JP2009179783A - Polylactic acid resin composition and molded body formed therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polylactic acid resin composition which is improved in moldability, heat resistance and chemical resistance. <P>SOLUTION: The polylactic acid resin composition contains an aromatic polyester which has as a main constitutional unit a trimethylene terephthalate skeleton and comprises a polylactic acid resin component having a melting point of 190°C or higher. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polylactic acid resin composition, and more particularly to a polylactic acid resin composition having improved moldability, heat resistance, and chemical resistance.

  From the viewpoint of resource conservation and environmental protection, bio-based polymers have attracted attention, and in particular, polylactic acid-based resins have recently been manufactured in large quantities and at low cost by L-lactic acid, which is a raw material, by the fermentation method. The field of use is expected to expand due to its excellent characteristics of being strong. However, even the most promising polylactic acid still has physical properties issues for practical use compared to conventional polymers made from petroleum resources. In particular, improvements in heat resistance, chemical resistance, impact resistance and the like are desired. Conventional polylactic acid is poly-L-lactic acid containing L-lactic acid as a main raw material, but stereocomplex polylactic acid containing D-lactic acid as a raw material is known (for example, see Non-Patent Document 1). .

  Stereocomplex polylactic acid is a crystalline resin having a remarkably higher melting point than conventional poly-L lactic acid, and can be expected to have properties that are significantly superior to conventional poly-L lactic acid. However, a technique for highly expressing a stereocomplex crystal with high reproducibility has not yet been completed.

  However, since plastic materials are resins that are mainly produced from petroleum, they consume petroleum resources and increase the amount of garbage when disposed after use, and are difficult to be decomposed in the natural environment. Even after treatment, it remains in the ground semipermanently. And when it is incinerated, there is a concern of increasing carbon dioxide in the atmosphere and promoting global warming. In addition, the discarded plastics are causing problems that directly adversely affect the ecosystem, such as damage to the landscape and destruction of the living environment of the ground and marine organisms. From the viewpoint of resource conservation and environmental protection in recent years, there has been a demand for environmentally friendly plastic materials that use non-petroleum resources as raw materials, reduce volume during disposal, ease of fine granulation, and biodegradability. I came.

  Under such circumstances, development of resin materials having both characteristics has been attempted by blending bio-based polymers and other resins. For example, structural materials mixed with a mixture of polyethylene terephthalate and polylactic acid, etc. Has been proposed (see, for example, Patent Document 1).

  According to this proposal, the ester bond part contained in the thermoplastic polyester is simultaneously decomposed by thermally decomposing or solvolyzing the aliphatic polyester contained in the structural material comprising the mixture of the aromatic polyester and the aliphatic polyester. Therefore, it is described that a molded product that can be easily disposed of after completion of use can be obtained.

  However, a resin composition in which an aliphatic polyester is blended with such an aromatic polyester is considered to be difficult to put into practical use as an engineering plastic because of poor thermal stability during melt molding and extremely poor moldability. It was.

  On the other hand, as an attempt to improve the moldability of a resin composition comprising polylactic acid and an aromatic polyester, a method is disclosed in which a high melting point aromatic polyester is contained in an amount of 15 wt% or less and is molded under the condition that it does not melt. (For example, refer to Patent Document 2).

  Further, a method for improving moldability by adding polyacetate in addition to polylactic acid and polybutylene terephthalate is disclosed (for example, see Patent Document 3). However, in this method, since the glass transition temperature is lowered, the heat resistance may be lowered.

Macromolecules 1987, 20, 904-906. JP-A-8-104797 JP 2006-36818 A Japanese Patent Laid-Open No. 2003-342459

  The present invention has been made in view of such circumstances, and an object thereof is to provide a polylactic acid resin composition having improved chemical resistance, moldability, heat resistance, and mechanical properties.

  The inventors of the present invention have made extensive studies to solve the above-mentioned problems, paying attention to polytrimethylene terephthalate (hereinafter sometimes abbreviated as PTT) as an engineering plastic, and as a result of further earnest studies, the present invention It came to complete.

That is, the object of the present invention is to
This can be achieved by a polylactic acid resin composition comprising an aromatic polyester having a trimethylene terephthalate skeleton as a main structural unit and comprising a polylactic acid resin component having a melting point of 190 ° C. or higher.

  According to the present invention, a polylactic acid resin composition having improved chemical resistance, moldability, heat resistance, and mechanical properties can be provided.

Hereinafter, the present invention will be described in detail.
The polylactic acid used in the present invention is a polylactic acid having a melting point of 190 ° C. or higher, and crystalline polylactic acid can be suitably used as long as it is mainly a polylactic acid stereocomplex.

  Stereocomplex polylactic acid is formed from poly-L-lactic acid and poly-D-lactic acid, and poly-L-lactic acid and poly-D-lactic acid are composed of L-lactic acid units and D-lactic acid units represented by the following formulae. Become substantial.

  The poly-L-lactic acid is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and 99 to 100 mol% for realizing a high melting point. More preferably, it is composed of ˜99 mol% L-lactic acid units. Examples of other units include D-lactic acid units and copolymer component units other than lactic acid. The D-lactic acid unit and the copolymer component unit other than lactic acid are preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 2 mol%.

  The poly-D-lactic acid is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and 99 to 100 mol% for realizing a high melting point. More preferably, it is composed of ˜99 mol% L-lactic acid units. Examples of other units include L-lactic acid units and copolymer component units other than lactic acid. L-lactic acid units and copolymer component units other than lactic acid are 0 to 10 mol%, preferably 0 to 5 mol%, more preferably 0 to 2 mol%.

  The copolymer component unit is a unit derived from dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid, lactone, etc. having a functional group capable of forming two or more ester bonds, and various polyesters, various polyethers composed of these various components, Examples are derived from various polycarbonates and the like.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Polyhydric alcohols include ethylene glycol, propylene glycol, propanediol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, and polyteoramethylene glycol. Aliphatic polyhydric alcohols such as aliphatic polyhydric alcohols, and aromatic polyhydric alcohols obtained by adding ethylene oxide to bisphenol. Examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, 4-hydroxybenzoic acid and the like. Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

  Stereocomplex polylactic acid is a mixture of poly-L-lactic acid and poly-D-lactic acid, and can form stereocomplex crystals. Both poly-L-lactic acid and poly-D-lactic acid preferably have a weight average molecular weight of 100,000 to 500,000, more preferably 150,000 to 350,000.

  Poly-L-lactic acid and poly-D-lactic acid can be produced by a known method. For example, L- or D-lactide can be produced by heating and ring-opening polymerization in the presence of a metal polymerization catalyst. Moreover, after crystallizing low molecular weight polylactic acid containing a metal polymerization catalyst, it can be produced by solid phase polymerization by heating under reduced pressure or in an inert gas stream. Further, it can be produced by a direct polymerization method in which lactic acid is subjected to dehydration condensation in the presence / absence of an organic solvent.

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

  Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid. For example, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and the like can be suitably used.

  In the solid phase polymerization method, a relatively low molecular weight lactic acid polyester obtained by the above-described ring-opening polymerization method or lactic acid direct polymerization method is used as a prepolymer. It can be said that the prepolymer is preferably crystallized in advance in the temperature range of the glass transition temperature (Tg) or higher and lower than the melting point (Tm) from the viewpoint of preventing fusion. The crystallized prepolymer is filled in a fixed vertical or horizontal reaction vessel, or a reaction vessel (rotary kiln, etc.) where the vessel itself rotates like a tumbler or kiln, and the prepolymer glass transition temperature (Tg) or higher. Heated to a temperature range below the melting point (Tm). There is no problem even if the polymerization temperature is raised stepwise as the polymerization proceeds. In addition, for the purpose of efficiently removing water generated during solid phase polymerization, a method of reducing the pressure inside the reaction vessels or circulating a heated inert gas stream is also preferably used.

  The weight ratio of poly-L-lactic acid to poly-D-lactic acid in stereocomplex polylactic acid is in the range of 90:10 to 10:90. It is preferably in the range of 75:25 to 25:75, more preferably in the range of 60:40 to 40:60, and preferably as close to 50:50 as possible.

  The stereocomplex polylactic acid has a weight average molecular weight of 100,000 to 500,000. More preferably, it is 100,000-300,000. The weight average molecular weight is a standard polystyrene equivalent weight average molecular weight value measured by gel permeation chromatography (GPC) using chloroform as an eluent.

  Stereocomplex polylactic acid consists of poly-L-lactic acid and poly-D-lactic acid and contains stereocomplex crystals. The content of stereocomplex crystals is preferably 80 to 100%, more preferably 95 to 100%. The stereocomplex polylactic acid referred to in the present invention has a melting peak at 195 ° C. or higher, preferably 80% or higher, more preferably 90% or higher, in the melting peak in the temperature rising process in the differential scanning calorimeter (DSC) measurement. More preferably, it is 95% or more. The melting point is in the range of 195 to 250 ° C, more preferably in the range of 200 to 220 ° C. The melting enthalpy is 20 J / g or more, preferably 30 J / g or more. Specifically, in the differential scanning calorimeter (DSC) measurement, the ratio of the melting peak at 195 ° C. or higher is 90% or higher and the melting point is in the range of 195 to 250 ° C. It is preferable that the melting enthalpy is 20 J / g or more.

Stereocomplex polylactic acid can be produced by coexisting and mixing poly-L-lactic acid and poly-D-lactic acid in a predetermined weight ratio.
Mixing can be performed in the presence of a solvent. The solvent is not particularly limited as long as it dissolves poly-L-lactic acid and poly-D-lactic acid. For example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methyl Pyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol, etc., alone or in combination of two or more are preferred.

  The mixing can be performed in the absence of a solvent. That is, a method of melting and kneading after mixing a predetermined amount of poly-L-lactic acid and poly-D-lactic acid, and a method of adding and kneading one of them after melting one of them can be employed.

Alternatively, stereoblock polylactic acid in which a poly-L-lactic acid segment and a poly-D-lactic acid segment are bonded can also be suitably used for the polylactic acid component of the present invention.
Stereoblock polylactic acid is a block polymer in which a poly-L-lactic acid segment and a poly-D-lactic acid segment are bonded in the molecule.

Such a block polymer is, for example, a method of producing by sequential ring-opening polymerization or a method of polymerizing poly-L-lactic acid and poly-D-lactic acid and then binding them with a chain exchange reaction or a chain extender. The above-mentioned basic methods such as a method of polymerizing poly-L-lactic acid and poly-D-lactic acid, blending and then solid-phase polymerizing to extend the chain, a method of producing from racemic lactide using a stereoselective ring-opening polymerization catalyst, etc. Any block copolymer having a structure can be used regardless of the production method.
However, it is more preferable from the viewpoint of ease of production to use a high-melting stereoblock polymer obtained by sequential ring-opening polymerization and a polymer obtained by a solid phase polymerization method.

The stereocomplex polylactic acid and stereoblock polylactic acid used in the present invention preferably have a stereogenicity of 90% or more, more preferably 100%. The degree of stereogenicity can be determined by the following formula (2) by comparing the enthalpies of the melting points in DSC measurement.
[Equation 1]
Degree of stereoization = [(ΔHms / ΔHms ⁰ ) / (ΔHmh / ΔHmh ⁰ + ΔHms / ΔHms ⁰ )] (2)
(However, ΔHms0 = 203.4 J / g, ΔHmh0 = 142 J / g, ΔHms = melting enthalpy of stereocomplex melting point, ΔHmh = melting enthalpy of homocrystal)

  It is preferable to add a specific additive to the polylactic acid component used in the present invention in order to improve the degree of stereoization. As such an additive, the metal phosphate shown by a following formula can be mentioned as a preferable example.

M is Na, K, Al, Mg, and Ca. In particular, K, Na, and Al can be preferably used.
These metal salts are preferably used in an amount of 10 ppm to 2 wt%, more preferably 50 ppm to 0.5 wt%, and still more preferably 100 ppm to 0.3 wt% with respect to the polylactic acid component. When the amount is too small, the effect of improving the degree of stereoization is small, and when too large, the resin itself is deteriorated, which is not preferable.

  Moreover, in order to improve the heat resistance of the polylactic acid resin composition, it is preferable to further add calcium silicate. As calcium silicate, what contains a hexagonal crystal can be used, for example, and the one where the particle diameter is low is preferable. For example, when the average primary particle diameter is in the range of 0.2 to 0.05 μm, the polylactic acid resin composition is appropriately dispersed, so that the heat resistance of the polylactic acid resin composition is good. Further, the addition amount is preferably in the range of 0.01 to 1 wt%, more preferably in the range of 0.05 to 0.5 wt%, based on the polylactic acid resin composition. If the amount is too large, the appearance tends to deteriorate, and if the amount is too small, no particular effect is exhibited, which is not preferable.

  In the present invention, the carboxyl end group concentration of the polylactic acid resin component in the polylactic acid resin composition is preferably 15 eq / ton or less. When it is within this range, a composition having good melt stability and wet heat durability can be obtained. In the case of 15 eq / ton or less, specifically, any of the known carboxyl end group concentration reduction methods can be employed in the polyester, such as addition of a terminal blocking agent, specifically, oxazolines. Addition of epoxy compounds, etc., addition of condensing agents such as monocarbodiimides, dicarbodiimides, polycarbodiimides, etc., or addition of terminal capping agents, condensing agents, and ester or amidation with alcohol or amine it can.

  The aromatic polyester used in the present invention has a trimethylene terephthalate skeleton as a main structural unit. Here, “mainly” means that the trimethylene terephthalate skeleton occupies a mole fraction of 50 mol% or more in the aromatic polyester. The trimethylene terephthalate skeleton is preferably contained in a molar fraction of 70% or more, more preferably 85% or more, and further preferably 95% or more from the viewpoint of improving moldability.

  The aromatic polyester used in the invention may contain a copolymer component in addition to the trimethylene terephthalate skeleton. Examples of the copolymer component include hydroxycarboxylic acid, dicarboxylic acid, diols and the like. For example, as the hydroxycarboxylic acid, glycolic acid, D-lactic acid, L-lactic acid, 3-hydroxypropionic acid, 4-hydroxybutanoic acid, 3-hydroxybutanoic acid, 6-hydroxycaproic acid, hydroxybenzoic acid, hydroxynaphthalenecarboxylic acid Examples of dicarboxylic acids include, for example, aromatic dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, diphenoxyethane carboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. Aliphatic dicarboxylic acids such as acids, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, p-β-hydroxyethoxybenzoic acid, ε-oxybenzoic acid, etc. Such as oxyacids Examples of diols such as bifunctional carboxylic acids include ethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol 2,2-bis (4′-hydroxyphenyl) propane, bis (4′-β-hydroxyethoxyphenyl) sulfonic acid, and the like.

The aromatic polyester of the present invention can be used without any problem as long as the intrinsic viscosity is 0.5 to 2.0.
In the present invention, the ratio of the aromatic polyester to the polymer component of the resin composition is preferably in the range of 20 wt% to 50 wt%. From the viewpoint of improving the chemical resistance and the like intended by the present invention and using a bio-based polymer, it is more preferably 20 wt% to 45 wt%, particularly preferably 30 wt% to 40 wt%.

  In producing the polylactic acid resin composition of the present invention, an aromatic polyester having a trimethylene terephthalate skeleton as a main structural unit and a polylactic acid resin having a melting point of 190 ° C. or higher are uniformly mixed without impairing the physical properties of both. It is preferable that it can be exhibited.

The aromatic polyester having a trimethylene terephthalate skeleton as the main structural unit has a carboxyl group terminal concentration of 10 to 60 eq / ton, with respect to compositional properties such as uniform mixing of both constituents of the resin composition of the present invention and melt stability. preferable. More preferably, a range of 20 to 50 eq / ton, particularly preferably 25 to 45 eq / ton is selected.
When it is within this range, neither the problem of melt stability nor the problem of uniform mixing of both components can occur.

  In order to make the carboxyl group terminal concentration within the above range, for example, in order to increase the carboxyl group concentration, the aromatic polyester may be added by a method of adding an acid component such as terephthalic acid or phthalic acid to the aromatic polyester. In order to reduce the terminal concentration, it can be easily achieved by applying the addition of a carboxy terminal blocking agent, a condensing agent and an alkali described in the section of polylactic acid.

  The aromatic polyester of the present invention preferably has a cyclic dimer content of 0.05 to 2.5 mol% per mol of ester bond. When the dimer content is in the above range, the cyclic dimer is precipitated on the surface of the molded product of the composition of the present invention, resulting in surface defects, and the interaction between the two components of the present invention is reduced and the physical properties are exhibited. There is no problem of lowering.

The aromatic polyester of the present invention is preferably copolymerized with 0.2 to 3 wt% of bis (3-hydroxypropyl) ether (hereinafter sometimes abbreviated as BPE).
A more preferable range is 0.2 to 2.5 wt%, a more preferable range is 0.3 to 2 wt%, and a particularly preferable range is 0.5 to 2 wt%.

  When the copolymerization exceeds the above range, the stability of the composition of the present invention against oxidation, particularly the stability against oxidation in a heated state, and the brittleness of the molded product of the present invention are also reduced. In order to control the amount of cyclic dimer and the amount of BPE, the method of adding the component at any stage from the start to the end of the polymerization, the solid phase polymerization, etc. under conditions where the PTT pellets are heated under high vacuum, heating or non-heating A desired value can be obtained by a combination of vacuum processing methods and the like.

  The aromatic polyester and the polylactic acid resin can be blended by any method as long as they can be mixed uniformly, such as melt blending and solution blending. In particular, it is preferable to knead in a molten state in a kneader, a single-screw kneader, a twin-screw kneader, a melt reactor, or the like.

  The kneading temperature may be a temperature at which both resins are melted, but taking into account the stability of the resin, the range of 240 to 280 degrees is preferable, and the range of 240 to 260 degrees is more preferable. In kneading, it is more preferable to use a compatibilizing agent because the uniformity of the resin is improved and the kneading temperature is lowered. Examples of the compatibilizer include an inorganic filler, a polymer compound obtained by grafting or copolymerizing a glycidyl compound or an acid anhydride, a graft polymer having an aromatic polycarbonate chain, and an organometallic compound. May be used.

  Further, the blending amount of the compatibilizer is preferably 15 wt% to 1 wt%, more preferably 10 wt% to 1 wt%, based on the polylactic acid resin composition, and if it is less than 1 wt%, the effect as the compatibilizer is small. If it exceeds 15 wt%, the mechanical properties deteriorate, which is not preferable.

  Needless to say, the polylactic acid resin composition of the present invention can be used as it is, but a mold release agent, surface smoothing agent, heat-and-moisture resistance improver, flame retardant, filler, stabilizer (antioxidant, UV Absorbent), plasticizer, nucleating agent, talc, flake, elastomer, antistatic agent, rubber-reinforced styrene resin, polyethylene terephthalate, polybutylene terephthalate, and polycarbonate.

  Any known release agent may be used, including plant waxes such as carnauba wax and rice wax, animal waxes such as beeswax and lanolin, montan wax, and montanic acid partially saponified ester wax. Mineral waxes, paraffin waxes, petroleum waxes such as polyethylene waxes, castor oil and derivatives thereof, and fats and oils waxes such as fatty acids and derivatives thereof, and montanic acid partially saponified ester waxes are particularly preferably used. Among the agents, it is particularly excellent in the effect of improving the high cycle property described later.

  Any known surface smoothing agent can be used, and examples thereof include silicone compounds, fluorine surfactants, and organic surfactants.

  As the heat-and-moisture resistance improver, any known one can be used, and examples thereof include a carbodiimide compound. Specifically, for example, diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, N -Triyl-N'-phenylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-p-methoxyphenylcarbodiimide, di -3,4-dichlorophenylcarbodiimide, di-2,5-dichlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, p-phenylene-bis-di-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide Mono- or dicarbodiimide compounds such as imide, p-phenylene-bis-di-p-chlorophenylcarbodiimide, ethylene-bis-diphenylcarbodiimide, poly (4,4-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly ( m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropylphenylenecarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), and the like. In this invention, a carbodiimide compound may be used independently or may be used in combination of 2 or more type.

  Any known flame retardant can be used. Specifically, brominated flame retardants, chlorine-based flame retardants, phosphorus-based flame retardants, nitrogen compound-based flame retardants, silicone-based flame retardants, other An inorganic flame retardant etc. can be mentioned.

  Specific examples of brominated flame retardants include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromophenoxy) ethane, ethylene Bistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, tris (2,3 -Dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobisphenol-A, te Bromobrominated bisphenol-A derivatives, tetrabrominated bisphenol-A-epoxy oligomers or polymers, tetrabrominated bisphenol-A-carbonate oligomers or polymers, brominated epoxy resins such as brominated phenol novolac epoxies, tetrabromobisphenol-A-bis (2 -Hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, tris (tribromo Neopentyl) phosphate, poly (pentabromobenzyl polyacrylate), octabromotrimethylphenylindane, dibromoneopentyl glycol, Printer bromobenzyl polyacrylates, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo phthalic imide. Of these, tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, and brominated epoxy resin are preferable.

  Specific examples of the chlorinated flame retardant include chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecane, and tetrachlorophthalic anhydride.

  Examples of phosphorus flame retardants include organic phosphorus compounds such as phosphate esters, condensed phosphate esters, and polyphosphates, and red phosphorus.

  Any known filler can be used, for example, silica, mica, calcium carbonate, glass fiber, glass beads, barium sulfate, magnesium hydroxide, wollastonite, calcium silicate fiber, carbon fiber, Examples thereof include magnesium oxysulfate fiber, potassium titanate fiber, titanium oxide, calcium sulfite, white carbon, clay, montmorillonite, and calcium sulfate.

  Any known stabilizer can be used, but lithium stearate, magnesium stearate, calcium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc laurate , Various metal soap stabilizers such as zinc ricinoleate and zinc stearate, various tantalum stabilizers such as laurate, malate and mercapto, and various lead stabilizers such as lead stearate and tribasic lead sulfate, epoxy Epoxy compounds such as modified vegetable oils, phosphite compounds such as alkylallyl phosphites and trialkyl phosphites, β-diketone compounds such as dibenzoylmethane and dehydroacetic acid, polyols such as sorbitol, mannitol and pentaerythritol, hydrides Examples include talcites and zeolites, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, oxalic anilide ultraviolet absorbers, and hindered amine light stabilizers. .

  As the plasticizer, any known ones can be used. Polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers, polyalkylene glycol plasticizers and An epoxy plasticizer can be used.

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

  Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.

  Specific examples of polycarboxylic acid ester plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, and butyl benzyl phthalate. Trimellitic acid esters such as tributyl acid, trioctyl trimellitic acid, trihexyl trimellitic acid, adipic acid esters such as diisodecyl adipate, n-octyl-n-decyl adipate, triethyl acetylcitrate, tributyl acetylcitrate In addition to citrate esters such as azelaic acid esters such as di-2-ethylhexyl azelate, dibutyl sebacate, and sebacic acid esters such as di-2-ethylhexyl sebacate, Recall) succinate, bis (butyl diglycol) succinate methyl diglycol butyl diglycol succinate, ethyl diglycol butyl diglycol succinate, propyl diglycol butyl diglycol succinate, benzyl methyl diglycol succinate, methoxycarbonylmethyl methyl Diglycol succinate, ethoxycarbonylmethyl methyl diglycol succinate, benzyl butyl diglycol succinate, bis (methyl diglycol) adipate, bis (butyl diglycol) adipate, methyl diglycol butyl diglycol adipate, ethyl diglycol butyl di Glycol adipate, propyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate Benzylbutyl diglycol adipate, methoxycarbonylmethylmethyl diglycol adipate, methoxycarbonylmethylbutyl diglycol adipate, ethoxycarbonylmethylmethyl diglycol adipate, ethoxycarbonylmethylbutyl diglycol adipate, dimethyldiglycol monobutyldiglycol adipate, benzyldimethyl Diglycol citrate, methoxycarbonyl methyl dimethyl citrate, methoxy carbonyl methyl diethyl citrate, methoxy carbonyl methyl dibutyl citrate, ethoxy carbonyl methyl dimethyl citrate, ethoxy carbonyl methyl dibutyl citrate, ethoxy carbonyl methyl dioctyl citrate, butoxy carbonyl methyl Dimethyl rhino Tray, Butoxycarbonylmethyldiethyl citrate, Butoxycarbonylmethyl dibutyl citrate, Dimethoxycarbonylmethyl monomethyl citrate, Dimethoxycarbonylmethyl monoethyl citrate, Dimethoxycarbonylmethyl monobutyl citrate, Diethoxycarbonylmethyl monomethyl citrate, Diethoxycarbonyl Methyl monobutyl citrate, diethoxycarbonylmethyl monooctyl citrate, dibutoxycarbonylmethyl monomethyl citrate, dibutoxycarbonylmethyl monoethyl citrate, dibutoxycarbonylmethyl monobutyl citrate, ethoxycarbonylmethyldimethyldiglycol citrate, Ethoxycarbonylmethyl dibutyl diglycol cytoley , Diethoxycarbonylmethyl monomethyl diglycol citrate, diethoxycarbonylmethyl monobutyl diglycol citrate, and the like. Among them, methyl diglycol butyl diglycol succinate, benzyl methyl diglycol succinate, benzyl butyl diglycol Succinate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, benzyl butyl diglycol adipate, methoxycarbonylmethyl dibutyl citrate, ethoxycarbonylmethyl dibutyl citrate, butoxycarbonylmethyl dibutyl citrate, dimethoxycarbonylmethyl monobutyl sight Rate, diethoxycarbonylmethyl monobutyl citrate, dibutoxycarboni It may be mentioned methyl monobutyl citrate.

  Examples of the phosphate plasticizer include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, and tricresyl phosphate.

  Polyalkylene glycol plasticizers include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, propylene oxide of bisphenols Examples thereof include polyalkylene glycols such as addition polymers and tetrahydrofuran addition polymers of bisphenols, or end-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

  Epoxy plasticizers include epoxy triglycerides composed of alkyl epoxy stearate and soybean oil. In addition, it is also possible to use epoxy resins mainly made of bisphenol A and epichlorohydrin. it can.

  In addition, benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, and triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearic acid amide, and aliphatic carboxylic acid esters such as butyl oleate And oxy acid esters such as methyl acetyl ricinoleate and butyl acetyl ricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.

  Any known nucleating agent can be used, and any of inorganic crystal nucleating agents and organic crystal nucleating agents can be used. Specific examples of the inorganic crystal nucleating agent include kaolinite, montmorillonite, synthetic mica, calcium sulfide, boron nitride, barium sulfate, aluminum oxide, neodymium oxide, and metal salts of phenylphosphonate. These inorganic crystal nucleating agents are preferably modified with an organic substance in order to enhance dispersibility in the composition.

  Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, Calcium oxide, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicylic acid , Metal salts of organic carboxylic acids such as aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid Amides, ethylene bislauric acid amides, palmitic acid amides, hydroxystearic acid amides, erucic acid amides, carboxylic acid amides such as trimesic acid tris (t-butylamide), benzylidene sorbitol and its derivatives, sodium-2,2′-methylenebis ( Examples include phosphorus compound metal salts such as 4,6-di-t-butylphenyl) phosphate and 2,2-methylbis (4,6-di-t-butylphenyl) sodium. You can.

  Any known talc can be used, but it may be treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent. The average particle diameter of talc is preferably 0.1 to 50 μm, more preferably 0.5 to 10 μm.

  Any known flakes can be used, and examples thereof include mica, glass flakes, and various metal foils.

  Any known elastomer can be used as the elastomer, but ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene-1 copolymer, various acrylic rubbers, ethylene-acrylic. Acid copolymers and alkali metal salts thereof (so-called ionomers), ethylene-glycidyl (meth) acrylate copolymers, ethylene-acrylic acid alkyl ester copolymers (for example, ethylene-ethyl acrylate copolymers, ethylene-acrylic acid) Butyl copolymer), acid-modified ethylene-propylene copolymer, diene rubber (eg polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (eg styrene-butadiene random copolymer, styrene- Butadiene block copolymer Styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene grafted with styrene, butadiene- Acrylonitrile copolymer), polyisobutylene, a copolymer of isobutylene and butadiene or isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber and the like.

  Any known antistatic agent can be used, but low molecular weight antistatic agents such as anionic antistatic agents, cationic antistatic agents, nonionic antistatic agents, and amphoteric antistatic agents. And a polymer type antistatic agent.

  Suitable anionic antistatic agents include sodium alkyl sulfonate, sodium alkyl benzene sulfonate and alkyl phosphate. As the alkyl group, a linear alkyl group having 4 to 20 carbon atoms is preferably used.

  Suitable cationic antistatic agents include phosphonium alkyl sulfonates, phosphonium alkylbenzene sulfonates and quaternary ammonium salt compounds. As the alkyl group, a linear alkyl group having 4 to 20 carbon atoms is preferably used.

  Suitable nonionic antistatic agents include polyoxyethylene derivatives, polyhydric alcohol derivatives, and alkylethanolamines. As the polyoxyethylene derivative, for example, polyethylene glycol having a number average molecular weight of 500 to 100,000 is preferably used.

  Suitable amphoteric antistatic agents include alkylbetaines and sulfobetaine derivatives. Suitable polymeric antistatic agents include polyethylene glycol methacrylate copolymers, polyether amides, polyether ester amides, polyether amide imides, polyalkylene oxide copolymers, polyethylene oxide-epichlorohydrin copolymers and polyether esters. Can be mentioned. These antistatic agents may be used in combination.

  Any known rubber-reinforced styrene-based resin can be used. For example, impact-resistant polystyrene, ABS resin, AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene). Propylene rubber-styrene copolymer).

  These additives can be used alone or in combination of two or more kinds depending on the properties to be imparted. For example, a stabilizer, a release agent and a filler can be added in combination.

Hereinafter, examples of characteristics and combinations to be particularly given will be described.
(1) High cycle performance:
High cycleability means a short injection molding cycle. In improving the high cycle property, for example, a stabilizer, talc, and a release agent may be used in combination.
The addition ratio of the release agent is 0.05 to 3.0 wt% based on the polylactic acid resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, and the addition ratio of talc is 1 to 10 wt%. If it is.

(2) Toughness and low temperature impact resistance:
Toughness means tenacity and is an index of resistance to fracture, and is generally evaluated by a Charpy impact test. In improving toughness and low temperature impact resistance, a release agent, a stabilizer and an elastomer may be used in combination, or a release agent, a stabilizer, an elastomer and a polycarbonate may be used in combination.
The addition ratio of the release agent is 0.05 to 3.0 wt% based on the polylactic acid resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, and the addition ratio of the elastomer is 1 to 10 wt%. The addition ratio of the polycarbonate may be 1 to 10 wt%.
The polylactic acid resin composition having toughness and low-temperature impact resistance can be suitably used particularly for harness connectors and bumper parts of automobile parts.

(3) Flame retardancy:
In order to improve the flame retardancy, it is only necessary to add a flame retardant, but it is preferable to use a combination of a release agent, a stabilizer, a flame retardant and a filler.
The addition ratio of the flame retardant is 0.05 to 5.0 wt% based on the polylactic acid resin composition, the addition ratio of the release agent is 0.05 to 3.0 wt%, and the addition ratio of the stabilizer is 0.05. -5.0 wt%, and the addition ratio of a filler should just be 1-10 wt%.

(4) Low warpage:
In improving the low warpage property, a release agent, a stabilizer, flakes and a filler may be used in combination, or a release agent, a stabilizer, a filler and a polycarbonate may be used in combination. In addition, polyethylene terephthalate may be added as an additive to the release agent, stabilizer, filler and polycarbonate.
Further, a release agent, a stabilizer, a filler, and a rubber-reinforced styrene resin may be used in combination.
The addition ratio of the release agent is 0.05 to 3.0 wt% based on the polylactic acid resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, and the addition ratio of the filler is 1 to 10 wt%. The addition ratio of polycarbonate is 1 to 10 wt%, the addition ratio of polyethylene terephthalate is 1 to 10 wt%, and the addition ratio of rubber-reinforced styrene resin is 1 to 10 wt%.
A polylactic acid resin composition having good low warpage can be suitably used for home appliances.

(5) Surface appearance:
The surface appearance is composed of surface smoothness and gloss when the resin composition is molded, and is generally determined by touch and visual observation.
In improving the surface appearance, a release agent, a stabilizer, a filler, and polyethylene terephthalate may be used in combination. Further, polycarbonate may be added as an additive to the release agent, stabilizer, filler and polyethylene terephthalate.
The addition ratio of the release agent is 0.05 to 3.0 wt based on the polylactic acid resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, the addition ratio of the filler is 1 to 10 wt%, The addition ratio of polycarbonate may be 1 to 10 wt%, and the addition ratio of polybutylene terephthalate may be 1 to 10 wt%.
The polylactic acid resin composition having a high surface appearance can be suitably used for home appliances.

(6) Hydrolysis resistance:
In order to improve the hydrolysis resistance, it is only necessary to add a moist heat resistance improver, but it is preferable to use a combination of a mold release agent, a stabilizer, a filler and a heat resistance improver.
Furthermore, it is preferable to lower the carboxyl end group concentration of the polylactic acid resin component and the carboxyl end group concentration of the aromatic polyester, and the carboxyl end group concentration can be lowered, for example, by a solid phase polymerization reaction.
The addition ratio of the release agent is 0.05 to 3.0 wt based on the polylactic acid resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, the addition ratio of the filler is 1 to 10 wt%, The addition ratio of the heat and heat resistance improving agent may be 0.05 to 5.0 wt%.
A polylactic acid resin composition having high hydrolysis resistance can be suitably used for automobile parts.

(7) Heat shock resistance:
The heat shock property means the degree of durability of the resin when the low temperature holding (about −40 ° C. for about 30 minutes) and the high temperature holding (about 100 ° C. for about 30 minutes) are repeated alternately.
In improving the heat shock resistance, it is preferable to use a combination of a release agent, a stabilizer, a filler, an elastomer, and a heat and heat resistance improver.
The addition ratio of the release agent is 0.05 to 3.0 wt based on the polylactic acid resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, the addition ratio of the filler is 1 to 10 wt%, The addition ratio of the elastomer may be 1 to 10 wt%, and the addition ratio of the heat and heat resistance improver may be 0.05 to 5.0 wt%.
A polylactic acid resin composition having good heat shock resistance can be suitably used for automobile parts.

(8) Tracking resistance:
Tracking resistance evaluates the degree of voltage that causes a permanent carbonized conductive path in a material, and the higher the better.
In improving the tracking resistance, it is preferable to use a combination of a release agent, a stabilizer, a flame retardant, talc and a filler.
The addition ratio of the release agent is 0.05 to 3.0 wt based on the polylactic acid resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, and the addition ratio of the flame retardant is 0.05 to 5 0.0 wt%, the talc addition ratio may be 1 to 10 wt%, and the filler addition ratio may be 1 to 10 wt%.
A polylactic acid resin composition having good tracking resistance can be suitably used for electrical parts, particularly relays, switches and the like.

(9) Light resistance:
In order to improve light resistance, it is sufficient to add a stabilizer, but it is preferable to use a combination of a release agent, a stabilizer, a filler, and a flame retardant.
The addition ratio of the release agent is 0.05 to 3.0 wt based on the polylactic acid resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, and the addition ratio of the flame retardant is 0.05. -5.0 wt%, and the addition ratio of a filler should just be 1-10 wt%.
A polylactic acid resin composition having good light resistance can be suitably used for lighting parts and the like.

(10) Silence:
The quietness means the quietness and vibration damping characteristics when used for a structural material having a noise source, electrical and electronic parts such as housings or relay parts, and a motor case.
In improving the silence, it is preferable to use a combination of a release agent, a stabilizer, an elastomer, talc and a filler.
The addition ratio of the release agent is 0.05 to 3.0 wt based on the polylactic acid resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, the addition ratio of the elastomer is 1 to 10 wt%, The talc addition ratio may be 1 to 10 wt%, and the filler addition ratio may be 1 to 10 wt%.
The polylactic acid resin composition having good quietness can be suitably used for a structural material having a noise source as described above, a housing or an electric / electronic component such as a relay component, a motor case, and the like.

(11) Low gasity Low gasity means that the amount of gas generated when the polylactic acid resin composition is used at a high temperature or for a long period of time is small, and the amount of sublimate during melt processing is small.
In improving the low gas property, a release agent, a stabilizer, a flame retardant and a filler may be used in combination, and it is preferable to add a transesterification inhibitor. Examples of the transesterification reaction inhibitor include sodium dihydrogen phosphate, potassium acetate, trimethyl phosphate, and phenylphosphonic acid.
The addition ratio of the release agent is 0.05 to 3.0 wt based on the polylactic acid resin composition, the addition ratio of the stabilizer is 0.05 to 5.0 wt%, and the addition ratio of the flame retardant is 0.05. ˜5.0 wt%, wt%, filler addition ratio may be 1 to 10 wt%, and transesterification reaction inhibitor addition ratio may be 0.01 to 5.0 wt%.
A polylactic acid resin composition having good low gas properties can be suitably used for electrical parts, particularly relays and the like.

(12) Antistatic property:
In order to improve the antistatic property, an antistatic agent may be added.
The addition ratio of the antistatic agent may be 0.1 to 10 wt% based on the polylactic acid resin composition.
A polylactic acid resin composition having good antistatic properties can be suitably used, for example, as a wafer carrier used during semiconductor production.

  The polylactic acid resin composition obtained by the present invention can be used as various molded articles and sheets by molding. As a molding method, a conventionally known melt molding resin molding method such as a method of molding after melting or a method of compressing and welding can be used. For example, injection molding, extrusion molding, blow molding, foam molding , Press molding and the like can be suitably used.

  The resin obtained by the present invention is excellent in moldability, and particularly when the molded product has a high crystallinity, the molding shrinkage is low and the heat resistance is excellent. In particular, a molded product having a degree of crystallinity exceeding 40% is preferable because of excellent heat resistance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention does not receive any limitation by this. In addition, each value in an Example was calculated | required according to the following method.

1) Quantitative determination of BPE Approximately 2 g of the pulverized sample was precisely weighed, added to 25 ml of 2N potassium hydroxide in methanol, solvolyzed over 4 hours under reflux, and the sample was used by gas chromatographic analysis. BPE was quantified according to the calibration curve.
Column: DURABOND DB-WAX; 0.25 mm * 30 m (coat thickness: 0.25 μm)
Carrier: He gas, 100 ml / min.
Temperature rise; temperature rise from 150 ° C to 230 ° C at 20 ° C / min

2) Quantification of cyclic dimer in PTT About 0.3 g of a sample was precisely weighed and dissolved in a mixed solvent of 5 ml of hexafluoroisopropanol and 5 ml of chloroform. The precipitated insoluble matter was filtered off, and the filtrate was received in a 300 ml flask. The insoluble matter was further washed with about 80 ml of acetonitrile, and acetonitrile was further added to the filtrate to make a total volume of 200 ml. This solution was analyzed by high performance liquid chromatography to quantify the cyclic dimer.
Column; μ Bondasphere 15 μ C-18-100A, 3.9 * 190 mm (manufactured by Waters), temperature 45 ° C.
Eluent: Water / acetonitrile (70/30) volume ratio, flow rate 1.5 ml / min
Detection; UV 242nm

3) Acid value, quantification of carboxyl end groups (PTT)
About 1 g of sample is precisely weighed and dissolved in 100 ml of purified benzyl alcohol, quickly dissolved at 200 ° C. under a nitrogen stream, cooled to room temperature, added with 100 ml of purified chloroform, phenol red as an indicator, benzyl alcohol of 0.1N sodium hydroxide Titrate with solution.

4) Intrinsic viscosity (PTT)
According to a conventional method, it was determined by measuring at 35 ° C. using orthochlorophenol as a solvent.

5) Weight average molecular weight (Mw) (polylactic acid)
The weight average molecular weight of the polymer was determined by GPC (column temperature 40 ° C., chloroform) in comparison with a polystyrene standard sample.

6) Melting point, crystal melting peak, crystal melting start temperature, crystal melting enthalpy measurement (polylactic acid)
TA-2920 differential scanning calorimeter DSC manufactured by TA Instruments was used.
In the measurement, 10 mg of a sample was heated from room temperature to 260 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. In the first scan, the homocrystal melting peak, homocrystal melting (starting) temperature, homocrystal melting enthalpy and stereocomplex crystal melting peak, stereocomplex crystal melting (starting) temperature and stereocomplex crystal melting enthalpy were determined.

7) Measurement of stereogenicity (polylactic acid)
In the present invention, the degree of stereogenicity was determined by measuring melting enthalpy using DSC (TA-2920 manufactured by TA Instrument Co., Ltd.), and obtaining the enthalpy from the enthalpy according to the following formula (2).
[Equation 2]
Degree of stereoization = [(ΔHms / ΔHms ⁰ ) / (ΔHmh / ΔHmh ⁰ + ΔHms / ΔHms ⁰ )] (2)
(However, ΔHms0 = 203.4 J / g, ΔHmh0 = 142 J / g, ΔHms = melting enthalpy of stereocomplex melting point, ΔHmh = melting enthalpy of homocrystal)

8) Chemical resistance of molded products:
The molded resin was immersed in the solvent shown in Table 1 and held at 25 ° C. for 1 day, and then its appearance and weight change were examined. The results are shown in Table 1.

9) Measurement of crystallinity:
The DSC (TA-2920 manufactured by TA Instrument Co., Ltd.) of the molded product was measured and determined from the enthalpy according to the following formula (3).
[Equation 3]
Dcry = {(ΔHms / ΔHms ⁰ ) + (ΔHmh / ΔHmh ⁰ )} × 100% (3)
(However, ΔHms0 = 203.4 J / g, ΔHmh0 = 142 J / g, ΔHms = melting enthalpy of stereocomplex melting point, ΔHmh = melting enthalpy of homocrystal)

[Production Example 1] Production of PTT resin: (PTT-1):
PTT-1 was produced by the following method. That is, 30.4 parts by weight of 1,3-propanediol and 33.2 parts by weight of terephthalic acid were placed in an esterification reaction tank, and the esterification reaction was carried out at 240 ° C. for 4 hours under a pressure of 3039 hPa, resulting in an esterification reaction rate of 95.6%. The esterification reaction product was obtained.
40 parts by weight of the obtained esterification reaction product was transferred to a polycondensation reaction tank, 2 × 10 ⁻⁴ mol of tetrabutyl titanate was added to 1 mol of terephthalic acid, and melt polymerization was carried out at 245 ° C. for 2 hours under a reduced pressure of 0.3 hPa. A prepolymer having an intrinsic viscosity of 0.65 was obtained. The obtained prepolymer was pre-dried at 130 ° C. for 1 hour, subjected to solid phase polymerization at 200 ° C. for 4 hours under a pressure of 2 hPa, and then PTT was melt-chipped at a cylinder temperature of 260 ° C. with a twin-screw extruder, and the intrinsic viscosity A PTT having a BPE content of 0.5 wt%, a cyclic dimer of 0.2 mol%, and a carboxyl end group concentration of 35 eq / ton was obtained.

[Production Example 2] (Production of poly-L-lactic acid)
To 100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%), 0.005 part by weight of tin octylate was added, and the reaction was carried out at 180 ° C. in a reactor equipped with a stirring blade in a nitrogen atmosphere. After reacting for 2 hours, the remaining lactide was removed by reducing the pressure and chipped to obtain poly-L-lactic acid.
The obtained poly-L-lactic acid had a weight average molecular weight of 130,000, a glass transition point (Tg) of 63 ° C., and a melting point of 180 ° C.

[Production Example 3] (Production of poly-D-lactic acid)
To 100 parts by weight of D-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%), 0.005 part by weight of octylate was added, and the reaction was carried out at 180 ° C. in a reactor equipped with a stirring blade in a nitrogen atmosphere. After reacting for 2 hours, the remaining lactide was removed by reducing the pressure and chipped to obtain poly-L-lactic acid.
The obtained poly-D-lactic acid had a weight average molecular weight of 130,000, a glass transition point (Tg) of 63 ° C., and a melting point of 180 ° C.

[Production Example 4] (Production of stereocomplex polylactic acid resin)
After weighing 50 parts by weight of each of the poly-L-lactic acid and poly-D-lactic acid obtained in Production Examples 1 and 2, the chips were mixed well, and then kneaded at Laboplast Mill S-15, screw temperature of 225 ° C. Extrusion was performed to take a strand in a water tank, and it was made into a chip by a chip cutter to obtain a stereocomplex resin. The obtained stereocomplex resin had Mw of 125,000, Tm observed at 180 ° C. and 223 ° C., and the degree of stereoification was 65%.

[Production Example 5] (Production of phosphate-containing stereocomplex polylactic acid resin)
The poly-L-lactic acid and poly-D-lactic acid obtained in Production Examples 2 and 3 were weighed out by 50 parts by weight, respectively, and a metal phosphate (“ADEKA STAB” NA-11 manufactured by ADEKA Corporation) 0.5 After thoroughly mixing the chips together with the parts by weight, Laboplast Mill S-15 was kneaded and extruded at a screw temperature of 225 ° C., a strand was taken in a water tank, and chipped with a chip cutter to obtain a stereocomplex resin. The obtained stereocomplex resin had Mw of 125,000, Tm observed at 180 ° C. and 220 ° C., and the degree of stereoification was 95%.

[Example 1]
50 parts by weight of the stereocomplex polylactic acid obtained in Production Example 4 and 50 parts by weight of the PTT resin (PTT-1) obtained in Production Example 1 were used at 250 ° C. and a feed rate of 1 kg / hr using a lab plast mill. The resin composition was obtained by kneading. The degree of stereoification of the obtained resin was 92%.
The obtained resin composition was injection molded at a mold temperature of 110 ° C. and a mold clamping time of 2 minutes to obtain a molded piece. The obtained molded product was white, the crystallinity was 33%, the stereogenicity was 82%, and the appearance was good.

[Example 2]
80 parts by weight of the stereocomplex polylactic acid obtained in Production Example 5 and 20 parts by weight of the PTT resin (PTT-1) obtained in Production Example 1 were used at 250 ° C. and a feed rate of 1 kg / hr using a lab plast mill. The resin composition was obtained by kneading. The degree of stereoification of the obtained resin was 100%.
The obtained resin composition was injection-molded at a mold temperature of 110 ° C. and a mold clamping time of 1 minute to obtain a molded piece. The obtained molded product was white, the crystallinity was 45%, the stereogenicity was 100%, and the appearance was good.

[Example 3]
60 parts by weight of stereocomplex polylactic acid obtained in Production Example 5, 40 parts by weight of PTT resin (PTT-1) obtained in Production Example 1, and 0.2 parts by weight of calcium silicate (manufactured by Nacalai Tesque Co., Ltd.) Using a plastmill, the mixture was kneaded at 250 ° C. and a feed rate of 1 kg / hr to obtain a resin composition. The degree of stereoification of the obtained resin was 100%.
The obtained resin composition was injection-molded at a mold temperature of 110 ° C. and a mold clamping time of 1 minute to obtain a molded piece. The obtained molded product was white, the crystallinity was 48%, the stereogenicity was 100%, and the appearance was good.

[Comparative Example 1]
Using Laboplast mill, 50 parts by weight of poly-L-lactic acid obtained in Production Example 2 and 50 parts by weight of PTT resin (PTT-1) obtained in Production Example 1 were fed at 250 ° C. and a feed rate of 1 kg / hr. And kneaded to obtain a resin composition.
The obtained resin composition was injection molded at a mold temperature of 110 ° C. and a mold clamping time of 4 minutes to obtain a molded piece. The obtained molded product was white, the crystallinity was 20%, and the appearance was good.
The following table summarizes the results of the chemical resistance test.

[Example 4]
60 parts by weight of stereocomplex polylactic acid obtained in Production Example 5, 40 parts by weight of PTT resin (PTT-1) obtained in Production Example 1, 0.2 part by weight of calcium silicate (manufactured by Nacalai Tesque Co., Ltd.), talc ( Nippon Talc Co., Ltd. P-2) 1 part by weight, “Irganox” 1010, 0.5 part by weight, 0.5 part by weight of montanic acid wax, 250 ° C., feed rate 1 kg / hr using a lab plast mill And kneaded to obtain a resin composition.
The obtained resin composition was injection-molded at a mold temperature of 110 ° C. and a mold clamping time of 1 minute to obtain a molded piece. The obtained molded product was white, the crystallinity was 45%, and the appearance was good.

[Example 5]
60 parts by weight of stereocomplex polylactic acid obtained in Production Example 5, 40 parts by weight of PTT resin (PTT-1) obtained in Production Example 1, 0.2 part by weight of calcium silicate (manufactured by Nacalai Tesque), glass chopped 30 parts by weight of a strand (Asahi Fiber Glass Co., Ltd.), 10 parts by weight of “Fireguard” 7500 (manufactured by Teijin Chemicals Ltd.), 0.5 by 10 parts of “Irganox”, 0.5 parts by weight of montanic acid wax Using a lab plast mill, the mixture was kneaded at 250 ° C. and a feed rate of 1 kg / hr to obtain a resin composition.
The obtained resin composition was injection molded at a mold temperature of 110 ° C. and a mold clamping time of 2 minutes to obtain a molded piece. The obtained molded product was white, the crystallinity was 45%, and the appearance was good. The result of the flame retardancy test was a determination of V1 in the vertical combustion test in the UL standard.

[Example 6]
60 parts by weight of stereocomplex polylactic acid obtained in Production Example 5, 40 parts by weight of PTT resin (PTT-1) obtained in Production Example 1, 0.2 part by weight of calcium silicate (manufactured by Nacalai Tesque), glass chopped 30 parts by weight of a strand (manufactured by Asahi Fiber Glass Co., Ltd.), 1 part by weight of “Carbodilite” LA-1 (manufactured by Nisshinbo Co., Ltd.), 0.5 part by weight of “Irganox” 1010, 0.5 part by weight of montanic acid wax Using a lab plast mill, the mixture was kneaded at 250 ° C. and a feed rate of 1 kg / hr to obtain a resin composition.
The obtained resin composition was injection molded at a mold temperature of 110 ° C. and a mold clamping time of 2 minutes to obtain a molded piece. The obtained molded product was white, the crystallinity was 45%, and the appearance was good.

[Example 7]
60 parts by weight of stereocomplex polylactic acid obtained in Production Example 5, 40 parts by weight of PTT resin (PTT-1) obtained in Production Example 1, 0.2 part by weight of calcium silicate (manufactured by Nacalai Tesque), glass chopped 30 parts by weight of strand (Asahi Fiber Glass Co., Ltd.), 5 parts by weight of thermoplastic elastomer (“Modiper” A5300 manufactured by NOF Corporation), 1 part by weight of “Carbodilite” LA-1 (Nisshinbo Co., Ltd.), 1010, 0.5 part by weight and montanic acid wax 0.5 part by weight were kneaded using a lab plast mill at 250 ° C. and a feed rate of 1 kg / hr to obtain a resin composition.
The obtained resin composition was injection molded at a mold temperature of 110 ° C. and a mold clamping time of 2 minutes to obtain a molded piece. The obtained molded product was white, the crystallinity was 45%, and the appearance was good.
The obtained molded product had excellent toughness and improved impact strength.
The following table summarizes the results of the chemical resistance test.

[Example 8]
60 parts by weight of stereocomplex polylactic acid obtained in Production Example 5, 40 parts by weight of PTT resin (PTT-1) obtained in Production Example 1, 0.2 part by weight of calcium silicate (manufactured by Nacalai Tesque), antistatic agent ( Mixture of sodium dodecylbenzenesulfonate and polyoxyethylene derivative): Takemoto Yushi Co., Ltd., trade name TPL-456, “Irganox” 1010, 0.5 parts by weight, montanic acid wax 0.5 parts by weight, Using a Laboplast mill, kneading was performed at 250 ° C. and a feed rate of 1 kg / hr to obtain a resin composition.
The obtained resin composition was injection molded at a mold temperature of 110 ° C. and a mold clamping time of 2 minutes to obtain a molded piece. The obtained molded product was white, the crystallinity was 45%, and the appearance was good.
The surface resistance of the obtained molded product was lowered.
The following table summarizes the results of the chemical resistance test.

Claims (14)

  A polylactic acid resin composition comprising an aromatic polyester having a trimethylene terephthalate skeleton as a main structural unit and comprising a polylactic acid resin component having a melting point of 190 ° C. or higher.   The polylactic acid resin composition according to claim 1, wherein the polylactic acid resin component forms a stereocomplex crystal.   The polylactic acid resin composition according to claim 2, which has a stereogenicity of 90% or more.   The polylactic acid resin composition according to any one of claims 1 to 3, comprising a phosphate metal salt in a range of 10 ppm to 2 wt%. The polylactic acid resin composition according to claim 4, wherein the phosphoric acid metal salt is represented by a general structure of the following formula (1).

  The polylactic acid composition according to any one of claims 1 to 5, wherein the carboxyl end group concentration of the polylactic acid resin component is 15 eq / ton or less.   The polylactic acid resin composition according to any one of claims 1 to 6, wherein the aromatic polyester is contained in a range of 10 wt% to 50 wt% based on the polylactic acid resin composition.   The polylactic acid resin composition according to any one of claims 1 to 7, wherein the aromatic polyester contains bis (3-hydroxypropyl) ether in a range of 0.1 to 3 wt%.   The polylactic acid resin composition according to any one of claims 1 to 8, wherein the aromatic polyester contains a cyclic dimer in a range of 0.05 to 2.5 mol% per mol of the ester bond.   The polylactic acid resin composition according to any one of claims 1 to 8, wherein the carboxyl end group concentration of the aromatic polyester is 10 to 60 eq / ton or less.   The polylactic acid resin composition according to any one of claims 1 to 10, wherein the polylactic acid resin composition further contains calcium silicate.   Polylactic acid resin composition is a mold release agent, surface smoothing agent, heat and humidity resistance improver, flame retardant, filler, stabilizer, plasticizer, nucleating agent, talc, flake, elastomer, antistatic agent, rubber reinforced styrene resin, The polylactic acid composition according to any one of claims 1 to 11, comprising at least an additive selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate and polycarbonate.   The polylactic acid composition according to any one of claims 1 to 12, wherein the polylactic acid resin composition contains at least a carbodiimide compound, an epoxy compound, and an isocyanate compound.   The molded object which consists of a polylactic acid resin composition in any one of Claims 1-13, and the crystallinity degree of a polylactic acid resin component is 30% or more.