JP2007191630A - Polylactic acid composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polylactic acid composition excellent in stereospecificity, crystallinity, moldability and mechanical properties, and to provide a method for producing the same. <P>SOLUTION: The polylactic acid composition comprises polylactic acid and a crystallization promoter and is 80% or greater in the stereospecificity(S) represented by the formula:S=[ΔHms/(ΔHms+ΔHmh)]×100( wherein, ΔHms(J/g) is enthalpy of crystal fusion at 190°C or higher determined by differential scanning calorimetry, and ΔHmh(J/g) is enthalpy of crystallization at 190°C or lower ). The method for producing the polylactic acid composition is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polylactic acid composition having a high degree of stereolation and a method for producing the same.

In recent years, for the purpose of protecting the global environment, biodegradable polymers that are decomposed in a natural environment have attracted attention and are being studied all over the world. As a biodegradable polymer, polyhydroxybutyrate, polycaprolactone, aliphatic polyester, polylactic acid and the like are known. Among these, polylactic acid can be produced from lactic acid or lactide, which is a raw material, from natural products, and its use as a general-purpose polymer is being studied, not just as a biodegradable polymer.
Compared with poly L-lactic acid (PLLA) having L-lactic acid units as main repeating units or poly D-lactic acid (PDLA) having D-lactic acid units as main repeating units, the crystal melting temperature is about 170 ° C. Since stereocomplex polylactic acid has a crystal melting temperature exceeding 200 ° C., is excellent in heat resistance, crystallinity and transparency, and is tough, it is expected as various heat resistant materials. However, since stereocomplex polylactic acid has a low crystallization speed, it has a drawback that it takes time to produce a product having a predetermined stereocrystallization degree and crystallinity.
Moreover, when stereocomplex polylactic acid is shape | molded, heat resistance falls under the influence of poly L-lactic acid and poly D-lactic acid which remain | survive, and the original property of stereocomplex polylactic acid may not be exhibited. For example, the injection molding cycle of stereocomplex polylactic acid needs to be lengthened, and heat treatment after molding is also required. Further, there is a drawback that the deformation temperature of the molded body under thermal stress (hereinafter sometimes referred to as load deflection temperature) is lowered.

In order to improve the crystallization speed of stereocomplex polylactic acid, application of a crystallization accelerator has been proposed. For example, in Patent Document 1, poly L-lactic acid and poly D-lactic acid and a crystallization nucleating agent such as talc are dry blended, melt-kneaded at 220 ° C. for 4 minutes with a twin screw rudder, extruded as a strand, and stereocomplex. It has been proposed to produce polylactic acid. However, if the crystallization nucleating agent is added in a state where the stereogenicity is low and the crystallization speed is increased, the rate of increase in stereogenicity is slow, and it takes a long time to reach the desired stereogenicity. Moreover, there is a high possibility of causing thermal decomposition of the resin by heating for a long time. Further, the obtained molded article having a low degree of stereoization has a low deformation temperature under thermal stress.
In order to improve moldability and heat distortion temperature, methods using organic and inorganic fillers have been studied. For example, Patent Document 2 proposes application of naturally-derived organic fillers, crystallization accelerators, and the like, but studies on improvement in stereogenicity and crystallinity are insufficient, and stereocomplex poly It has not yet reached the point where the characteristics inherent to lactic acid are fully exhibited.
JP 2003-192894 A Japanese Patent Laid-Open No. 2005-2174

  An object of the present invention is to provide a polylactic acid composition having excellent stereogenicity, crystallinity, moldability, and mechanical properties. It is another object of the present invention to provide a method for producing a polylactic acid composition having a high stereogenicity and a high crystallinity.

  As a result of intensive studies to solve the above problems, the present inventor has (i) melt kneaded at least twice to melt and knead polylactic acid to increase the degree of stereoification, and (ii) polylactic acid. After the degree of stereoification of the composition reaches at least 80%, by adding a crystallization accelerator and performing the second melt kneading at a temperature higher than the first time, the degree of stereoization is high, The present invention was completed by finding that a polylactic acid composition (A) excellent in crystallinity and moldability was obtained, and a molded article having a high deformation temperature under heat stress and excellent heat resistance was obtained.

That is, the present invention contains polylactic acid and a crystallization accelerator and has a crystal melting enthalpy of 190 ° C. or higher measured by a differential scanning calorimeter as ΔHms (J / g) and a crystallization enthalpy of 190 ° C. or lower as ΔHmh ( J / g), the following formula
S = {ΔHms / (ΔHms + Hmh)} × 100
Is a polylactic acid composition (A) having a stereogenicity (S) of 80% or more.

  The present invention also includes (1) crystalline polylactic acid (B) containing an L-lactic acid unit as a main component and 0 to 10 mol% of a D-lactic acid unit, and an L-lactic acid unit containing a D-lactic acid unit as a main component. Of 0 to 10 mol% of crystalline polylactic acid (C) is melt kneaded at a weight ratio (B / C) = 10/90 to 90/10, and the composition has a degree of stereo (S) of 80% or more A composition comprising: a first heat treatment step for obtaining a product (D); and (2) a second heat treatment step for adding a crystallization accelerator to the composition (D) and melt-kneading at 240 ° C. to 300 ° C. It is a manufacturing method. Moreover, this invention includes the molded object which consists of a polylactic acid composition (A).

  The polylactic acid composition (A) of the present invention is excellent in stereogenicity, crystallinity, moldability, and mechanical properties. Further, according to the method of the present invention, a polylactic acid composition (A) having a high stereogenicity and excellent crystallinity and moldability can be obtained. The molded article of the present invention is excellent in stereogenicity, crystallinity, moldability, and mechanical properties, has a high deformation temperature under thermal stress, and has excellent heat resistance.

The present invention will be described in further detail below.
<Polylactic acid composition (A)>
The polylactic acid composition (A) of the present invention contains polylactic acid and a crystallization accelerator. The polylactic acid composition (A) has a stereogenicity (S) of 80% or more.
The degree of stereoization (S) is given by
S = {ΔHms / (ΔHms + Hmh)} × 100
It is represented by Here, ΔHms (J / g) is a crystal melting enthalpy of 190 ° C. or higher measured by a differential scanning calorimeter (hereinafter sometimes abbreviated as DSC), and ΔHmh (J / g) is 190 ° C. or lower. Is the crystallization enthalpy.
The degree of stereolation (S) is preferably 95% or more, more preferably 98% or more, and particularly preferably 98 to 100%. The degree of stereoization is optimally 100%, but it is not practical from the viewpoint of cost-effectiveness to make it completely 100% due to the nature of the polymer. In practice, about 99.9% is sufficient. is there.
The weight average molecular weight of the polylactic acid composition (A) is selected in consideration of the relationship between the ease of molding processability and the mechanical and thermal properties of the resulting molded article. The weight average molecular weight of the polylactic acid composition (A) is preferably 100,000 or more, more preferably 110,000 or more, and further preferably 120,000 or more.

  However, the polylactic acid composition (A) having a high molecular weight has an exponential increase in melt viscosity, and when performing melt molding such as injection molding, the resin viscosity is within the moldable range, so the molding temperature must be set high. However, polylactic acid resin cannot withstand high molding temperatures as a characteristic of aliphatic polyester. In other words, if molding is performed at a temperature exceeding 300 ° C., the molded product may be colored due to thermal decomposition of the resin, and the value as a product may be low. Even if molding can be performed several times without coloring, when mass production is performed over a long period of time, the resin remaining in the molding machine gradually decomposes and the product is colored as the molding continues. The possibility of becoming significant becomes even greater. In order to stably carry out the coloring of the product, it is necessary to mold the polylactic acid composition (A) at less than 300 ° C. From the relationship of the melt viscosity, the weight average of the polylactic acid polylactic acid composition (A) The molecular weight is preferably 500,000 or less, more preferably 300,000 or less, and still more preferably 200,000 or less. Furthermore, from the viewpoint of placing particular emphasis on industrial productivity, it is preferable to use a product having 130,000 or less.

  Further, the large molecular weight dispersion (Mw / Mn) of the polylactic acid composition (A) means that the ratio of large molecules and small molecules is larger than the average molecular weight. That is, when the polylactic acid composition (A) having a large molecular weight dispersion, for example, a relatively high resin having a weight average molecular weight of about 200,000 is used, the proportion of molecules having a weight average molecular weight value of 250,000 may increase. In this case, the melt viscosity becomes large, which is not preferable for molding in the above sense. In addition, when a polylactic acid composition (A) having a relatively small weight average molecular weight of about 100,000 is used, the proportion of molecules having a weight average molecular weight value of less than 100,000 may increase. In this case, the mechanical properties of the molded article This is not preferable in terms of use. From this viewpoint, the range of Mw / Mn is preferably 1 to 3, more preferably 1 to 2.4, more preferably 1 to 2, and particularly preferably 1 to 1.8.

(Polylactic acid)
The polylactic acid is preferably composed of polylactic acid (B) having an L-lactic acid unit as a main component and polylactic acid (C) having a D-lactic acid unit as a main component. The polylactic acid (B) preferably contains an L-lactic acid unit as a main component and 0 to 10 mol% of a D-lactic acid unit. That is, the polylactic acid (B) contains L-lactic acid units, preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 97 to 100 mol%, and preferably D-lactic acid units. 0 to 10 mol%, more preferably 0 to 5 mol%, still more preferably 0 to 3 mol%.
The polylactic acid (C) preferably contains a D-lactic acid unit as a main component and 0 to 10 mol% of an L-lactic acid unit. That is, the polylactic acid (C) preferably contains 90 to 100 mol%, more preferably 95 to 100 mol%, more preferably 97 to 100 mol% of D-lactic acid units, and preferably contains L-lactic acid units. 0 to 10 mol%, more preferably 0 to 5 mol%, still more preferably 0 to 3 mol%.

The composition (A) of the present invention may contain components other than lactic acid as long as it does not contradict the spirit of the present invention. Constituents other than lactic acid include divalent alcohols such as ethylene glycol, propylene glycol, propanediol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, and 1,4-cyclohexanedimethanol. , Neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, etc., trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, aromatic hydroxy compounds such as hydroquinone, resorcin, bisphenol A, etc., divalent carboxylic acids such as succinic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, gluic acid Phosphoric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (4-carboxyphenyl) methane, anthracene dicarboxylic acid, bis (4-carboxyphenyl) ether, sodium 5-sulfoisophthalate, Trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, oxy acids other than lactic acid such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, and lactones For example, caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one and the like can be mentioned.
These components other than lactic acid can be copolymerized in order to achieve a desired purpose within a range not impairing the inherent biodegradability of polylactic acid, but the amount ratio thereof is 20 mol% of the total components. The upper limit should be set, and is preferably in the range of 0 to 10 mol%, more preferably 0 to 5 mol%.

The polylactic acid (B) and (C) is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol%, particularly preferably in the D-form or L-form among the total lactic acid components. Contains 98 mol% or more. The melting points of the polylactic acids (B) and (C) depend on the optical purity of the lactic acid component, and when the L-form or D-form is contained at 95% or more, the melting point is 150 ° C. or more. Polylactic acids (B) and (C) preferably have a melting point measured by DSC of 120 ° C. or higher, more preferably 130 ° C. or higher, and still more preferably 150 ° C. or higher.
Polylactic acids (B) and (C) can be produced by direct melt polymerization, solid phase polymerization, melt ring-opening polymerization of lactides, and the like. The polylactic acid (B) and (C) are preferably in the amorphous state for the reason described separately, and the direct melt polymerization method or the melt opening of the lactide can be obtained to obtain the amorphous polylactic acid (B) or (C). A method using a ring polymerization method is preferred, and a melt ring-opening polymerization method of lactides is more preferred from the viewpoint of economy and quality.
In order to obtain amorphous polylactic acid (B), (C), it is possible to obtain easily by applying a conventional method for obtaining a crystalline resin such as polyester in an amorphous state. That is, amorphous polylactic acid (B) and (C) can be obtained by rapidly cooling polylactic acid (B) and (C) in a molten state. For example, it is possible to obtain amorphous pellets by rapidly cooling and cutting molten strands in cold water at the time of pellet forming, and the pellets obtained by such a method are used in the polylactic acid resin composition (A) of the present invention. It can use suitably for manufacture of.

  When the polylactic acid resin (A) is produced by the melt ring-opening polymerization method, lactide is used to introduce the lactic acid component described above. That is, L-lactide and D-lactide are used to introduce L-form and D-form of lactic acid. Polylactic acids (B) and (C) were obtained by subjecting D-lactide or L-lactide having an optical purity of 90 to 100% to melt ring-opening polymerization in the presence of an alcohol-based initiator and a metal-containing catalyst, and converting the catalyst deactivator into a metal. It can be produced by adding 0.3 to 20 equivalents per equivalent of the metal element of the contained catalyst. When the polylactic acid (B) or (C) produced by this method is used, a polylactic acid composition (A) excellent in crystallinity, melt stability and wet heat stability can be obtained.

  Lactide melt-opening polymerization catalysts include alkali metals, alkaline earth metals, rare earths, transition metals, fatty acid salts such as aluminum, germanium, tin, antimony, carbonates, sulfates, phosphates, oxides, water Oxides, halides, alcoholates and the like can be mentioned.

  The metal-containing catalyst is preferably a catalyst containing at least one 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 butoxide, aluminum oxide, aluminum acetylacetonate, aluminum isopropoxide, aluminum-imine complex titanium tetrachloride, ethyl titanate, butyl titanate, glycol titanate, titanium tetrabutoxide, zinc chloride, zinc oxide, diethyl zinc And antimony trioxide, antimony tribromide, antimony acetate, calcium oxide, germanium oxide, manganese oxide, manganese carbonate, manganese acetate, magnesium oxide, yttrium alkoxide and the like.

Considering the catalytic activity and few side reactions, stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, stannous myristate, stannous octoate, stannous stearate Tin-containing compounds such as tetraphenyltin and aluminum-containing compounds such as aluminum acetylacetonate, aluminum butoxide, and aluminum-imine complexes are preferred. More preferable examples include diethoxytin, dinonyloxytin, tin myristate, tin octylate, tin stearate, tin chloride, aluminum acetylacetonate, aluminum isopropoxide and the like.
The amount of the catalyst used is 0.42 × 10 ^{−4 to} 100 × 10 ⁻⁴ (mol) per 1 kg of lactide, and 1.68 × 10 ^{−4 in} consideration of reactivity, color tone and stability of the resulting polylactide. To 42.1 × 10 ⁻⁴ (mol), particularly preferably 2.53 × 10 ^{−4 to} 6.8 × 10 ⁻⁴ (mol).

Examples of the deactivator used for catalyst deactivation of polylactic acid subjected to melt ring-opening polymerization in the presence of a metal-containing catalyst include the following compounds. That is, from an organic ligand consisting of a group of chelate ligands having an imino group and capable of coordinating to a specific metal-based polymerization catalyst, a phosphorus oxoacid, a phosphorus oxoacid ester, and an organic phosphorus oxoacid compound group represented by the formula (1) It is a resin containing at least one selected and added in an amount of 0.3 to 20 equivalents per equivalent of the metal element of the specific metal-containing catalyst.
^{_{X 1 -P (= O) m}} (OH) n (OX 2) 2-n (1)
In the formula, m is 0 or 1, n is 1 or 2, and X ¹ and X ² each independently represent a hydrocarbon group optionally having a substituent having 1 to 20 carbon atoms. The amount of the quenching agent used is more preferably in the range of 0.4 to 15 equivalents, particularly preferably 0.5 to 10 equivalents based on the above criteria.

  The imine compound used in the present invention is a tetradentate chelate ligand having an imino group in its structure and capable of coordinating with a metal polymerization catalyst. Since imine compounds are not Bronsted acids or bases like conventional catalyst deactivators, it is possible to improve thermal stability without degrading the hydrolysis resistance of the polylactic acid resin composition. 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- Phenylenediamine, 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-cyclohexanediamy, , N′-bis (2-cyanobenzylidene) -o-phenylenediamine, N, N′-bis (2-cyanobenzylidene) -m-phenylenediamine, N, N′-bis (2-cyanobenzylidene) -p- Examples thereof include phenylenediamine, N-methyliminomethylphenol, N-ethyliminomethylphenol, N-isopropyliminomethylphenol, Nt-butyliminomethylphenol, and particularly preferably N, N′-bis (salicylidene). Ethylenediamine, N, N′-bis (salicylidene) propanediamine.

Examples of the phosphorus oxoacid include dihydridooxoline (I) acid, dihydridotetraoxodiphosphoric acid (II, II) acid, hydridotrioxophosphoric acid (III) acid, dihydridopentaoxodiphosphoric acid (III) acid, hydridopentaoxodioxide. (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 triphosphate (V, IV, IV) acid acid, 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 Acid and a mixture thereof, metaphosphoric acid represented by x / y = 1, in particular, trimetaphosphoric acid, tetrametaphosphoric acid, 1> x / y> 0, and a network having part of the phosphorus pentoxide structure Examples include ultraphosphoric acid having a structure, monovalent and polyhydric alcohols of these acids, partial esters of polyalkylene glycols, and complete ethers. From the catalyst deactivation ability, acids or acidic esters are preferably used.

As the monohydric alcohol, alcohols represented by the formula (2) which may have a substituent having 1 to 22 carbon atoms are preferably used.
Y-OH (2)
In the formula, Y represents a hydrocarbon group which may have a substituent 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 (3) which may have a substituent having 2 to 22 carbon atoms.
X (-OH) a (3)
In the formula, X represents a hydrocarbon group which may have a substituent having 2 to 22 carbon atoms, and a represents an integer of 2 to 6. Polyhydric alcohols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, pentaerythritol, trimethylolpropane, polyethylene glycol, polypropylene glycol, myo-inositol, D -, L-inositol, neositol such as scyllo-inositol, cyclitol and the like.

  Particularly preferably, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, phenylphosphonic acid, benzylphosphinic acid, dibutyl phosphate, dinonyl phosphate, N′-bis (salicylidene) ethylenediamine , N, N′-bis (salicylidene) propanediamine, and phosphoric acid, phosphorous acid, and pyrophosphoric acid are particularly preferable. These deactivators may be used singly or in some cases in combination. These deactivators are 0.3 to 20 equivalents per equivalent of metal element of the catalyst, more preferably 0.5 to 15 equivalents, more preferably 0.5 to 10 equivalents, and particularly preferably 0.6 to 7 equivalents are used. If the amount of the deactivator used is too small, the activity of the catalyst metal cannot be lowered sufficiently, and if it is used excessively, the deactivator may cause decomposition of the resin, which is not preferable.

Examples of the alcohol initiator include a compound selected from an aliphatic monohydric alcohol represented by the formula (4), a polyhydric alcohol represented by the formula (5), and a polyalkylene glycol represented by the formula (6). It is done.
A-OH (4)
In the formula, A represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
B- (OH) _b (5)
In the formula, B represents a hydrocarbon group having 2 to 20 carbon atoms, and b represents an integer of 2 to 5.
HO— (C—O) _c —H (6)
In the formula, C represents an alkylene group having 2 to 5 carbon atoms, and c represents an integer of 2 to 100.

  Examples of monohydric alcohols include 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, and n-decyl. Examples include alcohol, n-dodecyl alcohol, hexadecyl alcohol, lauryl alcohol, ethyl lactate, and hexyl lactate. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, propanediol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentylglycol, trimethylolpropane, pentaerythritol and the like. Examples of the polyalkylene glycol include diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, ethylene oxide adducts of other phenols, and ethylene glycol adducts of bisphenol. Of these initiators, stearyl alcohol, lauryl alcohol, ethylene glycol, propanediol, butanediol, hexanediol, polyethylene glycol, polypropylene glycol, and the like are preferable from the viewpoint of reactivity and polylactide physical properties.

The amount of alcohol initiator used is primarily determined in consideration of the desired weight average molecular weight Mw. For example, in the case of a monohydric alcohol, when producing a polylactic acid resin having an Mw of 70,000 to 110,000, it is 0.009 to 0.03 (mol), particularly preferably 0.014 to 0.03, per 1 kg of lactide. 021 (mol) is used. Further, when producing a polylactic acid resin having an Mw of 100,000 to 200,000, 0.009 to 0.02 (mol), particularly preferably 0.01 to 0.018 (mol) is used per 1 kg of lactide. .
While the mixture of lactide, catalyst and alcohol-based initiator is in the temperature range of 180 to 230 (° C.), more preferably in the temperature range of 185 ° C. to 220 (° C.), according to a conventionally known method, Polymerization is carried out by taking a reaction time of 2 to 10 (hours) and by a continuous or batch process, a vertical polymerization tank, a horizontal polymerization tank, a tubular polymerization tank or a combination thereof. The reaction time and reaction temperature need to be appropriately selected by judging the progress of polymerization.

  The polylactic acid subjected to melt ring-opening polymerization usually contains 1% by weight or more of lactide, but the amount of lactide remaining in the resin is preferably from 0 to 5000 (ppm). The amount of lactide in polylactic acid is one of the factors that affect the melt stability of the resin composition during melt processing. If the lactide content is high, the melt stability is poor, the resin deteriorates, and the color tone deteriorates. May be disabled.

The lactide content can be reduced according to a conventionally known lactide weight loss method, that is, vacuum devolatilization in a single-screw or multi-screw extruder, or high vacuum treatment in a polymerization apparatus. Of these, the vacuum devolatilization method or the water addition devolatilization method in a single-screw or multi-screw extruder using an inert gas as a carrier is an efficient and preferable method.
The smaller the lactide content, the better the melt stability of the resin, but it is economical to make the content suitable for the desired purpose. Therefore, it is reasonable to set to 0 to 1000 (ppm) at which practical melt stability is achieved. More preferably, a range of 0 to 700 (ppm), particularly preferably 0 to 500 (ppm) is selected.

  The weight average molecular weights of the polylactic acids (B) and (C) are preferably 100,000 or more, more preferably 110,000 or more, and further preferably 120,000 or more. The upper limit is preferably 500,000 or less, more preferably 300,000 or less, still more preferably 200,000 or less, and particularly preferably 130,000 or less. The molecular weight dispersion (Mw / Mn) of the polylactic acid (B) and (C) is preferably 1 to 3, more preferably 1 to 2.4, still more preferably 1 to 2, particularly preferably 1 to 1.8. is there. Polylactic acids (B) and (C) are preferably crystalline in nature and have a crystallization temperature and a crystal melting peak when measured by DSC, but are substantially amorphous in X-ray diffraction measurement. Are preferably used. If the polylactic acids (B) and (C) have crystallinity by X-ray diffraction measurement before the first heat treatment, the stereoization speed is increased during the first heat treatment and the second heat treatment by melt kneading. Since it is slow, it takes a relatively long time to increase the degree of stereoization to a desired value, which increases the possibility of thermal degradation of polylactic acid, which is not preferable.

(Crystallization accelerator)
The polylactic acid composition (A) of the present invention contains a crystallization accelerator. The crystallization accelerator includes an organic type and an inorganic type. The crystallization accelerator improves the crystallization speed of the polylactic acid composition (A) and improves the moldability and heat resistance. The total amount of the crystallization accelerator is 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, more preferably 0.3 to 10 parts by weight, particularly preferably 0, per 100 parts by weight of polylactic acid. 3 to 7 parts by weight.
A crystallization accelerator is an agent developed to promote crystallization of a crystalline resin, and it is known that homocrystallization is promoted when the crystallization accelerator is applied to polylactic acid having a low stereogenicity. ing. Furthermore, the crystallization accelerator may decrease the degree of stereolification of polylactic acid immediately after addition. Therefore, poly L-lactic acid and D-lactic acid may remain in the polylactic acid, or it may take a long time to reach a desired degree of stereolation. A long-time heat treatment in the presence of a crystallization accelerator not only promotes thermal decomposition of polylactic acid but also decreases production efficiency, which is not preferable in a double sense. However, by adding a crystallization accelerator to polylactic acid according to the method of the present invention, the degree of stereolization of the polylactic acid composition (A) can be improved and the crystallinity can be improved, and mechanical properties and heat resistance can be improved. And the composition (A) excellent in mold moldability can be obtained.
When the amount of the crystallization accelerator used is less than 0.1 parts by weight, the effect of promoting the crystallization rate is hardly recognized. On the other hand, if it exceeds 20 parts by weight, the effect of promoting the thermal decomposition of the resin composition is increased, and at the same time, the effect of reducing the rate of stereogenicity is further increased. Increases the likelihood of causing a reaction.
The crystallization accelerator used in the present invention can be selected from a wide variety of compounds, but the crystal nucleating agent that promotes the formation of polymer crystal nuclei and the polymer can be softened and moved to promote crystal growth. A plasticizer is preferably used. As the crystallization nucleating agent used in the present invention, those generally used as a polymer nucleating agent can be used without particular limitation, and any of an inorganic crystal nucleating agent and an organic crystal nucleating agent can be used.

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

(Organic crystallization accelerator)
As organic crystallization accelerators, calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, sodium laurate , Potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacoate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearic acid Barium, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicylic acid Organic metal carboxylic acid salts such as lead, aluminum dibenzoate, sodium β-naphthoate, potassium β-naphthoate, sodium cyclohexanecarboxylate, organic sulfonic acid metal salts such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearin Organic carboxylic acid amides such as acid amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide), low density polyethylene, high density polyethylene, polyisopropylene, polybutene , Polymers such as poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high-melting polylactic acid, ethylene-acrylic acid copolymer sodium Salt, sodium salt of styrene-maleic anhydride copolymer (so-called ionomer), melamine resin, styrene resin, silicone resin, organophosphate metal salt, sodium phenylphosphonate, potassium phenylphosphonate, calcium phenylphosphonate, Examples include phosphonic acid metal salts such as zinc phenylphosphonate, benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.

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

Polyvalent carboxylic acid plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellitic acid tributyl, trimellitic acid trioctyl, Trimellitic acid esters such as trihexyl meritate, isodecyl adipate, adipate such as adipate-n-decyl-n-octyl, citrate such as acetyltributyl citrate, bis (2-ethylhexyl) azelate, etc. Examples thereof include sebacic acid esters such as azelaic acid ester, dibutyl sebacate, and bis (2-ethylhexyl) sebacate.
Examples of the phosphate ester plasticizer include tributyl phosphate, tris phosphate (2-ethylhexyl), trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylhexyl phosphate, and the like.
Polyalkylene glycol plasticizers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide.propylene oxide) 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 an epoxy alkyl stearate and soybean oil, and other so-called epoxy resins using bisphenol A and epichlorohydrin as raw materials.

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

  As the crystallization accelerator, at least one selected from the group consisting of a phosphate ester metal salt, a melamine resin, a styrene resin, and a silicone resin is preferably used. As the phosphoric acid ester metal salt, the compounds proposed in Japanese Patent Publication No. 2003-192848, and NA-10, NA-11 and NA-21 commercially available from Asahi Denka Kogyo Co., Ltd. are most preferable. . Talc having an average particle diameter of 1 to 10 μm is most preferable. The crystallization accelerator of the present invention may be applied alone, or two or more kinds may be used in combination.

<Production of polylactic acid composition>
The method for producing the polylactic acid composition of the present invention comprises a first heat treatment step and a second heat treatment step.
(First heat treatment process)
The first heat treatment step includes polylactic acid (B) containing L-lactic acid units as a main component and containing 0 to 10 mol% of D-lactic acid units, and D-lactic acid units as a main component and containing L-lactic acid units of 0 to 0. A polylactic acid (C) containing 10 mol% is melt-kneaded at a weight ratio (B / C) = 10/90 to 90/10 to obtain a composition (D) having a stereolation degree (S) of 80% or more. It is a process to obtain.
Polylactic acid (B) and polylactic acid (C) are as described in the section of polylactic acid composition. Polylactic acid (B) and polylactic acid (C) are preferably crystalline. The weight ratio of polylactic acid (B) to polylactic acid (C) is such that (B) / (C) is 10/90 to 90/10, preferably 25/75 to 75-25, more preferably 40/60 to 60/40. If the weight ratio of one polylactic acid is less than 10 or exceeds 90, homocrystallization is prioritized and it is difficult to form a stereocomplex.

The melt kneading temperature (T1) is preferably 220 to 300 ° C, more preferably 230 to 290 ° C, and further preferably 240 to 270 ° C. When the heat treatment temperature is low, the increase in the degree of stereoization is slow and inefficient. On the other hand, if the temperature is high, the stereo-ization speed is high, but the thermal decomposition of the resin is also promoted, so that the balance between the two is set. A melt kneading time as short as possible is not only economically advantageous, but also preferable from the viewpoint of suppressing the thermal decomposition of the composition to a low level. Specifically, it is 0.2 to 30 minutes, preferably 0.5 to 20 minutes, particularly preferably 1 to 10 minutes from the viewpoint of industrial productivity and the degree of stereogenicity improvement. As the atmosphere at the time of melt kneading, either an inert gas atmosphere at normal pressure, or reduced pressure or pressurized pressure can be applied. The apparatus used for melt kneading can be used as long as it can be heated while adjusting the atmosphere. For example, a batch type melt kneader, a continuous melt kneader, a biaxial or uniaxial extruder, Using a press machine or a flow tube type extruder, a method of processing while forming can be employed. Of these, a uniaxial or biaxial extruder can be preferably used.
The melt-kneading is performed until the degree of stereolation (S) of the resulting composition (D) is 80% or more, preferably 90%, more preferably 95% or more. After the first heat treatment step, the composition (D) is preferably solidified and then subjected to the second heat treatment step. It is preferable that the solidified composition (D) is substantially in an amorphous state. Moreover, a 2nd heat treatment process can also be performed as it is with the composition (D) of a molten state.

(Second heat treatment step)
The second heat treatment step is a step of adding a crystallization accelerator to the composition (D) and melt-kneading at 240 ° C to 300 ° C. The crystallization accelerator is as described in the section of the polylactic acid composition (A). The second heat treatment temperature (T2) is 240 to 300 ° C, preferably 250 to 300 ° C, more preferably 270 to 290 ° C. When the heat treatment temperature is low, the increase in the degree of stereoization is slow and inefficient. On the other hand, if the temperature is high, the stereo-ization speed is high, but the thermal decomposition of the resin is also promoted, so that the balance between the two is set. Furthermore, the temperature difference (T2−T1) between T1 and T2 is preferably 10 to 40 ° C., more preferably 20 to 40 ° C.
A shorter second heat treatment time is not only economically advantageous, but is also a preferable condition from the viewpoint of suppressing the thermal decomposition of the resin composition to a low level. Specifically, it is 0.2 to 30 minutes, preferably 0.5 to 20 minutes, particularly preferably 1 to 10 minutes from the viewpoint of industrial productivity and the degree of stereogenicity improvement. As an atmosphere during the heat treatment, an inert gas atmosphere at normal pressure, or any of reduced pressure and pressurized pressure can be applied. As the apparatus and method used for the heat treatment, any apparatus or method that can be heated while adjusting the atmosphere can be used. It is possible to use a method of processing while forming using a ruder or the like, a press machine, or a flow tube type extruder. Of these, a uniaxial or biaxial extruder can be preferably used.

The crystallization accelerator is preferably added in the second heat treatment step. Since the crystallization accelerator has the effect of increasing the homocrystallization rate of polylactic acid and at the same time lowering the stereolization rate of the polylactic acid resin and keeping the degree of stereolization in mind, the polylactic acid composition (D It is preferable to blend in a stage where the degree of stereoization of The crystallization accelerator may further accelerate the thermal decomposition of polylactic acid or may itself thermally decompose. For this reason, blending with polylactic acid should be blended at a stage where the degree of stereoization is sufficiently increased and further heat treatment time is allowed. Further, when the above discussion is further extended, the crystallization accelerator is blended more than once, and the final stage of melt-kneading, that is, the degree of stereogenicity is sufficiently increased, and the blended crystallization accelerator is uniformly dispersed. It is preferable to mix at the stage. That is, heat treatment is performed by melt-kneading polylactic acid (B) and polylactic acid (C), and when the stereogenicity of the composition reaches at least 80%, preferably at least 90%, more preferably When at least 95% is reached, it is preferably blended, melt-kneaded to achieve uniform dispersion of the crystallization accelerator and the desired degree of stereolation.
When the crystallization accelerator is intentionally divided into a plurality of times, for example, when it is absolutely necessary to combine the crystallization accelerators twice, the mixing ratio between the first time and the second time is 0/100 by weight. To 30/70. More preferably, it is divided and blended at a ratio of 0/100 to 10/90, more preferably 0/100 to 5/95.

  In the second heat treatment step, the crystallization accelerator to be blended preferably contains talc as one component. The blending amount of talc is selected to be at least 10% by weight, preferably 20 to 100% by weight, more preferably 30 to 100% by weight of the total crystallization accelerator. In the first heat treatment step by melt-kneading the crystallization accelerator, or a method in which heat treatment is added at one time before that, the degree of stereo-ization reaches a peak and is not easily improved. In addition, the resin composition is not thermally decomposed. The present invention proposes after analyzing such a problem. The compounding method of the crystallization accelerator was a crystallization accelerator alone, polylactic acid (B) or (C) or (B), (C) mixture, diluted with polylactic acid stereocomplex resin, so-called master blend. The product is dry blended with polylactic acid or polylactic acid resin composition pellets at a predetermined ratio and supplied to the heat treatment apparatus, or separately, or blended in the melt of polylactic acid or polylactic acid resin composition Although there are various methods such as these, in any method, the crystallization accelerator can be blended without any problem.

A higher heat treatment temperature is more efficient for increasing the degree of stereoization efficiently, but the above-mentioned temperature range is selected in consideration of thermal decomposition of the polymer and the agent. In the heat treatment, it is preferable that the polylactic acid (B) and (C) are in intimate contact, and when both components are subjected to heat treatment by melt kneading, it is preferable to melt knead in the presence of shear stress.
A uniaxial or biaxial ruder is exemplified as an apparatus for effectively applying a shear stress during the melt-kneading. In order to increase the shear stress of the ruder, the ruder screw preferably includes a material seal portion and a kneading portion, and preferably includes a plurality of such units. The material seal part includes reverse flight, seal ring, or reverse kneading as structural units, and the kneading part preferably contains structural units such as neutral kneading and / or forward kneading and / or reverse kneading. Used to increase stress.

  In addition to the method of consistently producing the polylactic acid composition (A) from the polylactic acid (B) and (C), the stereogenicity (S value) of the polylactic acid composition (D) is at least 80%. At that time, after the polylactic acid resin composition (D) is solidified once, a crystallization accelerator is added, and a second heat treatment is performed by melt kneading at 240 ° C. to 300 ° C. Producing the composition (A) is also a method that can be advantageously used in quality control, process control, and the like.

  When the polylactic acid resin composition is solidified, if the S value is less than 80%, when performing the second heat treatment step, a step for increasing the S value to at least 80% is necessary for the reason described above, which is preferable in terms of production efficiency. Absent. The S of the solidified composition is more preferably 90% or more, particularly preferably 95% or more. That is, when the S value reaches at least 80%, the polylactic acid composition (D) can be solidified once, but the composition (D) is substantially amorphous, that is, polylactic acid (B). , (C) homocrystals are preferably not included. When the composition (D) contains the homocrystals of polylactic acid (B) and (C), in the second heat treatment, the homocrystal can be melted and stereolated in the presence of a crystallization accelerator. Compared to melting and stereoifying the amorphous polylactic acid (B) and (C) components, it takes a long time and is not only inefficient, but also the quality such as hue may deteriorate during this time This is because it is large. That is, in order to eliminate such a problem, a method in which the second heat treatment step is carried out while the polylactic acid composition (D) obtained in the first heat treatment step is kept in a molten state is preferably employed.

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

These organic fillers may be those 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 cardboard, cardboard, paper tube, etc., and any paper processed from plant fiber may be used. To newspaper paper and cardboard pulverized products such as corrugated cardboard, cardboard and paper tubes are preferred. The wood may be any kind of softwood such as pine, cedar, firewood or fir, or hardwood such as beech, shii or eucalyptus.
The paper powder is not particularly limited as long as the requirements of the present invention are satisfied, but it is preferable to contain an adhesive from the viewpoint of moldability. The adhesive is not particularly limited as long as it is usually used when processing paper, and emulsion adhesives such as vinyl acetate resin emulsion and acrylic resin emulsion. Examples thereof include polyvinyl alcohol-based adhesives, cellulose-based adhesives, natural rubber-based adhesives, starch paste, and hot-melt adhesives such as ethylene-vinyl acetate copolymer resin adhesives and polyamide-based adhesives. Of these, emulsion adhesives, polyvinyl alcohol adhesives and hot melt adhesives are preferred, and emulsion adhesives and polyvinyl alcohol adhesives are more preferred.

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

  As paper powder, chemicals generally used as papermaking raw materials from the viewpoint of moldability, for example, sizing agents such as rosin, alkyl ketene dimer and alkenyl succinic anhydrides, paper strength enhancers 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 Cleaning agents such as hydrogen, organic substances such as antifoaming agents, pigment dispersants and lubricants, aluminum sulfate used as a fixing agent for sizing agents, as well as sodium hydroxide and magnesium hydroxide used as raw materials for papermaking Including inorganic substances such as sodium sulfate, sodium silicate, aluminum chloride, sodium chlorate Preferred.

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

  As the inorganic filler used in the present invention, a fibrous, plate-like, or powder-like material used for reinforcing ordinary thermoplastic resins can be used. Specifically, for example, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, imogolite, sepiolite, asbestos, slag fiber , Zonolite, Elestite, Gypsum fiber, Silica fiber, Silica. Fibrous inorganic fillers such as alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, layered silicate, layered silicate exchanged with organic onium ions, glass flakes, non-swellable mica, graphite, metal Foil, ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, powdered silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, Examples thereof include plate-like and granular inorganic fillers such as titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dosonite and clay.

A layered silicate exchanged with organic onium ions is an inclusion compound in which exchangeable cations existing between layers are exchanged with organic onium ions. Layered silicates with exchangeable cations between layers have a structure in which plates with a width of 0.05 to 0.5 μm and a thickness of 0.6 to 1.5 nm are stacked, and exchanges between the layers of the plates Have positive cations. The cation exchange capacity is 0.2 to 3 meq / g, and the cation exchange capacity is preferably 0.8 to 1.5 meq / g.
Specific examples of the layered silicate include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halosite, kanemite, and kenyanite, Li-type fluorine teniolite, Examples thereof include swellable mica such as Na-type fluorine teniolite, Li-type tetrasilicon fluorine mica, and Na-type tetrasilicon fluorine mica, which may be natural or synthetic. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Li type fluorine teniolite and Na type tetrasilicon fluorine mica are preferable. Examples of the exchanged cation and organic onium ion include ammonium ion, phosphonium ion, and sulfonium ion. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred because of their high ion exchange properties. The ammonium ion may be any of primary to quaternary ammonium ions.

  Examples of the primary ammonium ion include decyl, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like. Examples of secondary ammonium ions include methyl dodecyl ammonium and methyl octadecammonium. Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium. Examples of quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium, trimethyloctylammonium, trimethyldodecylammonium, trimethyl. Examples include alkyltrimethylammonium ions such as octadecylammonium, dimethyldioctylammonium, dimethyldidodecylammonium, dimethyldioctadecylammonium, dimethyldialkylammonium ion, trioctylammonium, tridecylammonium ion, and benzethonium ion having two benzene rings. That.

  In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, having an amino group at the terminal Examples also include ammonium ions derived from polyalkylene glycols. Among these ammonium ions, trioctylmethylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium and the like can be mentioned. These ammonium ions are generally available as a mixture, so in this case the compound should be understood as the name of a representative compound containing a small amount of analog. These may be used alone or in combination. 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.

The layered silicate in which the exchangeable cation existing between the layers used in the present invention is exchanged with the organic onium ion is reacted with the layered silicate having the exchangeable cation between the layer and the organic onium ion by a known method. Can be easily manufactured. For example, it can be produced by a method using an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method in which a liquid or molten ammonium salt is directly reacted with a layered silicate.
In the present invention, the amount of the organic onium ion used for the layered silicate is the cation exchange capacity of the layered silicate from the viewpoint of the dispersibility of the layered silicate, the thermal stability at the time of melting, the gas generated at the time of molding, and the generation of odor. On the other hand, it is in the range of 0.4 to 2 equivalents, more preferably 0.8 to 1.2 equivalents.

These layered silicates are preferably pretreated with a coupling agent having a reactive functional group in addition to the organic onium salt in order to obtain better mechanical properties. Examples of the coupling agent having such a reactive functional group include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.
Among these inorganic fillers, fibrous or plate-like inorganic fillers are preferable, and glass fiber, wollastonite, aluminum borate whisker, potassium titanate whisker, mica, and kaolin, a cation-exchanged layered silicate. Is preferred. The aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more. Such a filler may be coated or converged with a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, and may be treated with a coupling agent such as aminosilane or epoxysilane. Also good.
The blending amount of the inorganic filler of the present invention is preferably used in the range of 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 50 parts by weight with respect to 100 parts by weight of polylactic acid. Particularly preferably, a range of 1 to 30 parts by weight, most preferably 1 to 20 parts by weight is selected.

(Thermoplastic resin (H))
The polylactic acid resin composition (A) of the present invention can contain a thermoplastic resin other than the polylactic acid resin, if desired. The thermoplastic resin is not particularly limited, and is not limited to polyester resin other than polylactic acid resin, polyamide resin, polyacetal resin, polyolefin resin such as polyethylene resin and polypropylene resin, polystyrene resin, acrylic resin, polyurethane resin, chlorinated resin. Polyethylene resin, chlorinated polypropylene resin, aromatic and aliphatic polyketone resin, fluorine resin, polyphenylene sulfide resin, polyether ketone resin, polyimide resin, thermoplastic starch resin, AS resin, ABS resin, AES resin, ACS resin, poly Vinyl chloride resin, polyvinylidene chloride resin, vinyl ester resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenol Alkylene oxide resins, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, and thermoplastic resins such as polyvinyl alcohol resins. In particular, it is preferable to blend at least one selected from polyester resins other than polyacetal resins and polylactic acid resins, for example, polyester resins such as PET, PPT, BPT, and PEN, and polyamide resins. By blending these resins, it becomes possible to obtain compositions and molded articles having the excellent characteristics of these resins.

The polyacetal resin may be a polymer having an oxymethylene unit as a main repeating unit and a so-called polyacetal homopolymer made of formaldehyde or trioxane as a raw material, or mainly composed of oxymethylene units and having 2 to 8 adjacent groups in the main chain. It may be any of so-called polyacetal copolymers containing 15 mol% or less of oxyalkylene units having carbon atoms, and may be any of copolymers containing other constituent units, that is, block copolymers, terpolymers, and crosslinked polymers. These may be used alone or in combination of two or more.
Of these, a polyacetal copolymer is preferable, and a copolymer containing 2% by weight or less of an oxyalkylene unit having 2 adjacent carbon atoms in the main chain or an oxyalkylene unit having 4 adjacent carbon atoms in the main chain is 0%. More preferred are copolymers containing from 2 to 1.4% by weight or less, copolymers containing up to 2% by weight of oxyalkylene units having 2 adjacent carbon atoms in the main chain or 4 adjacent in the main chain Particularly preferred are copolymers containing from 0.5 to 3% by weight of oxyalkylene units having carbon atoms.
The viscosity of the polyacetal resin is not particularly limited as long as it can be used as a molding material, but the melt flow rate (MFR) can be measured by the ASTM 1238 method, and the MFR is in the range of 1.0 to 50 g / 10 min. Those of 1.3 to 35 g / 10 min are particularly preferred.

  The polyacetal resin includes 2,2′-methylenebis (4-methyl-6-tert-butylphenol), calcium ricinoleate, cyanoguanidine, hexamethylenebis (3,5-ditert-butyl-4-hydroxyhydrocyanate), Melanin-formaldehyde resin, nylon 6/66, nylon 66/610/6, nylon 612/6, tetrakis [methylene (3.5-di-t-butyl-4-hydroxyhydrocyanate)] methane, 1,6-hexane Diol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol [3- (3,5-di-t-butyl-5-methyl-4-hydroxyphenyl) propionate] It is preferable that at least one kind is contained. By blending the polyacetal resin in the present invention, a molded article having excellent surface properties, moldability, mechanical properties, durability, and toughness, and a composition that provides the molded article can be obtained.

In the present invention, the polyester resin is selected from (i) a dicarboxylic acid or an ester-forming derivative thereof and dial or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or an ester-forming derivative thereof, and (c) a lactone. It is a polymer or copolymer formed by gun condensation of more than one species, and is a thermoplastic polyester resin other than polylactic acid.
Examples of the dicarboxylic acid or its ester-forming derivative include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and bis (4-carboxyl). Phenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium sulfoisophthalic acid, 5-sodium sulfoisophthalic acid, and other aromatic dicarboxylic acids, oxalic acid, succinic acid, dimer acid, etc. Examples thereof include alicyclic dicarboxylic acid units such as aliphatic dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

Examples of the diol or its ester-forming derivative include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, 1,3-trimethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neo Pentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, dimer diol, or the like, or a long-chain glycol having a molecular weight of 200 to 100,000, That is, polyethylene glycol, polytrimethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl, hydroquinone, t-butyl hydro Examples include quinone, bisphenol A, bisphenol S, bisphenol F, and ester-forming derivatives thereof.
Examples of the hydroxycarboxylic acid include glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, oligo or polycaprolactone, and ester-forming derivatives thereof. Can be mentioned. Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

  Examples of these polymers or copolymers include polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene naphthalate, poly 1,3-trimethylene terephthalate, poly 1,3-trimethylene (terephthalate / isophthalate), Poly 1,3-trimethylene naphthalate, polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene naphthalate, polybutylene (terephthalate / isophthalate), polybutylene terephthalate. Polybutylene adipate block copolymer, polybutylene terephthalate. Poly-ε-caprolactone copolymer, bisphenol A (terephthalate / isophthalate), poly (cyclohexanedimethylene / ethylene) terephthalate, poly (1,4-cyclohexanedimethylene / ethylene) (terephthalate / isophthalate), polybutylene (terephthalate) / Isophthalate) / bisphenol A, polyethylene ((terephthalate / isophthalate) / bisphenol A) and other aromatic polyesters, polyethylene (terephthalate / succinate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sulfoisophthalate / adipate) , Polyethylene (terephthalate / adipate), polyethylene (terephthalate / sebacate), polycyclohexanedimethylene tele Talate, polycyclohexanedimethylene (terephthalate / isophthalate), polybutylene (terephthalate / succinate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polyethylene terephthalate-polyethylene glycol polyether ester copolymer, polybutylene terephthalate -Polyethylene glycol polyether ester copolymer, polybutylene terephthalate-poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate-poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate- Poly (polyethylene oxide / polypropylene oxide) glycol block copolymer Polybutylene (terephthalate / isophthalate) -poly (polyethylene oxide / polypropylene oxide) glycol block copolymer, polybutylene terephthalate-polybutylene adipate block copolymer, polybutylene terephthalate, poly-ε-caprolactone copolymer, etc. Alternatively, a copolymer obtained by copolymerizing an aliphatic polyester with an aromatic polyester, polyethylene oxalate, polybutylene oxalate, polyneopentyl glycol oxalate, polyethylene succinate, polybutylene succinate, polybutylene adipate, polyethylene adipate, polybutylene (Succinate / adipate), polyethylene (succinate / adipate), polyhydroxybutyric acid and β-hydroxybutyric acid and β- Polyhydroxyalkanoate such as copolymer of Dorokishi valeric acid, polycaprolactone, polybutylene succinate. Examples thereof include aliphatic polyesters such as carbonate, and copolymerized liquid crystalline polyesters such as p-oxybenzoic acid / polyethylene terephthalate and p-oxybenzoic acid / 6-oxy-2-naphthoic acid.

  Among these, a polymer obtained by polycondensation of aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof as main components is preferable. Specifically, polybutylene terephthalate, polytriethylene is preferable. Methylene terephthalate, polyethylene terephthalate, poly (cyclohexanedimethylene / ethylene) terephthalate, polybutylene naphthalate, polybutylene terephthalate / isophthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate. Polyether glycol copolymer of polyethylene glycol, polyethylene terephthalate. Polyether ester copolymer of polyethylene glycol, polybutylene terephthalate. Poly (tetramethylene oxide) glycol polyether ester copolymer, polybutylene terephthalate / isophthalate-poly (tetramethylene oxide) glycol polyether ester copolymer, polybutylene (terephthalate / adipate), polyethylene (terephthalate / adipate) Can be preferably mentioned.

  Ratio of aromatic dicarboxylic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of the above aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components Is more preferably 50 mol% or more, and more preferably 60 mol% or more.

  Among these, a polymer obtained by polycondensation of terephthalic acid or its ester-forming derivative and butanediol or its ester-forming derivative as main components is more preferred. Specifically, polybutylene terephthalate, polybutylene (terephthalate / Isophthalate), polybutylene terephthalate-polyethylene glycol polyether ester copolymer, polybutylene terephthalate. Preferred examples include poly (tetramethylene oxide) glycol polyether ester copolymers, polybutylene (terephthalate / isophthalate) -poly (tetramethylene oxide) glycol polyether ester copolymers, and polybutylene (terephthalate / adipate). . The ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of terephthalic acid or its ester-forming derivative and butanediol or its ester-forming derivative as a main component is 50 mol%. More preferably, it is more preferably 60 mol% or more.

  Preferable examples of the thermoplastic polyester resin used in the present invention include polyester carbonate and polyhydroxyalkanoate. Specifically, polybutylene succinate. Preferable examples include carbonate, polyhydroxybutyric acid, and a copolymer of β-hydroxybutyric acid and β-hydroxyvaleric acid. These may be used alone or in combination of two or more. In the present invention, a resin composition excellent in surface properties, moldability, mechanical properties, heat resistance, and toughness can be obtained by blending thermoplastic polyester.

  In the present invention, the polyamide resin is a thermoplastic resin having an amide bond starting from an amino acid, lactam or diamine and dicarboxylic acid. Examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid, and examples of lactam include ε-caprolactam and ω-laurolactam.

Examples of diamines include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 5-methylnonamethylene diamine, 2,4-dimethyloctamethylene diamine, and metaxylylene diene. Amine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3,8-bis (aminomethyl) tricyclodecane, bis (4-Aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine and the like can be mentioned.
Dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5- Examples include sodium sulfoisophthalic acid, hexahydroterephthalic acid, and diglycolic acid.

  Preferred examples of the polyamide used in the present invention include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (mylon 66), polyhexamethylene sebacamide (nylon 610). ), Polyhexamethylene dodecamide (nylon 612), polyundecane methylene adipamide (nylon 116), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polyterephthalamide (nylon 11T (H)) And their copolymerized polyamides and mixed polyamides. Among these, nylon 6, nylon 11, nylon 12, nylon 610, nylon 612, nylon 116, and copolymerized polyamides and mixed polyamides thereof are preferable, and nylon 6, nylon 11, and nylon 12 are particularly preferable. The melting point of the polyamide resin used from the viewpoint of the thermal stability of the polylactic acid resin and the filler is preferably 90 to 230 ° C. By blending a polyamide resin in the present invention, a resin composition and a molded article excellent in surface properties, moldability, mechanical properties, heat resistance and toughness can be obtained.

The polycarbonate used in the present invention has a repeating unit of the formula (7)
—O—K ¹ —O—CO— (7)
(In the formula, K ¹ is an alkylene group which may have a substituent having 2 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 6 to 20 carbon atoms, or a substitution having 6 to 20 carbon atoms. An arylene group which may have a group, an arylenealkylenearylene group or an arylenealkylidenearylene group), and K ¹ may be composed of a plurality of groups. . Such a polycarbonate is produced by a reaction between a dihydroxy compound and a carbonate bond-forming compound. Currently industrially, interfacial polymerization is employed when phosgene is used as the carbonate-forming compound, and melt polymerization is employed when diphenyl carbonate is used. The polycarbonate of the present invention can be used satisfactorily even if it is produced by either the interfacial polymerization method or the melt polymerization method.

  Examples of the aliphatic dihydroxy compound used in the present invention include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, 1,3-trimethylene glycol, 1,2-propylene glycol, 1,4-butanediol, Neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, dimer diol, etc., or a long chain with a molecular weight of 200 to 100,000 Examples of the glycol include polyethylene glycol, polytrimethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Specific examples of the aromatic dihydroxy compound include 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxy). Phenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4 -Hydroxy-3-phenylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis ( 4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, α, α ′ -Bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane 2,2,2 ′, 2′-tetrahydro-3,3,3 ′, 3′-tetramethyl-1,1′-spirobis [1H-indene] -6,6′-diol, 4,4′-dihydroxydiphenylsulfone 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl ether, etc., which may be used alone or in combination of two or more. Can be used.

  Among them, bisphenol A, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) Fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m -A homopolymer or a copolymer obtained by using at least one bisphenol selected from the group consisting of diisopropylbenzene is preferred, and a homopolymer of bisphenol A and a copolymer mainly comprising bisphenol A are preferably used. Is done. In addition, it is also possible to incorporate various monomers other than the above-mentioned one into the polycarbonate main chain with a desired purpose within a range not contrary to the purpose of the present invention by a conventionally known method.

For example, in a polymer having a carbonate unit of an aromatic dihydroxy compound as a main repeating unit, ethylene glycol, 1,4-butanediol, polyethylene glycol, 1,4-cyclohexanedimethanol, 3,9-bis (1,1-dimethyl) 2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, tricyclodecane dimethanol, and other aliphatic and cycloaliphatic diols and polyols to achieve the desired purpose It is possible to introduce it.
Furthermore, aromatic polyhydroxy compounds such as 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane as monomers that can be introduced Aliphatic, aromatic oxycarboxylic acids such as lactic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, adipic acid, dodecanedioic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, pyromellitic acid And dicarboxylic acids such as trimellitic acid, polycarboxylic acids and the like. By blending a carbonate resin in the present invention, a resin composition and a molded article excellent in surface properties, moldability, mechanical properties, heat resistance and toughness can be obtained.

(Impact resistance improver)
The impact resistance improver used in the present invention can be used to improve the impact resistance of thermoplastic resins, and is not particularly limited. For example, at least one selected from the following various impact resistance improved goods 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 Its 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) Coalescence, styrene Soprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene graft copolymerized with styrene, butadiene-acrylonitrile copolymer), polyisobutylene, isobutylene and butadiene Or a copolymer with isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber and the like can be mentioned.

In addition, it is composed of various cross-linking degrees, various micro structures such as cis structure, trans structure, etc., a core layer and one or more shell layers covering it, and adjacent layers are composed of heterogeneous polymers. A so-called core-shell type multi-layer structure polymer can also be used. Furthermore, the various (co) polymers mentioned in the above specific examples may be any of randomand copolymers, block copolymers, block copolymers, etc., and can be used as the impact resistance improver of the present invention. In producing these (co) polymers, it is also possible to copolymerize monomers such as other olefins, dienes, aromatic vinyl compounds, (meth) acrylic acid, (meth) acrylic acid esters, etc. is there.
Among these impact modifiers, a polymer containing an acrylic unit and a copolymer containing a unit having an acid anhydride and / or a glycidyl group are preferred. Preferred examples of the (meth) acrylic unit here include a methyl methacrylate unit, an ethyl acrylate unit, a methyl acrylate unit and a butyl acrylate unit, and a unit having an acid anhydride group or a glycidyl group. Preferable examples include maleic anhydride units and glycidyl methacrylate units.

Further, the impact resistance improving material is preferably a multilayer polymer called a so-called core-shell type, which is composed of a core layer and one or more shell layers covering the core layer, and an adjacent layer is composed of a different polymer. It is more preferable that it is a multilayer structure polymer which contains a methyl (meth) acrylate unit in a shell layer. Such a multilayer structure polymer preferably contains a (meth) 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 resistance improver is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.
In the present invention, the amount of the thermoplastic resin other than polylactic acid is preferably in the range of 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of polylactic acid. More preferably, it is -70 weight part, and it is especially preferable that it is 5-50 weight part.

(Stabilizer (I))
In the present invention, various stabilizers are preferably blended. As the stabilizer (E) used in the present invention, those usually used for stabilizers for thermoplastic resins 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 body excellent in mechanical properties, moldability, heat resistance and durability of the composition organism.

(Antioxidant)
Examples of the antioxidant used in the present invention include hindered phenol compounds, hindered amine compounds, phosphite compounds, and thioether compounds. Examples of hindered phenol compounds used in the present invention include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- ( 3'-methyl-5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1, 6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) -propionate], 2,2′-methylene-bis (4-methyl-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl) Til-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, 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.

Specifically, the phosphite compound used in the present invention is preferably one in which at least one P—O bond is bonded to an aromatic group. 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 phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl-ditridecyl) phosphite, 1,1,3- Tris (2-methyl-4-ditridecyl phosphite-5-t-butylphenyl) butane, tris (mixed mono and dinonylphenyl) And phosphite, 4,4′-isopropylidenebis (phenyl-dialkylphosphite) and the like, tris (2,6-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t) -Butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, tetrakis (2,6-di-t-butylphenyl) 4,4'- Biphenylene phosphite and the like can be preferably used.
Specific examples of the thioether compound 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-myristyl) Thiopropionate), pentaerythritol tetrakis (3-stearyl thiopropionate) and the like.

(Light stabilizer)
Specific examples of the light stabilizer used in the present invention include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds and hindered amine compounds. it can.
Specific examples of the benzohenone compound include benzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,2′4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4- Dodecyloxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy -4-methoxy-2 ' Carboxy benzophenone, 2-hydroxy-4- (2-hydroxy-3-methylcyclohexyl acryloxy-isopropoxyphenyl) benzophenone.

  Specific examples of benzotriazole compounds include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-t-butyl-4′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′ , 5′-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) Phenyl] -2H- benzotriazole, 2- (4'Okutokishi 2'-hydroxyphenyl) benzotriazole and the like.

Specific examples of the aromatic benzoate compound include alkylphenyl salicylates such as pt-butylphenyl salicylate and p-octylphenyl salicylate.
Specific examples of oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, 2- And ethoxy-3′-dodecyl oxalic acid bisanilide.
Specific examples of the cyanoacrylate compound include ethyl-2-cyano-3,3′-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, and the like.

  Specific examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2. , 2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy -2,2,6,6-tetramethylpiperidine, 4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyl Oxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- ( Tylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6 , 6-Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethylpi-4-peridyl) adipate Bis (2,2,6,6-tetramethylpi-4-peridyl) terephthalate, 1,2-bis (2,2,6,6-tetramethylpi-4 Peridyloxy) -ethane, α, α′-bis (2,2,6,6-tetramethylpi-4-peridyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) -tolylene- 2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4- Piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- "2- {3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2, , 6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethanol Things can be mentioned.

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

(Carboxyl group reactive terminal blocking agent (G))
In this invention, it is preferable to mix | blend a carboxyl group reactive terminal blocker. The carboxyl group-reactive end capping agent used in the present invention is not particularly limited as long as it is an agent capable of capping the carboxyl end group of the polymer. In the present invention, the carboxyl group-reactive 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 such a carboxy group reactive end-capping agent, it is preferable to use at least one compound selected from a carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound, and an isocyanate compound, and among them, a carbodiimide compound, an epoxy compound, Oxazoline compounds and isocyanate compounds are preferred.

  The carbodiimide compound used in the present invention is a compound having one or more carbodiimide groups in the molecule, preferably containing 0.1 to 5% by weight of isocyanate groups, and having a carbodiimide equivalent of 200 to 500. By containing a small amount of an isocyanate group, the wet heat stability of the composition of the carbodiimide compound and the polylactic acid resin is further improved, which is preferable for the purpose of the present invention. When the isocyanate group is present in the carbodiimide compound, not only the effect of the combined use of the isocyanate compound appears, but 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, geo-toluylcarbodiimide, di-p-toluylcarbodiimide, bis (P-nitrophenyl) carbodiimide, bis (p-aminophenyl) carbodiimide, bis (p Hydroxyphenyl) carbodiimide, bis (p-chlorophenyl) carbodiimide, bis (o-chlorophenyl) carbodiimide, bis (o-ethylphenyl) carbodiimide, bis (p-ethylphenyl) carbodiimide bis (o-isopropylphenyl) carbodiimide, bis (p -Isopropylphenyl) carbodiimide, bis (o-isobutylphenyl) carbodiimide, bis (p-isobutylphenyl) carbodiimide, bis (2,5-dichlorophenyl) carbodiimide, p-phenylenebis (o-toluylcarbodiimide), p-phenylenebis ( Cyclohexylcarbodiimide, p-phenylene bis (p-chlorophenylcarbodiimide), 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide, hexa Tylene bis (cyclohexylcarbodiimide), ethylenebis (phenylcarbodiimide), ethylenebis (cyclohexylcarbodiimide), bis (2,6-dimethylphenyl) carbodiimide, bis (2,6-diethylphenyl) carbodiimide, bis (2-ethyl-6- Isopropylphenyl) carbodiimide, bis (2-butyl-6-isopropylphenyl) carbodiimide, bis (2,6-diisopropylphenyl) carbodiimide, bis (2,6-di-t-butylphenyl) carbodiimide, bis (2,4,6 -Trimethylphenyl) carbodiimide, bis (2,4,6-triisopropylphenyl) carbodiimide, bis (2,4,6-tributylphenyl) carbodiimide, di-β-naphthylcarbosiimide, N-tolyl-N ′ Examples include mono- or dicarbodiimide compounds such as -cyclohexylcarbosiimide and N-tolyl-N'-phenylcarbosiimide.

Of these, bis (2,6-diisopropylphenyl) carbodiimide and 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide are preferable from the viewpoint of reactivity and stability.
Of these, industrially available dicyclohexylcarbodiimide and diisopropylcarbodiimide are also suitable. Moreover, what was manufactured by the various method can be used suitably for the polycarbodiimide compound contained in the said carbodiimide compound.

A conventionally known method for producing a polycarbodiimide compound, for example, US Pat. No. 2,941,956, Japanese Patent Publication No. 47-33279, Org. Chem. 28, 2069-2075 (1963), Chemical Review 1981, Vol. 81 no. 4, p619-621 etc. can be used.
For example, poly (1,6-cyclohexanecarbodiimide), poly (4,4′-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4, 4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly ( Examples thereof include polycarbodiimides such as p-tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyldisopropylphenylenecarbodiimide), and poly (triethylphenylenecarbodiimide). Furthermore, a commercially available polycarbodiimide compound as the polycarbodiimide compound can be suitably used without the need for synthesis. Examples of such commercially available polycarbodiimide compounds include Carbodilite LA-1 and HMV-8CA sold under the trade name of Carbodilite commercially available from Nisshinbo Co., Ltd. Examples of the organic diisocyanate preferably used as a raw material for producing such polycarbodiimide include aromatic, aliphatic and alicyclic diisocyanates and mixtures thereof.

  Specific compounds include 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-triisocyanate. Diisocyanate, 2,6-tolylene diisocyanate, (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate) mixture, hexamethylene diisocyanate, cyclohexane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate , Dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl It can be exemplified 1,4-diisocyanate, and the like. By appropriately using a monoisocyanate compound at the time of production of the polycarbodiimide, the degree of polymerization can be controlled by reacting with the terminal isocyanate of the polycarbodiimide compound. Examples of such monoisocyanate compounds include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.

The end-capping agent that seals the end of the polycarbodiimide compound and controls the degree of polymerization thereof is not limited to the above-mentioned monoisocyanate, but is an active hydrogen compound that can react with an isocyanate group, such as aliphatic or aromatic. Or an alicyclic compound having one OH group, ═NH group, —NH ₂ group, —COOH group, —SH group or epoxy group in the molecule, methanol, ethanol, phenol, cyclohexanol, N -Methylethanolamine, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, diethylamine, dicyclohexylamine, butylamine, cyclohexylamine, butyric acid, benzoic acid, cyclohexane acid, ethyl mercaptan, allyl mercaptan, thiophenol Etc. can be illustrated. The carbodiimide production reaction is based on a decarboxylation condensation reaction of an organic isocyanate in the presence of a carbodiimidization catalyst. Examples of the carbodiimidization catalyst include conventionally known catalysts such as organophosphorus compounds and organometallic compounds.

As the organic phosphorus compound, phospholene oxides are preferable from the viewpoint of catalytic activity. Specifically, for example, 3-methyl-1-phenyl-2-phospholene-1-oxide, 3-methyl-1-ethyl-2-phospholene-1-oxide, 1,3-dimethyl-2-phospholene-1-oxide 1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 1-methyl-2-phospholene-1-oxide and their double bond isomers. Of these, 3-methyl-1-phenyl-2-phospholene-1-oxide, which is easily available industrially, is preferable.
The organometallic compound is represented by the formula (8)
D- (OE) d (8)
(Wherein D is sodium, potassium, calcium, barium, titanium, vanadium, tungsten, hafnium, zirconium, lead, manganese, nickel, E is an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms. Or an aryl group, where d represents the valence of the metal element D.)
As an epoxy compound that can be used as a carboxyl group-reactive end-capping agent in the present invention, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, a glycidyl amide compound, and an alicyclic epoxy compound are preferable. Can be used. By blending such an agent, a polylactic acid resin composition and a molded article excellent in mechanical properties, moldability, heat resistance, and durability can be obtained.

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

  Examples of glycidyl ester compounds include, for example, glycidyl benzoate, glycidyl p-toluate, glycidyl cyclohexane carboxylic acid, glycidyl stearate, glycidyl stearate, glycidyl palmitate, glycidyl palmitate, glycidyl oleate Ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, methyl terephthalic acid glycidyl ester, hexahydrophthalic acid diglycidyl ester , Tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl Ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, etc. Can be mentioned. Of these, glycidyl benzoate and glycidyl versatate are preferred.

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

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

  Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexyl-3,4-cyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl- 4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic And acid imide, N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-toluene 4,5-epoxycyclohexane-1,2-dicarboxylic imide, and the like. As other epoxy compounds, epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and the like can be used.

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

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

  Further, 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′- Ethylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-propylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-butylene bis (5 6-dihydro-4H-1,3-oxazine), 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylenebis (5,6 -Dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-naphthylene (5,6-dihydro-4H) -1,3-oxazine), 2,2'-P, P'- Phenylene bis (5,6-dihydro-4H-1,3-oxazine), and the like. Furthermore, the polyoxazine compound etc. which contain the above-mentioned compound as a monomer unit are mentioned. Among the oxazoline compounds and oxazine compounds, 2,2'-m-phenylenebis (2-oxazoline) and 2,2'-p-phenylenebis (2-oxazoline) are preferably selected.

  As an example of the isocyanate compound that can be used as the carboxyl group-reactive end-capping agent used in the present invention, for example, aromatic, aliphatic, 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. Specific examples of the diisocyanate include 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2 , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate) mixture, hexamethylene diisocyanate, cyclohexane-4,4′-diisocyanate, xylylene diisocyanate , Isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2, - it can be exemplified diisopropylphenyl-1,4-diisocyanate, and the like. Among these isocyanate compounds, aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate and phenyl isocyanate are preferable.

The carboxyl group reactive end-capping agent can be used by appropriately selecting one or more compounds. The resin composition of the present invention may be sealed with a carboxyl group terminal or an acidic low molecular compound depending on the use to be used as a molded body. From the viewpoint of hydrolysis resistance, the acid value in the resin composition is preferably 20 equivalents / 10 ⁶ g or less, more preferably 10 equivalents / 10 ⁶ g or less, and more preferably 5 equivalents / 10 ^6. It is particularly preferred that it is g or less.

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

  In the present invention, when a carboxyl group-reactive end capping agent is used, a reaction catalyst for the end capping agent may be used. The reaction catalyst is a compound having an effect of promoting the reaction between the carboxyl group-reactive end-capping agent and the polymer end, or the carboxyl group of the acidic low molecular weight compound, and a compound capable of promoting the reaction with a small amount of addition. Is preferred. Examples of such compounds include alkali (earth) metal compounds, tertiary amines, imidazole compounds, quaternary ammonium salts, phosphine compounds, phosphonium compounds, phosphate esters, organic acids, Lewis acids, and the like.

  Specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, Potassium stearate, lithium stearate, sodium benzoate, potassium benzoate, lithium benzoate, sodium borohydride, potassium borohydride, lithium borohydride, sodium phenylborate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid Alkali metal compounds such as dilithium hydrogen, bisphenol A disodium, bisphenol A dipotassium, bisphenol A dilithium, bisphenol A dicesium, calcium hydroxide, barium hydroxide, magnesium hydroxide Strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, stearin Alkaline earth metal compounds such as barium acid, magnesium stearate, strontium stearate, triethylamine, tributylamine, trihexylamine, triamylamine, triethanolamine, dimethylaminoethanol, N, N, N ′, N′-tetra Methyltriethylenediamine, dimethylaniline, dimethylbenzylamine, 2- (dimethylaminomethyl) phenol, pyridine, picoline, 1,8-di Tertiary amines such as zabicyclo (5,4,0) undecene-7, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-ethyl-4-methylimidazole, 2-methyl-4-phenylimidazole, etc. A quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzyl hydroxide, trimethylbenzyl chloride, triethylbenzyl chloride, tripropylbenzyl chloride, N-methylpyridinium chloride, Phosphine compounds such as tributylphosphine, trioctylphosphine, triphenylphosphine, tetramethylphosphonium hydroxide, tetramethylphosphonium Phosphonium salts such as um chloride, tetrabutylphosphonium chloride, tetraphenylphosphonium hydroxide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, trimethylbenzylphosphonium hydroxide, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tris (butoxyethyl) Phosphates, triphenyl phosphates, tricresyl phosphates, trixyl phosphates, cresyl diphenyl phosphates, octyl diphenyl phosphates and other phosphate esters, succinic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, etc. Organic acid, boron trifluoride, aluminum trichloride, titanium tetrachloride Emissions, and the like Lewis acids such as tin tetrachloride.

  These can be used alone or in combination of two or more. Among them, it is preferable to use an alkali metal compound, an alkaline earth metal compound, and a phosphoric acid ester, and an alkali or alkaline earth metal acid salt is particularly preferable. Particularly preferred are sodium stearate, potassium stearate, calcium stearate, magnesium stearate, sodium benzoate, sodium acetate, potassium acetate, calcium acetate and megnesium acetate. The addition amount of the reaction catalyst is not particularly limited, but is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight per 100 parts by weight of the polylactic acid resin (A). More preferably, the content is 01 to 0.1 parts by weight.

(Release agent (J))
In this invention, it is preferable to mix | blend a mold release agent. As the mold release agent used in the present invention, those used for ordinary thermoplastic resins can be used. In particular, fatty acids, fatty acid metal salts, oxy fatty acids, paraffin low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid partial saponified esters, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acid higher alcohols. Examples include esters, fatty acid polyhydric alcohol partial esters, fatty acid polyglycol esters, and modified silicones. By blending these, a polylactic acid resin composition and a molded article excellent in mechanical properties, moldability, and heat resistance can be obtained.
Fatty acids having 6 to 40 carbon atoms are preferred. Specifically, oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montan Examples thereof include acids and mixtures thereof. As the fatty acid metal salt, an antari (earth) metal salt of a fatty acid having 6 to 40 carbon atoms is preferable, and specific examples include calcium stearate, sodium montanate, calcium montanate, and the like. Examples of the oxy fatty acid include 1,2-oxysteric acid. Examples of the fatty acid 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 the fatty acid partial saponified ester include a montanic acid partial saponified ester.

As paraffin, those having 18 or more carbon atoms are preferable, and liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like can be mentioned. As low-molecular-weight polyolefin, for example, those having a molecular weight of 5000 or less are preferable. Examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidation 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. The fatty acid ester preferably has 6 or more carbon atoms, and examples thereof include ethyl stearate, butyl stearate, ethyl behenate, stearyl stearate, stearyl oleate, and rice wax.

Fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol Monostearate, pentaerythritol adipate stearate, 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. In the present invention, the release agent may be used alone or in combination of two or more. The compounding amount of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, based on 100 parts by weight of the polylactic acid resin (A).

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

(Other additives)
Moreover, in this invention, you may contain thermosetting resins, such as a phenol resin, a melamine resin, a thermosetting polyester resin, a silicone resin, an epoxy resin, in the range which is not contrary to the meaning of this invention. Further, in the present invention, a colorant containing a brominated flame retardant, a phosphorus flame retardant, a silicone flame retardant, a flame retardant such as an antimony compound, an organic or inorganic dye, or a pigment within the scope not departing from the gist of the present invention. For example, oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as bitumen, chromates such as zinc chromate, sulfates such as barium sulfate, calcium carbonate, etc. Examples thereof include carbonates, silicates such as ultramarine blue, phosphates such as manganese violet, carbon such as carbon black, and metal colorants such as bronze powder and aluminum powder.
Nitroso series such as naphthol green B, nitro series such as naphthol yellow S, azo series such as naphthol red and chromophthal yellow, phthalocyanine series such as phthalocyanine blue and fast sky blue, condensed polycyclic colorants such as indanthrone blue, etc. Additives such as slidability improvers such as graphite and fluorine resin may be contained. These additives can be used alone or in combination of two or more.
Arbitrary methods are employ | adopted to mix | blend various additives. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a nauter mixer, a Banbury mixer, a kneading roll, a monoaxial or biaxial extruder or the like is appropriately used. A method of molding the polylactic acid resin composition thus obtained can be preferably employed as it is or after it is once formed into pellets with a melt extruder. The shape of the pellet preferably has a shape suitable for molding the pellet by various molding methods. Specifically, the pellet length is preferably 1 to 7 mm, the major axis 3 to 5 mm, and the minor axis 1 to 4 mm. Further, it is preferable that the shape does not vary.

(Molding method)
The polylactic acid resin composition of the present invention is a composition having its own special characteristics, and can be processed into various molded products by methods such as injection molding and extrusion molding. At the time of injection molding, the mold temperature is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and more preferably 70 ° C. or higher from the viewpoint of increasing the crystallization of the molded product and the molding cycle. However, in order to prevent deformation of the product, it is necessary to set it to 140 ° C. or lower. More preferably, 120 ° C. or lower, particularly preferably 110 ° C. or lower is selected. It is practically preferable to set an appropriate temperature in consideration of the characteristics of the device used in such a temperature range.

(Molded body)
Examples of the molded body comprising the composition of the present invention include injection molded bodies, extruded molded bodies, vacuum, compressed air molded bodies, blow molded bodies, etc., and composites with films, sheets, sheet nonwoven fabrics, fibers, cloths, and 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 are used for various housings, gears, gears, etc. It can be used for various applications such as electronic parts, building members, civil engineering members, agricultural materials, automobile parts (interior and exterior parts, etc.) and daily parts. Specifically, notebook PC housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, CDs, DVDs, PDs, FDDs Such as recording medium drive housings and internal parts, copier housings and internal parts, housings and internal parts such as facsimiles, and parabolic antennas. Mention electronic components.
Furthermore, VTR housings and internal parts, TV housings and internal parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio. Homes such as laser disk (registered trademark), audio equipment parts such as compact disks, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Mention office equipment parts.

  Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, motor cases, switches, capacitors, variable capacitor cases , Optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder Electricity such as transformer members and coil bobbins. Electronic parts, sash door pulleys, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, heat insulation walls, adjusters, plastic restraints, ceiling fishing gear, stairs, doors, Building materials such as floors, fishing lines, fish nets, seaweed aquaculture nets, fishing food bags and other fishery related parts, vegetation nets, vegetation mats, grass protection bags, grass protection nets, curing sheets, slope protection sheets, fly ash holding sheets, Drain sheet, water retention sheet, sludge. Civil engineering parts such as sludge dehydration bags, concrete formwork, air flow meters, air pumps, thermostat housings, engine mounts, ignition bobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pumps Case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base, actuator case for ABS, 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 Caps, vapor canister housings, air cleaner housings, timing belt covers, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various underpants for automobiles, torque control levers, safety Automotive interior parts such as belt parts, register blades, washer levers, window regulator handles, window regulator handle knobs, pasig light levers, sun visor brackets, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, hoods Louver, wheel cover, wheel cap, grill apron cover frame, lamp reflector, lamp base Automotive exterior parts such as cable and door handles, 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, teeth, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, bird-proof sheets, vegetation protection nonwovens, seedling pots, Vegetation pile, seed string tape, germination sheet, house lining sheet, vinyl stopper for agriculture, slow-release fertilizer, rooting sheet, garden net, insect net, young tree net, print laminate, fertilizer bag, sandbag, Agricultural materials such as pest prevention nets, attracting strings, windproof nets, paper diapers, sanitary goods packaging materials, cotton swabs Sanitary products such as carp and toilet seat wipes, medical non-woven fabrics (for sutures, anti-adhesion membranes, prosthetic repair materials, etc.), wound dressings, wound tape bandages, adhesive base fabrics, surgical sutures, fracture reinforcements Calendars for medical supplies such as medical films, packaging films for stationery, clothing, food, trays, blisters, knives, forks, spoons, plastic cans, pouches, containers, tanks, baskets, etc. Tableware, hot fill containers, microwave cooking containers, cosmetic containers, wraps, foam cushioning materials, paper laminates, shampoo bottles, beverage bottles, cups, candy packaging, shrink labels, lid materials, window wipes, envelopes, fruit bowls, Hand cut tape, easy peel packaging, egg pack, HDD packaging, compost bag, recording media packaging, shopping bag, electricity. Container for electronic parts wrapping film. Packaging, natural fiber composite polo shirts, T-shirts, innerwear, uniforms, sweaters, socks, ties and other clothing, curtains, chairs, carpets, tablecloths, futon mats, wallpaper, furoshiki and other interior goods, carrier tape, prints Laminate, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, non-woven fabric hot melt binder, magnetic material, zinc sulfide, electrode material Binders, optical elements, conductive embossed tape, IC trays, golf tees, garbage bags, plastic bags, various nets, toothbrushes, stationery, draining nets, body towels, hand towels, tea packs, drain ditch filters, clear files, Coating agent, adhesive, Emissions, available chairs, tables, cooler boxes, rakes, hose reels, planters, hose nozzles, dining table, the surface of the desk, furniture panels, kitchen cabinets, pen caps, as such as gas lighters.

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples. Each physical property value was also determined by the following method.
1. Measuring method (1) Weight average molecular weight and number average molecular weight (Mn) of polymer:
The weight average molecular weight 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 Shimadzu RID-6A
Column: Toso-TSKgelG3000HXL, TSKgelG4000HXL, TSKgelG5000HXL and TSKguardcocumHXL-L connected in series, or Toso-TSKgelG2000HXL, TSKgelG3000HXL and TSKguardLumX used. Chloroform was used as an eluent, flowed at a temperature of 40 ° C. and a flow rate of 1.0 ml / min, and 10 μl of a sample having a concentration of 1 mg / ml (chloroform containing 1% hexafluoroisopropanol) was injected and measured.
(2) Reduced viscosity (ηsp / c):
1.2 mg of a sample was dissolved in 100 ml of [tetrachloroethane / phenol (volume ratio 1/1) wt mixed solvent] and the reduced viscosity (mL / g) was measured at 35 ° C. using an Ubbelohde viscosity tube.
(3) Crystallization point, melting point, melting enthalpy and proportion of melting peak at 195 ° C. or higher:
Shimadzu DSC-60 differential scanning calorimeter DSC was used. In the measurement, 10 mg of a sample was heated from room temperature to 250 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, allowed to cool for 20 minutes, and again heated to 250 ° C. at 10 ° C./min. Homocrystal melting temperature (Tmh) and stereocomplex crystal melting temperature (Tms), homocrystal melting heat (ΔHmh) and stereocomplex crystal melting heat (ΔHms) in the first scan, crystallization temperature (Tc) in the second scan Asked. The relative crystallinity was determined by measuring the total crystal formation heat (ΔHc) and stereocomplex crystal fusion heat (ΔHms) of homolactic acid and polylactic acid stereocomplex in the first scan using 10 mg of the molded sample. Asked.
Relative crystallinity = {(ΔHms−ΔHc) / ΔHms} * 100
(4) Polylactic acid composition (A) Visual appearance test determination method of molded article:
The visual test was accepted when the molded piece was not deformed and there was no indentation due to the notch pin or it was slight.
A: No deformation in the thickness direction and no deformation by notch pins.
○: There is no deformation in the thickness direction, and slight deformation by the notch pin.
Δ: Slight deformation in the thickness direction, but dents due to notch pins.
X: Deformation in the thickness direction, deformation due to notch pins.

2. The materials used in the examples are as follows.
(1) Polylactic acid resin (B), (C)
B-1: manufactured by Mitsui Chemicals, L-polylactic acid Lacia H100J weight average molecular weight 160,000 B-2: Shimadzu Corporation L-polylactic acid lacty weight average molecular weight, 180,000 B-3: optical purity of 99% or more L-polylactic acid by melt ring-opening polymerization of L-lactide, weight average molecular weight 105,000, molecular weight dispersion = 1.6
C-1: D-polylactic acid by D-lactide melt ring-opening polymerization having an optical purity of 99% or more, weight average molecular weight of 102,000, molecular weight dispersion = 1.6

Polylactic acid B-3 and polylactic acid C-1 were synthesized by the following method.
(Synthesis of polylactic acid B-3)
A vertical stirring tank (40 L) equipped with a full-zone blade equipped with a vacuum pipe, a nitrogen gas pipe, a catalyst, an L-lactide solution addition pipe, and an alcohol initiator addition pipe was purged with nitrogen, and then L-lactide 30 kg, stearyl alcohol 0.69 kg ( 0.023 mol / kg-LD), tin octylate 6.14 g (5.05 × 10 ⁻⁴ mol / 1 Kg LD) was charged, and the temperature was raised to 150 under an atmosphere of nitrogen pressure 106.4 kPa. When dissolved, stirring was started and the internal temperature was further raised to 190 ° C. Since the reaction started when the internal temperature exceeded 180 ° C., cooling was started, and the internal temperature was maintained from 185 ° C. to 190 ° C., and the reaction was continued for 2 hours.
Next, the internal pressure was increased from 2 atmospheres to 5 atmospheres, and the contents were fed to a stirring vessel equipped with a Max Blend blade. While stirring, the reaction was performed at a nitrogen pressure of 106.4 kPa and an internal temperature of 200 ° C. to 210 ° C. for 2 hours, and then the stirring was stopped. The internal pressure was reduced to 13.3 kPa and the amount of lactide was adjusted for 20 minutes. Thereafter, the internal pressure was increased from 2 to 3 atm by nitrogen pressure, and the prepolymer was extruded into a chip cutter to pelletize a prepolymer having a weight average molecular weight of 650,000 and a molecular weight dispersion of 1.5.
After the batch reaction was performed three times, the prepolymer was fed at a rate of 16 kg / hr to the first non-axial vertical stirring blade polymerization apparatus having a volume of 60 L, the catalyst, L-lactide 16 kg / hr, and the tin octylate catalyst. 5.05 × 10 ⁻⁴ mol / 1 kg L-LD per 1 kg of lactide was sent and polymerized at 200 to 210 ° C. for a residence time of 1.2 hours. Transfer, 1.05 mole of phosphoric acid as a deactivator per mole of catalyst was added at the inlet, and the lactide was reduced by an internal pressure of 1.33 kPa and a residence time of 0.5 hours. Turned into. The lactide-reduced polylactic acid B-3 had a weight average molecular weight of 105,000, a molecular weight dispersion of 1.6, and a lactide content of 0.005% by weight.
(Synthesis of polylactic acid C-1)
A similar synthetic experiment was performed using D-lactide to obtain polylactic acid C-1 having a weight average molecular weight of 102,000, a molecular weight dispersion of 1.6, and a lactide content of 0.005% by weight.

(2) Crystallization accelerator (E)
E-1: Talc, Nippon Talc Co., Ltd., fine talc, Micro Ace P6 (average particle size, 4 μm)
E-2: phosphoric acid ester metal salt NA-10 manufactured by Asahi Denka Kogyo Co., Ltd.
E-3: Same NA-11
E-4: Same NA-21
(3) Filler (F)
F-1: Glass fiber made by Nippon Electric Glass Co., Ltd., urethane bundling treatment chopped strand ECS-03T-511
F-2: Wollastonite Partek wickroll 10
F-3: Kaolin: Translink 555 manufactured by Engelhard
(4) Carboxyl group reactive end-capping agent (G)
G-1: Bisphenol A diglycidyl ether, Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.
G-2: Nisshinbo Co., Ltd. Carbodilite LA-1, isocyanate group content 1.5 wt%, carbodiimide equivalent 247
G-3: Carbodilite HMV-8CA manufactured by Nisshinbo Co., Ltd., carbodiimide equivalent 293
G-4: Polycarbodiimide of Synthesis Example 1, isocyanate group content 1.5% by weight, carbodiimide equivalent 214
G-5: Polycarbodiimide of Synthesis Example 2, isocyanate group content 1.7% by weight, carbodiimide equivalent 244

(Synthesis Example 1)
Polycarbodiimide was synthesized based on a synthesis example of a carbodiimide compound described in JP-A-11-80522. That is, 590 parts by weight of 4,4′-dicyclohexylmethane diisocyanate, 62.6 parts by weight of cyclohexyl isocyanate, carbodiimidization catalyst, 6.12 parts by weight of 3-methyl-1-phenyl-2-phospholene-1-oxide were added at 180 ° C., 48 A poly (4,4′-dicyclohexylcarbodiimide) having a polymerization degree of 10 was synthesized by reacting for a period of time.

(Synthesis Example 2)
Polymerization was carried out by reacting 549 parts by weight of tetramethylbiphenylene diisocyanate, 49.5 parts by weight of n-butyl isocyanate, carbodiimidization catalyst and 5.99 parts by weight of 3-methyl-1-phenyl-2-phospholene-1-oxide at 180 ° C. for 48 hours. A poly (tetramethylene carbodiimide) having a degree of 10 was synthesized.

(5) Thermoplastic resin (H)
H-1: Polybutylene (terephthalate / adipate) resin BASF Co., Ltd. Ecoflex H-2: Polybutylene (succinate / adipate) Showa High Polymer Bionere 3001
H-3: Polybutylene succinate. Carbonate Mitsubishi Gas Chemical Co., Ltd. Upec H-4: Bisphenol A polycarbonate; Teijin Chemicals L1250
H-5: Polyamide Toray Co., Ltd. Amilan CM4000
H-6: Butadiene-alkyl acrylate-alkyl methacrylate copolymer, EXL-2602, manufactured by Kureha Chemical Industry Co., Ltd.
H-7 Core-shell type elastomer Mitsubishi Rayon-made Metablen S2001
(6) Stabilizer (I)
I-1: n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, Chiba-Geigy Corp. Made Irganox 1076
I-2: 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, Chiba-Geigy Corp. Made Tinuvin 320
I-3: Tris (2,4-di-t-butylphenyl) phosphite, Chiba-Geigy Corp. Made by Irgafos 168
(7) Release agent (J)
J-1: Partially saponified ester of montanic acid manufactured by Clariant Co., Ltd. Rico wax OP
J-2: Ethylene bis stearamide Nippon Kasei Co., Ltd. SLIPAX E

<Example 1>
(First heat treatment process)
50 parts by weight of polylactic acid B-1 and 50 parts by weight of polylactic acid C-1 were uniformly mixed using a tumbler, and a 30 mmφ vented twin screw extruder (KTX-30 manufactured by Kobe Steel) The mixture was kneaded for 4 minutes while degassing at a cylinder temperature of 240 ° C. and a vacuum of 10 mmHg, and then extruded into cold water from a nozzle to obtain a pellet-shaped composition (D). The resulting composition (D) was in an amorphous state and the stereogenicity was 85%.
(Second heat treatment step)
The obtained composition (D) was dried at 110 ° C. for 5 hours. Thereafter, the composition (D) and 0.3 part by weight of the crystallization accelerator E-1 were uniformly mixed using a tumbler, and a 30 mmφ vented twin screw extruder (Kobe Steel Co., Ltd., KTX-30). Then, the mixture was kneaded for 3 minutes while being deaerated at a cylinder temperature of 260 ° C. and a vacuum degree of 10 mmHg, and then extruded into cold water from a nozzle to obtain a pellet-shaped composition (A). The resulting composition (A) had a stereogenicity of 93%.
(Molding)
After drying the obtained composition (A) at 110 ° C. for 5 hours, using an injection molding machine (SG150U model manufactured by Sumitomo Heavy Industries, Ltd.), the cylinder temperature is 260 ° C. and the mold temperature is 100 ° C. A molded piece for ASTM measurement having a thickness of 3 mm was prepared. At this time, the shortest time in which the test piece was reliably obtained without deformation was taken as the molding cycle. A visual appearance test of the obtained molded piece was performed, and a tensile test was performed according to ASTM method D638. In addition, the crystallization start temperature (Tcc), crystallization enthalpy (ΔHc), and heat of crystal melting and melting (ΔHm) derived from polylactic acid were measured by DSC.

<Examples 2 to 10 and Comparative Examples 1 to 3>
The same operations as in Example 1 were carried out except that the types and amounts of polylactic acid (B), polylactic acid (C), and crystallization accelerator (E) shown in Table 1 were kneaded at the temperatures and times shown in Table 1. Repeated. Table 1 shows the measurement results of the physical properties of the obtained compositions (D) and (A) and the molded pieces. However, only in Example 2, the second heat treatment step was continuously performed without solidifying the composition (D). In Comparative Example 2, the crystallization accelerator (E) was added in the first heat treatment step.
As can be seen from Table 1, the composition (A) of the present invention is excellent in crystallinity and molding cycle. As can be seen from Table 1, the composition (A) blended with the crystallization accelerator (E) after the composition (D) has a degree of stereoification of 80% or more has a high degree of stereoization. It can be seen that it has a relative crystallinity and good moldability.

<Examples 11-13, Comparative Examples 4-6>
In the second heat treatment step, when the crystallization accelerator (E) is added, the carboxyl group-terminal reactive sealant (G), stabilizer (I), mold release agent (type and amount shown in Table 2) A pellet-shaped composition (A) was obtained in the same manner as in Example 1 except that J) was added to the composition (D). However, in Comparative Example 5, as in Comparative Example 2, the crystallization accelerator (E) was added in the first heat treatment step. The results are shown in Table 2. The composition (A) of the present invention had high stereogenicity and crystallinity, good moldability, and high load deflection temperature.

<Examples 14-17, Comparative Examples 7-9>
In the second heat treatment step, when the crystallization accelerator (E) is added, the kinds and amounts of the carboxyl group-terminal reactive sealing agent (G), the stabilizer (I), the release agent ( J) A pellet-shaped composition (A) was obtained in the same manner as in Example 1 except that the filler (F) was added to the composition (D). However, in Comparative Example 8, as in Comparative Example 2, the crystallization accelerator (E) was added in the first heat treatment step. The results are shown in Table 3. The composition (A) of the present invention had high stereogenicity and crystallinity, good moldability, and high load deflection temperature.

<Examples 18-24, Comparative Examples 10-12>
In the second heat treatment step, when the crystallization accelerator (E) is added, the carboxyl group-terminal reactive sealant (G), stabilizer (I), mold release agent (type and amount shown in Table 4) A pellet-shaped composition (A) was obtained in the same manner as in Example 1 except that J), the filler (F), and the thermoplastic resin (H) were added to the composition (D). However, in Comparative Example 11, the crystallization accelerator (E) was added in the first heat treatment step as in Comparative Example 2. The results are shown in Table 4. The composition (A) of the present invention had high stereogenicity and crystallinity, good moldability, and high load deflection temperature.

<Example 25>
0.5 parts by weight of glycerol distearate as a release agent (J) per 100 parts by weight of the composition (A) obtained in Example 1, a 30 mm biaxial ruder (cylinder temperature 190 ° C.) And sent to the T-die of the molding machine. The unstretched film having a thickness of 0.1 mm and a width of 500 mm was obtained by being sandwiched or touched on one side by a mirror surface cooling roll and a mirror surface roll and melt-extruded. The obtained film was a good film having an intensity of 147/127 MPa in the MD / TD direction, a light transmittance of 91%, and 8 fish eyes determined visually in a 100 mm square film cut at random.

Claims (13)

It contains polylactic acid and a crystallization accelerator, and the crystal melting enthalpy of 190 ° C. or higher measured by a differential scanning calorimeter is ΔHms (J / g), and the crystallization enthalpy of 190 ° C. or lower is ΔHmh (J / g). When the following formula
S = {ΔHms / (ΔHms + Hmh)} × 100
The polylactic acid composition (A) whose stereogenicity degree (S) represented by is 80% or more. The composition according to claim 1, wherein the stereogenicity (S) is 95% or more. The composition according to claim 1, comprising 0.1 to 20 parts by weight of a crystallization accelerator per 100 parts by weight of polylactic acid. The composition according to claim 1, wherein the crystallization accelerator is talc having an average particle diameter of 1 to 10 μm. The composition according to claim 1, wherein the crystallization accelerator is at least one selected from the group consisting of a phosphate ester metal salt, a melamine resin, a styrene resin, and a silicone resin. The composition of claim 1 containing a filler. The composition according to claim 6, wherein the filler is glass fiber. (1) Crystalline polylactic acid (B) containing an L-lactic acid unit as a main component and containing 0 to 10 mol% of a D-lactic acid unit, and 0 to 10 mol of an L-lactic acid unit containing a D-lactic acid unit as a main component % Crystalline polylactic acid (C) is melt-kneaded at a weight ratio (B / C) = 10/90 to 90/10 to obtain a composition (D) having a stereogenicity (S) of 80% or more. A first heat treatment step to be obtained, and (2) a second heat treatment step in which a crystallization accelerator is added to the composition (D) and melt-kneaded at 240 ° C to 300 ° C.
A method for producing a composition comprising: The method according to claim 8, wherein a composition (D) having an S value of 95% or more is obtained in the first heat treatment step. The method according to claim 8 or 9, wherein the second heat treatment step is performed after the composition (D) obtained in the first heat treatment step is solidified. The method according to claim 10, wherein the solidified composition (D) is substantially in an amorphous state. The method according to claim 8 or 9, wherein the second heat treatment step is performed while the composition (D) obtained in the first heat treatment step is in a molten state. The molded object which consists of a composition (A) of Claim 1.