As is apparent from Table 4, when the additive concentration is high, the tackiness of the composition (X) increases and the dispersion becomes poor. On the other hand, if the additive concentration is too low, dispersibility will be poor even if the solvent is diluted.

<Synthesis Example 1> Production of L-PL (2) (apparatus)
The polymerization apparatus includes a charging tank, a first polymerization tank, a devolatilizer, and a pelletizer.
The charging tank is an anchor blade-equipped vertical stirring charging dissolution tank (capacity 250 L) equipped with a vacuum pipe, a nitrogen gas pipe and a heating / cooling device.
The first polymerization tank is a vertical stirring tank (120 L) equipped with a spiral blade equipped with a vacuum pipe, a nitrogen gas pipe, a catalyst / lactide solution addition pipe, an alcohol initiator addition pipe and a cooling device.
The devolatilization device is a chip feeding device by a hopper, a deactivator mixed liquid addition precision pump, a biaxial ruder equipped with a two-stage vacuum vent, or a monoaxial ruder equipped with a two-stage vacuum vent. A pelletizer was placed at the exit of the ruder.

(Operating conditions)
The charging tank was maintained at 140 ° C. and nitrogen gas at an internal pressure of 111.5 kPa. 60 kg of L-lactide having an optical purity of 99%, 0.44 mol of stearyl alcohol as an initiator, and 9.0 × 10 ⁻³ mol of tin octylate as a polymerization catalyst are charged into a first polymerization tank from a charging tank, Polymerization was performed at 3 kPa for 1 hour to produce L-PL (2). Mw of L-PL (2) was 264,000, and the lactide content was 6% by weight.

<Synthesis Example 2> Production of D-PL (2) D-PL (2) was produced in the same manner as in Synthesis Example 1 except that D-lactide having an optical purity of 99% was used. Mw of D-PL (2) was 263,000, and the lactide content was 5% by weight.

<Synthesis Example 3> Production of D / L-PL (2) In the same manner as in Synthesis Example 1 except that D-lactide having an optical purity of 99% / L-lactide having an optical purity of 99% = 50/50 molar mixture was used. D / L-PL (2) was manufactured. The Mw of D / L-PL (2) was 264,000, and the lactide content was 6% by weight.
Example 5 and Comparative Example 5 Preparation of Composition (Y) Composition (X) MS1-1 to 18 and polylactide (2) were kneaded using an extruder shown in FIG.
The extruder shown in FIG. 1 has first to third three-stage treatment zones (13, 14, 15), two resin supply ports (4, 5), and three-stage inert gas supply ports ( 7, 8 and 9), a 20 mmφ twin screw extruder of the same direction rotation type having a three-stage vacuum vent port (10).

The polylactide was supplied to the pressure of 10 kg / cm ² by the gear pump (2) via the line (1) and supplied from the supply port (24) at a supply amount of 32 kg / hour, while the composition (X) MS1- 1-18 were supplied to the extruder through the supply port (5) from the side feeder (6).

The extruder has a resin temperature of 220 ° C., a rotation speed of 100 rpm, an inert gas supply port (7, 8, 9) is supplied with 20 normal liters of nitrogen gas per kg of polylactide, a first treatment zone vent pressure of 13.33 kPa, After performing the devolatilization treatment in the second treatment zone vent pressure of 2 kPa, the third treatment zone vent pressure of 0.67 kPa, and each zone treatment time of 3 seconds for a total of 18 seconds, chips were formed with a chip cutter.
Table 5 shows the evaluation results of the physical properties of the chip of the composition (Y) obtained. It can be seen that the dispersibility of the composition (Y) derived from the granular material having a small particle size is not good.

<Example 6 and Comparative Example 6>
A chip of the composition (Y) was produced in the same manner as in Example 5 except that MS1-6 to 10 were used. Table 6 shows the evaluation results of the physical properties of the obtained chip. It can be seen that the dispersibility of the composition (Y) derived from the granular material having a small crystallization enthalpy is not good.

<Example 7>
A chip of the composition (Y) was produced in the same manner as in Example 5 except that MS1-7 and L-PL (2), D-PL (2) or D / L-PL (2) were kneaded. . Table 7 shows the evaluation results of the physical properties of the obtained chip. All the chips showed good dispersibility.

<Example 8 and Comparative Example 8>
A chip of the composition (Y) was produced in the same manner as in Example 5 except that MS1-11-1 was used. Table 8 shows the evaluation results of the physical properties of the obtained chip. The dispersibility of the composition (Y) derived from the composition (X) having a high concentration of the additive becomes poor.

<Example 9>
A chip of the composition (Y) was produced in the same manner as in Example 5 except that MS1-16 to 18 were used. Table 9 shows the evaluation results of the physical properties of the obtained chip. Even if the kind of the additive was changed, good dispersibility and thermal stability were obtained.

<Example 10> Production of polylactide stereocomplex Equivalent amounts of the compositions (Y) obtained in Examples 8-2 and 9-1 were added to a flask, and after nitrogen substitution, the temperature was raised to 260 ° C, and the temperature was 260 ° C. Melt blending was performed for 10 minutes. The weight average molecular weight of the obtained resin was 160,000.
DSC measurement was performed on this resin. As a result, a melting peak with a melting point of 201 ° C. was observed on the DSC chart, and the melting enthalpy was 34 J / g. The melting peak at 140 to 180 ° C. was not observed, and the ratio of the melting peak at 200 ° C. or higher (R _{200 or higher} ) was 100%. The crystallization point was 111 ° C.

  By using the granular material of the present invention, various molded articles for agriculture, fishery, civil engineering, and medical use can be obtained.

1 is a schematic view of an apparatus for producing a polylactide composition used in Examples.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Connection line with melt polymerization apparatus of melt ring-opening polymerization method 2 Gear pump 3 Co-rotating twin screw extruder 4 First supply port 5 Second supply port 6 Side feeder 7 Nitrogen gas supply line 8 Nitrogen gas supply line 9 Nitrogen Gas supply line 10 Vacuum pump 11 Cooling bath 12 Strand cutter 13 First treatment zone 14 Second treatment zone 15 Third treatment zone

Claims (12)

A granular material comprising a polylactide having a crystallization enthalpy of 5 to 20 J / g by a differential scanning calorimeter and having an average particle size of 0.1 to 4 mm. The melt-opening polymerization of lactide in the presence of an initiator and a metal catalyst, followed by heat treatment at 60 to 140 ° C for 0.5 to 10 hours before or after pulverization. A method for producing a granular material. The method according to claim 2, wherein the optical purity of lactide is 90 to 100%. (i) A polylactide having a crystallization enthalpy of 5 to 20 J / g measured by a differential scanning calorimeter, and 100 parts by weight of a granular material having an average particle size of 0.1 to 5 mm,
(ii) 0.01-5 parts by weight of phosphoric acid, metaphosphoric acid, phosphorous acid, pyrophosphoric acid, imine compound, phosphorus oxoacid, phosphorus oxoacid ester and the following formula (1)
R ⁵ -P (═O) _q (OH) _s (OR ⁴ ) _2-s (1)
(In formula (1), q is 0 or 1, s is 1 or 2, and R ⁴ and R ⁵ each independently represents a hydrocarbon group optionally having a substituent having 1 to 20 carbon atoms.)
A composition (X) containing at least one deactivator (component A) selected from the group consisting of organic phosphorus oxoacid compounds represented by the formula: (i) For 100 parts by weight of the powder,
(iii) 0.5 to 10 parts by weight of an aliphatic carboxylic acid ester (component B) and / or
(iv) The composition (X) according to claim 4, comprising 0.1 to 10 parts by weight of a sterically hindered phenol compound (component C). (i) 100 parts by weight of a granular material comprising a polylactide having a crystallization enthalpy of 5 to 20 J / g by a differential scanning calorimeter and having an average particle size of 0.1 to 5 mm;
(ii) 0.01-5 parts by weight of phosphoric acid, metaphosphoric acid, imine compound, phosphorus oxo acid, phosphorus oxo acid ester and the following formula (1)
R ⁵ -P (═O) _q (OH) _s (OR ⁴ ) _2-s (1)
(In formula (1), q is 0 or 1, s is 1 or 2, and R ⁴ and R ⁵ each independently represents a hydrocarbon group optionally having a substituent having 1 to 20 carbon atoms.)
At least one deactivator (component A) selected from the group consisting of organic phosphorus oxoacid compounds represented by:
A method for producing a composition (X), comprising mixing in an atmosphere having a relative humidity of 0 to 60% and a cleanliness class of 100,000 or less. A composition (Y) containing the composition (X) according to claim 4 and a thermoplastic resin. A method for producing a composition (Y), comprising melt-kneading the composition (X) according to claim 4 and a thermoplastic resin. The process according to claim 8, wherein the thermoplastic resin is polylactide (2) obtained by melt ring-opening polymerization of lactide in the presence of an initiator and a metal catalyst. The method according to claim 9, wherein the lactide has an optical purity of 90 to 100%. The method of using the composition (Y) of Claim 7 for manufacture of a polylactide stereocomplex composition. A polylactide stereocomplex composition produced by the method according to claim 11.

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