JP5167807B2 - Molded product and manufacturing method thereof - Google Patents

Description

  The present invention relates to a molded article containing a polylactic acid resin and a method for producing the same, and more particularly to a molded article comprising a resin composition containing a polylactic acid resin having excellent transparency and heat resistance, and a method for producing the same. Is.

  In recent years, biodegradable polymers that are decomposed in the natural environment by the action of microorganisms existing in soil or water have attracted attention from the viewpoint of global environmental conservation, and various biodegradable polymers have been developed. Among these, biodegradable polymers that can be melt-formed include, for example, polyhydroxybutyrate, polycaprolactone, aliphatic dicarboxylic acid components such as succinic acid and adipic acid, and glycol components such as ethylene glycol and butanediol. Aliphatic polyesters and polylactic acid are well known. Among these, polylactic acid resin can be produced at low cost by fermentation using microorganisms, using lactic acid as a raw material for lactic acid as a raw material, and has transparency and a melting point of about 170. It is expected to be a biopolymer that can be melt-molded at a high temperature and is being used for various molded products such as food containers by taking advantage of such properties.

  However, the polylactic acid resin has a glass transition temperature of around 60 ° C., and has a large thermal deformation and a decrease in rigidity near this temperature. On the other hand, there is a problem in that it becomes opaque when crystallized in order to improve heat resistance, and a polylactic acid resin material excellent in transparency and heat resistance has been desired.

In Patent Documents 1 to 3, a resin composition excellent in transparency and heat resistance is obtained by blending a crystal nucleating agent such as an amide compound and a plasticizer such as an ester plasticizer, and depending on the case, heat treatment at a specific temperature. Although it is described that a product and its molded product can be obtained, the effect is still insufficient and further improvement has been strongly demanded.
JP 11-5849 A (pages 2-3 and 9-10) International Publication No. 2003/042302 (Pages 2-5, 20-26) JP 2006-176747 A (pages 2-4 and 15-29)

  An object of the present invention is to provide a molded article made of a resin composition containing a polylactic acid resin having excellent transparency and heat resistance, and a method for producing the same.

  The present invention employs the following means in order to solve such problems.

That is, the present invention is as follows.
(1) (A) It consists of the resin composition which mix | blends 0.5-50 weight part of crystallization promoter with respect to 100 weight part of polylactic acid resin, (A) polylactic acid resin is (a) polylactic acid. Among the total lactic acid components of the resin, a polylactic acid resin containing 80% or more of L-form or 80% or more of D-form, and / or (b) a polylactic acid stereocomplex, and the crystallization accelerator is (B) a crystal nucleating agent and (C) a plasticizer, (B) the crystal nucleating agent is at least one selected from an amide compound and a hydrazide compound, and (C) the plasticizer is two or more plastics. The molded article contains no spherulites, has a relative crystallinity of 50% or more, and a total light transmittance of 70% or more. Contains particulate matter with an average particle size of 300 nm or less Molded product to be.
(2) The molded article according to (1) , wherein at least one of the (C) plasticizer is a polyalkylene glycol plasticizer.
(3) The molded article according to any one of (1) to (2) , wherein the thickness of the molded article is less than 3 mm.
(4) The polylactic acid resin composition comprises (D) 0.1 to 200 parts by weight of an impact resistance improver and (E) 0.01 to 30 parts by weight of a reactive compound with respect to 100 parts by weight of the (A) polylactic acid resin. And (F) The molded article according to any one of (1) to (3) , which is a composition comprising at least one selected from 0.1 to 50 parts by weight of inorganic particles.
(5) (A) 0.5 to 50 parts by weight of a crystallization accelerator is blended with 100 parts by weight of a polylactic acid resin, and the (A) polylactic acid resin is (a) the total lactic acid of the polylactic acid resin. Among the components, polylactic acid resin containing 80% or more of L-form or 80% or more of D-form, and / or (b) polylactic acid stereocomplex, wherein the crystallization accelerator is (B) crystal Containing a nucleating agent and (C) a plasticizer, (B) the crystal nucleating agent is at least one selected from amide compounds and hydrazide compounds, and (C) the plasticizer contains two or more plasticizers The resin composition contains a particulate matter having a number average particle size in the major axis direction of 300 nm or less in observation with an electron microscope.
(6) The mold temperature is set to a temperature range not lower than the glass transition temperature and not higher than the melting point derived from the polylactic acid resin in the resin composition, and injection molding is performed in a molding cycle of 150 seconds or less (1) The manufacturing method of the molded article of any one of (4) .

  ADVANTAGE OF THE INVENTION According to this invention, the molded article which consists of a resin composition containing the polylactic acid resin excellent in transparency and heat resistance, and its manufacturing method can be provided.

  The (A) polylactic acid resin used in the present invention is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. As a polymerization component, it is less than 50 mol%, and it is preferable that it is 30 mol% or less from a heat resistant point, and it is more preferable that it is 10 mol% or less. Examples of such other copolymer component units include polycarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, and lactones. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5- Polyvalent carboxylic acids such as tetrabutylphosphonium sulfoisophthalic acid, ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopenty Glycol, glycerin, pentaerythritol, bisphenol A, polyhydric alcohols such as dihydric alcohol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., glycolic acid, Hydroxycarboxylic acids such as 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid or hydroxybenzoic acid, glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ- Lactones such as butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone can be used.

  In the present invention, it is preferable to use a polylactic acid resin having a high optical purity of the lactic acid component from the viewpoint of heat resistance. That is, among the total lactic acid components of the polylactic acid resin, it is preferable that the L isomer is contained at 80% or more, or the D isomer is contained at 80% or more, the L isomer is contained at 90% or more, or the D isomer is 90% or more. More preferably, the L-form is contained at 95% or more, or the D-form is more preferably contained at 95% or more, the L-form is contained at 98% or more, or the D-form is contained at 98% or more. It is particularly preferable that the L-form is contained in 99% or more, or the D-form is contained in 99% or more. Moreover, the upper limit of the content of L-form or D-form is 100%.

  (A) The molecular weight and molecular weight distribution of the polylactic acid resin are not particularly limited as long as they can be substantially molded, but the weight average molecular weight is preferably 10,000 from the viewpoint of heat resistance. More preferably, it is 40,000 or more, more preferably 80,000 or more, particularly preferably 100,000 or more, and most preferably 130,000 or more. The upper limit is not particularly limited, but is preferably 500,000 or less, more preferably 300,000 or less, still more preferably 250,000 or less, and particularly preferably less than 200,000 in terms of fluidity. The weight average molecular weight here is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  (A) Although it does not specifically limit about melting | fusing point of polylactic acid resin, From a point of a moldability and heat resistance, it is preferable that it is 120 degreeC or more, It is more preferable that it is 150 degreeC or more, 170 degreeC More preferably, it is more preferably 200 ° C. or higher. The melting point here is the temperature at the peak top of the endothermic peak measured by a differential scanning calorimeter (DSC).

  (A) As a manufacturing method of polylactic acid resin, a well-known polymerization method can be used, for example, the direct polymerization method from lactic acid or the ring-opening polymerization method via lactide can be used.

  In addition, as the polylactic acid resin (A) used in the present invention, it is preferable to use a polylactic acid stereocomplex in terms of heat resistance and crystallization characteristics. As a method of forming a polylactic acid stereocomplex, for example, L-form is 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and D-form is 90 mol% or more. A method of mixing 95 mol% or more, more preferably 98 mol% or more of poly-D-lactic acid by melt kneading, solution kneading, solid phase kneading or the like can be mentioned. In the method for obtaining a polylactic acid stereocomplex by mixing, the poly-L-lactic acid or poly-D-lactic acid may have a weight average molecular weight of 100,000 or more, but the poly-L-lactic acid or poly-D- It is preferable to apply a combination in which the weight average molecular weight of any one of lactic acid is 100,000 or less, preferably 50,000 or less, and the other weight average molecular weight is more than 100,000, preferably 120,000 or more. Another method is a method in which poly-L-lactic acid and poly-D-lactic acid are made into a block copolymer, that is, stereoblock polylactic acid, and a polylactic acid stereocomplex can be easily formed. In this respect, a method using poly-L-lactic acid and poly-D-lactic acid as a block copolymer is preferable.

  The polylactic acid resin (A) used in the present invention may be used alone, but for example, poly-L-lactic acid or poly-D-lactic acid having a high L-form or D-form content and a polylactic acid stereocomplex that forms a polylactic acid stereocomplex. A block copolymer of -L-lactic acid and poly-D-lactic acid can be used in combination.

  The present invention is characterized in that 0.5 to 50 parts by weight of a crystallization accelerator is blended with 100 parts by weight of the (A) polylactic acid resin. In the present invention, the crystallization accelerator is preferably composed of (B) a crystal nucleating agent and / or (C) a plasticizer. It is preferable to blend 10 parts by weight and (C) 1 to 50 parts by weight of a plasticizer.

  The (B) crystal nucleating agent used in the present invention may be any as long as it can obtain a molded article excellent in transparency and heat resistance. For example, aliphatic carboxylic amide, alicyclic carboxylic amide, aromatic Examples include organic nucleating agents such as amide compounds such as group carboxylic acid amides, hydrazide compounds, organic carboxylic acid metal salts, and organic sulfonic acid metal salts.

  In the amide compound used in the present invention, the aliphatic carboxylic acid amide includes lauric acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide or 12-hydroxystearic acid amide. Aliphatic monocarboxylic amide, N-lauryl lauric acid amide, N-palmityl palmitic acid amide, N-oleyl palmitic acid amide, N-oleyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl Stearic acid amide, N-stearyl oleic acid amide, N-stearyl erucic acid amide, N-stearyl-12-hydroxystearic acid amide, N-oleyl-12-hydroxystearic acid amide, methylol stearic acid amide, methylo N-substituted aliphatic monocarboxylic acid amides such as rubehenic acid amide or 12-hydroxystearic acid monoethanolamide, methylene bis stearic acid amide, methylene bis lauric acid amide, methylene bis-12-hydroxy stearic acid amide, ethylene biscaprin Acid amide, ethylene bis lauric acid amide, ethylene bis oleic acid amide, ethylene bis stearic acid amide, ethylene bis erucic acid amide, ethylene bis behenic acid amide, ethylene bis isostearic acid amide, ethylene bis-12-hydroxystearic acid amide, butylene Bis-stearic acid amide, hexamethylene bis-oleic acid amide, hexamethylene bis-stearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bis-12-hydride Such as xistearic acid amide, N, N′-dioleyl sebacic acid amide, N, N′-dioleyl adipic acid amide, N, N-distearyl adipic acid amide or N, N′-distearyl sebacic acid amide Examples of the aliphatic carboxylic acid bisamide include N, N′-dicyclohexanecarbonyl-1,4-diaminocyclohexane, 1,4-cyclohexanedicarboxamide, 1,4- Cyclohexanedicarboxylic acid diaminocyclohexane, 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, N, N′-bis (3-hydroxypropyl) -1,4-cubanedicarboxamide, N, N ′-( 1,4-cyclohexanediyl) bis (acetamide) and the like, aromatic Carboxylic acid amides include 1,4-cyclohexanedicarboxylic acid dianilide, 1,4-cyclohexanedicarboxylic acid dibenzylamide, trimesic acid tris (t-butylamide), trimesic acid tricyclohexylamide, trimesic acid tri (2-methylcyclohexylamide) ), Trimesic acid tri (4-cyclohexylamide), 2,6-naphthalene acid dicarboxylic acid dicyclohexylamide, N, N′-dibenzylcyclohexane-1,4-dicarboxamide, N, N′-distearylisophthalamide, N , N′-distearyl terephthalic acid amide, m-xylylene bis-stearic acid amide, or m-xylylene bis-12-hydroxystearic acid amide, and the like. Aliphatic carboxylic acid bisamide is more preferable, ethylene biscapric acid amide, ethylene bisoleic acid amide, ethylene bislauric acid amide, ethylene bis stearic acid amide, ethylene bis-12-hydroxystearic acid amide, hexamethylene bis- 12-hydroxystearic acid amide is more preferable, and ethylene bislauric acid amide, ethylene bis-stearic acid amide, and ethylene bis-12-hydroxystearic acid amide are particularly preferable.

  Examples of the hydrazide compound used in the present invention include acetic hydrazide, propionic acid hydrazide, benzoic acid hydrazide, carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedihydrazide, isophthalic acid dihydrazide, 3-hydroxy-2-naphthoic acid hydrazide, 1, 3-cyclohexanedicarbohydrazide, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylenedi-p-phenylene) disemicarbazide Hydrazide compounds such as N '-(2-benzylcarbamoylethyl) isonicotinic acid hydrazide or N, N'-dibenzoyl sebacic acid dihydrazide, and N, N'- in terms of transparency and heat resistance Dibenzoyl sebacin Dihydrazide is preferable.

  In the organic carboxylic acid metal salt used in the present invention, the aliphatic carboxylic acid metal salt includes sodium laurate, potassium laurate, magnesium laurate, calcium laurate, zinc laurate, sodium myristate, potassium myristate, magnesium myristate. , Calcium myristate, zinc myristate, lithium palmitate, potassium palmitate, magnesium palmitate, calcium palmitate, zinc palmitate, copper palmitate, lead palmitate, thallium palmitate, cobalt palmitate, sodium oleate, olein Potassium acid, magnesium oleate, calcium oleate, zinc oleate, lead oleate, thallium oleate, copper oleate, nickel oleate, stearic acid Tium, sodium stearate, potassium stearate, magnesium stearate, calcium stearate, barium stearate, aluminum stearate, thallium stearate, lead stearate, nickel stearate, beryllium stearate, sodium montanate, potassium montanate, montan Examples include magnesium oxide, calcium montanate, barium montanate, aluminum montanate, zinc montanate, nickel montanate, calcium oxalate, sodium succinate, etc., and aromatic carboxylic acid metal salts include sodium benzoate, Potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, tele Potassium Tal, sodium toluate, sodium salicylate, potassium salicylate, and the like zinc salicylate.

  Examples of the organic carboxylic acid metal salt used in the present invention include sodium benzenesulfonate, sodium dodecylbenzenesulfonate, sodium p-toluenesulfonate, sodium sulfoisophthalate and the like.

  Other crystal nucleating agents include glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, serine, threonine, methionine, cysteine, tryptophan, asparagine, glutamine, aspartic acid, glutamic acid, tyrosine, lysine, arginine, histidine. Amino acid-based compounds such as sodium salt of ethylene / acrylic acid or methacrylic acid copolymer, sodium salt or potassium salt of a polymer having a carboxyl group such as sodium salt of styrene / maleic anhydride copolymer (so-called ionomer), Benzylidene sorbitol and derivatives thereof, phosphorus compound metal salts such as sodium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate or 2,2-methylbis (4 -Di-t-butylphenyl) sodium and the like, and amino acid compounds are preferable in terms of transparency, heat resistance and moldability. Among them, L-tryptophan, D-tryptophan, DL-tryptophan, dehydrotryptophan More preferred are tryptophans such as α-methyltryptophan and N-acetyl-DL-tryptophan.

  In the present invention, it is preferable that the crystal nucleating agent (B) is at least one selected from an amide compound, a hydrazide compound, and an amino acid compound in that the effect of improving transparency and heat resistance is great. It is preferably at least one selected from amide compounds and hydrazide compounds, more preferably aliphatic carboxylic acid amides and / or hydrazide compounds, and even more preferably aliphatic carboxylic acid amides. In the present invention, (B) the crystal nucleating agent may be used alone or in combination of two or more, but when used in combination of two or more, transparency and In some cases, a molded product made of a resin composition having excellent heat resistance may be obtained.

  In the present invention, the blending amount of (B) crystal nucleating agent is from 0.6 to 100 parts by weight of (A) polylactic acid resin in terms of moldability, transparency, heat resistance, impact resistance and durability. The range of 8 parts by weight is preferable, the range of 0.8 to 5 parts by weight is more preferable, the range of 1 to 4 parts by weight is more preferable, and the range of 1 to 2.9 parts by weight is particularly preferable.

  As the plasticizer (C) used in the present invention, any plasticizer can be used as long as it can obtain a molded article excellent in transparency and heat resistance, and any general known plasticizer can be used without limitation. Examples thereof include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, epoxy plasticizers, and castor oil plasticizers.

  Examples of the polyester plasticizer used in the present invention include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, propylene glycol, 1,3-butanediol, 1,4- Examples thereof include polyesters composed of diol components such as butanediol, 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, glycerin monoacetomonomontanate, and glycerin triacetate. In addition, an alkylene oxide unit such as ethylene oxide or propylene oxide may be added such as polyoxyethylene glycerin triacetate.

  Examples of the polyvalent carboxylic acid plasticizer used in the present invention include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate or butyl benzyl phthalate, trimellit Trimellitic acid esters such as tributyl acid, trioctyl trimellitic acid or trihexyl trimellitic acid, succinic acid esters such as isodecyl succinate, triethylene glycol monomethyl ether succinate or benzyl methyl diglycol succinate, diisodecyl adipate, adipine Acid n-octyl-n-decyl ester, adipic acid diethylene glycol monomethyl ether ester, adipic acid methyl diglycol butyl diglycol ester, adipic acid Adipic acid esters such as dimethyl methyl glycol, adipic acid or benzyl butyl diglycol adipic acid, azelaic acid esters such as di-2-ethylhexyl azelate, sebacic acid such as dibutyl sebacate or di-2-ethylhexyl sebacate Examples include esters.

  Examples of the polyalkylene glycol plasticizer used in the present invention include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, and bisphenols. Polyalkylene glycols such as propylene oxide addition polymers, and bisphenol tetrahydrofuran addition polymers, and end-capping compounds such as terminal epoxy-modified compounds or terminal ether-modified compounds, and the like. Glycols, polypropylene glycols, poly (ethylene oxide / propylene oxide) blocks and / or random copolymers are preferred.

  The epoxy plasticizer used in the present invention generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, etc. In addition, mainly using bisphenol A and epichlorohydrin as raw materials So-called epoxy resins can also be used.

  The castor oil plasticizer used in the present invention may be any castor oil and derivatives thereof, such as castor oil, dehydrated castor oil, castor hydrogenated oil, castor oil fatty acid, dehydrated castor oil fatty acid, ricinoleic acid, Ricinoleic acid, 12-hydroxystearic acid, sebacic acid, undecylenic acid, heptylic acid, castor oil fatty acid condensate, castor oil fatty acid ester, methyl ricinolate, ethyl ricinolate, isopropyl ricinolate, butyl ricinolate, ethylene glycol monolysylate , Propylene glycol monolysylate, trimethylolpropane monolysylate, sorbitan monolysylate, castor oil fatty acid polyethylene glycol ester, castor oil ethylene oxide adduct, castor oil-based polyol, castor oil-based toluol or In addition, castor oil fatty acid ester, methyl ricinolate, ethyl ricinolate, isopropyl ricinolate, butyl ricinolate, ethylene glycol monolysylate, propylene glycol monolysylate, Trimethylolpropane monolysylate, sorbitan monolysylate, castor oil fatty acid polyethylene glycol ester, castor oil ethylene oxide adduct, castor oil-based polyol, castor oil-based toluol or castor oil-based diol are preferred.

  Other plasticizers include neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethyl butyrate, polyoxyethylene diacetate, polyoxyethylene di (2-ethylhexanoate), poly Polyol esters such as oxypropylene monolaurate, polyoxypropylene monostearate, polyoxyethylene dibenzoate, polyoxypropylene dibenzoate, aliphatic carboxylic acid esters such as butyl oleate, triethyl acetylcitrate, tributyl acetylcitrate, Oxyacid esters such as ethoxycarbonylmethyldibutyl citrate, di-2-ethylhexyl citrate, methyl acetylricinoleate or butyl acetylricinoleate, soybeans , Soybean oil fatty acid, soybean oil fatty acid ester, epoxidized soybean oil, rapeseed oil, rapeseed oil fatty acid, rapeseed oil fatty acid ester, epoxidized rapeseed oil, linseed oil, linseed oil fatty acid, linseed oil fatty acid ester, epoxidized linseed oil, coconut oil or coconut oil Examples include vegetable oil-based compounds such as fatty acids, pentaerythritol, sorbitol, polyacrylic acid esters, silicone oils, and paraffins.

  The plasticizer (C) of the present invention may be one type or a combination of two or more types, but preferably contains two or more types in terms of moldability, transparency and heat resistance, and at least 1 More preferably, the seed is a polyalkylene glycol plasticizer. Two or more polyalkylene glycol plasticizers can be used in combination. A combination of a polyalkylene glycol plasticizer and a castor oil plasticizer is also preferred.

  In the present invention, the blending amount of the plasticizer (C) is 1 to 20 parts by weight with respect to 100 parts by weight of the polylactic acid resin (A) in terms of moldability, transparency, heat resistance, impact resistance and durability. The range is preferably 2 to 10 parts by weight, more preferably 2 to 7 parts by weight.

  In the present invention, it is preferable to add an impact resistance improver in terms of excellent impact resistance. The impact resistance improver used in the present invention is not particularly limited as long as it can be used to improve the impact resistance of a thermoplastic resin, but is a rubber-like substance exhibiting rubber elasticity at room temperature, for example At least one selected from the following various impact resistance improvers can be used.

  That is, specific examples of the impact modifier include ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene-1 copolymer, various acrylic rubbers, ethylene-acrylic acid copolymer. Copolymer and alkali metal salt thereof (so-called ionomer), ethylene-glycidyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid alkyl ester copolymer (for example, ethylene-methyl acrylate copolymer, ethylene-acrylic acid) Ethyl copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer), ethylene-vinyl acetate copolymer, acid-modified ethylene-propylene copolymer, diene rubber (for example, polybutadiene, polyisoprene, Polychloroprene), diene and vinyl monomer Polymers and hydrogenated products thereof (for example, 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, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, polybutadiene grafted with styrene, butadiene-acrylonitrile copolymer Polymer), polyisobutylene, copolymer of isobutylene and butadiene or isoprene, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, silicone rubber, polyurethane rubber, polyether rubber Epichlorohydrin rubber, such as polyester elastomer or polyamide elastomer can be cited. Further, those having various cross-linking degrees, those having various microstructures such as cis structure and trans structure, and multilayer polymers composed of a core layer and one or more shell layers covering it are also used. be able to. In the present invention, as the impact resistance improver, the various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers or graft copolymers. it can. Furthermore, when producing these (co) polymers, it is also possible to copolymerize monomers such as other olefins, dienes, aromatic vinyl compounds, acrylic acid, acrylic ester or methacrylic ester. is there.

  Among these impact resistance improvers, a polymer containing an acrylic unit and a polymer containing a unit having an acid anhydride group and / or a glycidyl group are preferable. Preferable examples of the acrylic unit here include methyl methacrylate units, methyl acrylate units, ethyl acrylate units or butyl acrylate units, and preferable examples of units having an acid anhydride group or glycidyl group. May include maleic anhydride units or glycidyl methacrylate units.

  In the present invention, the impact resistance improver is more preferably a multilayer polymer composed of a core layer and one or more shell layers covering the core layer in that it is particularly excellent in impact resistance. The shell layer is more preferably a multilayer structure polymer composed of a polymer containing methyl methacrylate units and / or methyl acrylate units. In the present invention, the multilayer structure polymer is composed of a core layer and one or more shell layers covering the core layer, and a so-called core-shell type structure in which adjacent layers are composed of different polymers. It is a polymer having. In addition, the number of layers constituting the multilayer structure polymer is not particularly limited, and may be two or more, and may be three or more or four or more.

  The multilayer structure polymer used in the present invention is preferably a multilayer structure polymer having at least one rubber layer therein. Here, the type of the rubber layer is not particularly limited as long as it is composed of a polymer component having rubber elasticity. For example, the rubber | gum comprised from what polymerized the (meth) acryl component, the silicone component, the styrene component, the nitrile component, the conjugated diene component, the urethane component, or the ethylene propylene component can be mentioned. Preferred rubbers include, for example, (meth) acrylic components such as ethyl (meth) acrylate units, butyl (meth) acrylate units, (meth) acrylic acid-2-ethylhexyl units or benzyl (meth) acrylate units, dimethyl Polymerize silicone components such as siloxane units and phenylmethylsiloxane units, styrene components such as styrene units and α-methylstyrene units, nitrile components such as acrylonitrile units and methacrylonitrile units, or conjugated diene components such as butanediene units and isoprene units. It is a rubber made of In addition to these components, a crosslinked rubber obtained by copolymerizing and crosslinking a crosslinkable component such as a divinylbenzene unit, an allyl (meth) acrylate unit, or a butylene glycol diacrylate unit is also preferable. Among these, in terms of transparency and impact resistance, the rubber layer is preferably a crosslinked rubber, more preferably a crosslinked rubber having a glass transition temperature of 0 ° C. or less. , Ethyl acrylate units, 2-ethylhexyl acrylate units, butyl acrylate units, benzyl acrylate units, and allyl methacrylate units are suitably selected and used in combination, and allyl methacrylate units are preferably used as rubber layer constituent units. It is particularly preferable to use in the range of 0.005 to 3% by weight.

  In the present invention, in the multilayer structure polymer, the type of layers other than the rubber layer is not particularly limited as long as it is composed of a polymer component having thermoplasticity, but transparency, heat resistance and resistance From the viewpoint of impact, it is preferably a polymer component having a glass transition temperature higher than that of the rubber layer. Polymers having thermoplastic properties include unsaturated carboxylic acid alkyl ester units, glycidyl group-containing vinyl units, unsaturated dicarboxylic anhydride units, aliphatic vinyl units, aromatic vinyl units, and vinyl cyanide units. Examples include polymers containing at least one unit selected from units, maleimide units, unsaturated dicarboxylic acid units and other vinyl units, among others, unsaturated carboxylic acid alkyl ester units, A polymer containing at least one unit selected from an unsaturated glycidyl group-containing unit and an unsaturated dicarboxylic acid anhydride unit is preferred, and further selected from an unsaturated glycidyl group-containing unit or an unsaturated dicarboxylic acid anhydride unit. More preferred is a polymer containing at least one unit.

  The unsaturated carboxylic acid alkyl ester unit is not particularly limited, but (meth) acrylic acid alkyl ester is preferably used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic N-hexyl acid, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, ( Chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6 (meth) acrylic acid -Pentahydroxyhexyl, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, amino acid acrylate Examples include ethyl, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, and the like, which are highly effective in improving impact resistance. Methyl (meth) acrylate is preferably used. These units can be used alone or in combination of two or more.

  The glycidyl group-containing vinyl-based unit is not particularly limited, and examples thereof include glycidyl (meth) acrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether, and 4-glycidyl styrene. The glycidyl (meth) acrylate is preferably used in that it has a great effect of improving impact resistance. These units can be used alone or in combination of two or more.

  Examples of the unsaturated dicarboxylic anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, or aconitic anhydride, etc., from the viewpoint that the effect of improving impact resistance is great. Maleic anhydride is preferably used. These units can be used alone or in combination of two or more.

  The aliphatic vinyl unit may be ethylene, propylene or butadiene, and the aromatic vinyl unit may be styrene, α-methylstyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexyl. Styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene, halogenated styrene, etc., as vinyl cyanide units, acrylonitrile, methacrylonitrile, ethacrylonitrile, etc. maleimide Units include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, N- (chlorophenyl) maleimide and other unsaturated dicarboxylic acid units such as maleic acid, maleic acid monoethyl ester, itaconic acid and phthalic acid, and other vinyl units such as acrylamide, methacrylamide, N-methylacrylamide, Butoxymethylacrylamide, N-propylmethacrylamide, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2 -Acroyl-oxazoline or 2-styryl-oxazoline can be mentioned, and these units can be used alone or in combination of two or more.

  As the multilayer structure polymer used in the present invention, the type of the shell layer is not particularly limited, and is an unsaturated carboxylic acid alkyl ester unit, a glycidyl group-containing vinyl unit, an aliphatic vinyl unit, an aromatic Examples include polymers containing vinyl units, vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic anhydride units and / or other vinyl units, and transparency. From the viewpoint of impact resistance, a multilayer structure polymer composed of a polymer containing methyl methacrylate units and / or methyl acrylate units is preferable.

  As the multilayer structure polymer used in the present invention, a commercially available product may be used as a material satisfying the above-mentioned conditions, and it can also be produced by a known method. "Metablene", Kaneka "Kane Ace", Rohm and Haas "Paraloid", Gantz Kasei "Staffyroid" or Kuraray "Paraface" can be used, and these should be used alone or in combination of two or more. Can do.

  As a known method, an emulsion polymerization method is more preferable. As a production method, a desired monomer mixture is first emulsion-polymerized to form core particles, and then another monomer mixture is emulsion-polymerized in the presence of the core particles to form a shell layer around the core particles. Make core-shell particles to form. Further, in the presence of the particles, another monomer mixture is emulsion-polymerized to form core-shell particles that form another shell layer. Such a reaction is repeated to obtain a multilayer polymer composed of a desired core layer and one or more shell layers covering it. The polymerization temperature for forming the (co) polymer of each layer is preferably 0 to 120 ° C, more preferably 5 to 90 ° C for each layer.

  The emulsifier used in the emulsion polymerization is not particularly limited, but is selected depending on the polymerization stability and a desired average primary particle size, and a known emulsifier such as an anionic surfactant, a cationic surfactant, or a nonionic surfactant is used alone or It is preferable to use 2 or more types, and an anionic surfactant is more preferable. Examples of the anionic surfactant include sodium stearate, sodium myristate, sodium carboxylate such as sodium N-lauroyl sarcosine, sulfonate such as sodium dioctyl sulfosuccinate and sodium dodecylbenzene sulfonate, and sodium lauryl sulfate. Examples thereof include sulfate ester salts and phosphate ester salts such as sodium mono-n-butylphenylpentaoxyethylene phosphate. The addition amount of the emulsifier is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the total amount of monomers used.

  The polymerization initiator used for emulsion polymerization is not particularly limited, but includes inorganic peroxides such as potassium persulfate and ammonium persulfate, hydrogen peroxide-ferrous salt, potassium persulfate-acidic sodium sulfite, Start of water-soluble redox initiators such as ammonium sulfate-acidic sodium sulfite, water-soluble redox systems such as cumene hydroperoxide-sodium formaldehyde sulfoxylate, tert-butyl hydroperoxide-sodium formaldehyde sulfoxylate Among them, inorganic peroxide initiators and water-oil-soluble redox initiators are preferable. The addition amount of the polymerization initiator is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the total monomers used.

The multilayer structure polymer used in the present invention preferably satisfies at least one of the following conditions in terms of transparency and impact resistance.
(C) Refractive index 1.44-1.49
(D) including a constituent having a glass transition temperature of 30 ° C. or lower

  Furthermore, the refractive index of the multilayer structure polymer is more preferably 1.45 to 1.48 from the viewpoint of excellent transparency. In the present invention, the refractive index is a value measured at 23 ° C. and a wavelength of 589 nm using an Abbe refractometer.

  Furthermore, in terms of excellent impact resistance, the glass transition temperature is more preferably a component containing 0 ° C. or less, more preferably a component containing −30 ° C. or less, and a composition of −40 ° C. or less. It is particularly preferred that it contains components. In the present invention, the glass transition temperature is a value measured using a differential scanning calorimeter at a rate of temperature increase of 20 ° C./min.

  In the present invention, the average primary particle diameter of the multilayer structure polymer is not particularly limited, but is preferably 10 to 10000 nm, more preferably 20 to 1000 nm in terms of transparency and impact resistance. It is more preferable that it is 50-700 nm, and it is most preferable that it is 100-500 nm.

  In the present invention, the blending amount of the impact modifier is not particularly limited, but is preferably 0.1 to 200 parts by weight with respect to 100 parts by weight of the polylactic acid resin in terms of impact resistance. -100 parts by weight is more preferable, 5-50 parts by weight is further preferable, and 10-30 parts by weight is particularly preferable.

  In the present invention, it is preferable that a reactive compound is further blended in that transparency, heat resistance and impact resistance can be improved, and hydrolysis resistance can be improved. In the present invention, the reactive compound is more preferably a compound having a functional group reactive with a hydroxyl group and / or a carboxyl group, and at least one selected from a glycidyl group, an acid anhydride group, a carbodiimide group, and an oxazoline group. More preferably, a reactive compound containing the above functional group is added. In the present invention, when a multilayer structure polymer is blended, it is preferable to blend a reactive compound because the dispersibility of the multilayer structure polymer is improved and the impact resistance improving effect is increased.

  In the present invention, as the reactive compound containing a glycidyl group, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, and an alicyclic epoxy compound can be preferably used. By blending these, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.

  Examples of glycidyl ether compounds include butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene oxide phenol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol Diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane trig Bisphenols such as sidyl ether, pentaerythritol polyglycidyl ether, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone; Examples thereof include a bisphenol A diglycidyl ether type epoxy resin, a bisphenol F diglycidyl ether type epoxy resin, a bisphenol S diglycidyl ether type epoxy resin obtained from a condensation reaction with epichlorohydrin. Among these, bisphenol A diglycidyl ether type epoxy resin is preferable.

  Examples of glycidyl ester compounds include benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester 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, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester , Hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, Hexanedicarboxylic 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 tetra A glycidyl ester etc. can be mentioned. Among these, benzoic acid glycidyl ester and versatic acid glycidyl ester are preferable.

  Examples of glycidylamine compounds include tetraglycidylaminodiphenylmethane, triglycidyl-paraaminophenol, triglycidyl-metaaminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, tetraglycidylbisamino Examples include methylcyclohexane, triglycidyl cyanurate, and triglycidyl isocyanurate.

  Examples of glycidylimide compounds include N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3-methylphthalimide, N-glycidyl-3,6- Dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl-3,4,5,6-tetrabromophthalimide, N -Glycidyl-4-n-butyl-5-bromophthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleimide, N- Glycidyl-α, β-dimethyl Succinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylsteramide, etc. be able to. Of these, N-glycidylphthalimide is preferable.

  Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 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 imide N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, and the like. In addition, epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, cresol nozolac type epoxy resins, and the like can be used.

  In the present invention, examples of the reactive compound containing an acid anhydride group include succinic anhydride, maleic anhydride, and phthalic anhydride. Furthermore, the polymer etc. which contain an above-described compound as a monomer unit can be mentioned.

  In the present invention, the reactive compound containing a carbodiimide group is a compound having at least one carbodiimide group represented by (—N═C═N—) in the molecule, for example, in the presence of a suitable catalyst. The organic isocyanate can be heated and produced by a decarboxylation reaction.

  Examples of carbodiimide compounds include diphenylcarbodiimide, di-cyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, di-p- Nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2 , 5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene- Su-di-p-chlorophenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, hexamethylene-bis-cyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, ethylene-bis-dicyclohexylcarbodiimide, N , N′-di-o-triylcarbodiimide, N, N′-diphenylcarbodiimide, N, N′-dioctyldecylcarbodiimide, N, N′-di-2,6-dimethylphenylcarbodiimide, N-triyl-N ′ -Cyclohexylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide, N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N-toluyl-N'-phenylcarbodiimide, N, N'-di-p-nitrof Phenylcarbodiimide, N, N′-di-p-aminophenylcarbodiimide, N, N′-di-p-hydroxyphenylcarbodiimide, N, N′-di-cyclohexylcarbodiimide, N, N′-di-p-tolylcarbodiimide N, N′-benzylcarbodiimide, N-octadecyl-N′-phenylcarbodiimide, N-benzyl-N′-phenylcarbodiimide, N-octadecyl-N′-tolylcarbodiimide, N-cyclohexyl-N′-tolylcarbodiimide, N -Phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide, N, N'- Di-o-isopropylphenylcarbodiimide, N, '-Di-p-isopropylphenylcarbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N, N'-di-2,6-diethylphenylcarbodiimide N, N′-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N′-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N′-di-2,4,6-trimethylphenyl Mono- or dicarbodiimide compounds such as carbodiimide, N, N′-di-2,4,6-triisopropylphenylcarbodiimide, N, N′-di-2,4,6-triisobutylphenylcarbodiimide, poly (1,6 -Hexamethylenecarbodiimide), poly (4,4'-methylenebiscyclohexylcarbodi) Imide), 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 (tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly ( Examples thereof include polycarbodiimides such as triethylphenylene carbodiimide) and poly (triisopropylphenylene carbodiimide). Of these, N, N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide or polycarbodiimide is preferable.

  In the present invention, examples of the reactive compound containing an oxazoline group include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, 2-butoxy-2-oxazoline, 2 -Pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-nonyloxy-2-oxazoline, 2-decyloxy-2-oxazoline 2-cyclopentyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-crotyloxy-2-oxazoline, 2-phenoxy-2 -Oxazoline, 2-Credit 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-propyl-2-oxazoline, 2-butyl-2 -Oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline 2-cyclopentyl-2-oxazoline, 2-cyclohexyl-2- Xazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-o-ethylphenyl-2-oxazoline, 2-o-propyl Phenyl-2-oxazoline, 2-o-phenylphenyl-2-oxazoline, 2-m-ethylphenyl-2-oxazoline, 2-m-propylphenyl-2-oxazoline, 2-p-phenylphenyl-2-oxazoline, 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2′-bis (4,4′-dimethyl-2-oxazoline), 2,2 '-Bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4'-diethyl-2-oxazoline), 2,2'-bis (4-propyl (Lopyl-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′-dimethyl-2-oxazoline), 2,2′-m-phenylenebis (4-methyl-2-oxazoline), 2,2′-m-phenylene Screw (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'-tetramethylene Bis (4,4′-dimethyl-2-oxazoline), 2,2′-9,9′-diphenoxyethanebis (2-oxazoline), 2,2′-cyclohexylenebis (2-oxazoline), 2, And 2'-diphenylenebis (2-oxazoline). Furthermore, the polyoxazoline compound etc. which contain the above-mentioned compound as a monomer unit can be mentioned.

  In the present invention, the reactive compound is preferably a polymer having a weight average molecular weight of 1,000 to 300,000, and more preferably 5,000 to 250,000, in that bleeding out can be suppressed. Here, the weight average molecular weight is a PMMA equivalent weight average molecular weight measured by GPC using hexafluoroisopropanol as a solvent. Such a reactive compound is a polymer in which at least one functional group selected from a glycidyl group, an acid anhydride group, a carbodiimide group and an oxazoline group is introduced into the main chain or side chain in the molecule. Preferably, the polymer may be either a homopolymer or a copolymer, and any of a random copolymer, a block copolymer, a graft copolymer, and the like can be used as the copolymer.

  In the present invention, the reactive compound is preferably a polymer containing a glycidyl group-containing vinyl-based unit in terms of transparency, heat resistance and impact resistance.

  In the present invention, specific examples of the raw material monomer for forming the glycidyl group-containing vinyl unit include glycidyl esters of unsaturated monocarboxylic acids such as glycidyl (meth) acrylate and glycidyl p-styrylcarboxylate, maleic acid, itaconic acid Examples thereof include monoglycidyl esters or polyglycidyl esters of unsaturated polycarboxylic acids such as unsaturated glycidyl ethers such as allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-4-glycidyl ether. Among these, glycidyl acrylate or glycidyl methacrylate is preferably used in terms of radical polymerizability. These can be used alone or in combination of two or more.

  In the present invention, the polymer containing a glycidyl group-containing vinyl-based unit preferably contains a vinyl-based unit other than the glycidyl group-containing vinyl-based unit as a copolymerization component. Can be adjusted. As vinyl units other than glycidyl group-containing vinyl units, acrylic vinyl units, carboxylic acid vinyl ester units, aromatic vinyl units, unsaturated dicarboxylic anhydride units, unsaturated dicarboxylic acid units, aliphatic types Examples thereof include vinyl units, maleimide units, and other vinyl units.

  Specific examples of the raw material monomer for forming the acrylic vinyl unit include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, and n-butyl acrylate. , N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate , Isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, Roxypropyl, hydroxypropyl methacrylate, acrylic acid ester or methacrylate ester of polyethylene glycol or polypropylene glycol, trimethoxysilylpropyl acrylate, trimethoxysilylpropyl methacrylate, methyldimethoxysilylpropyl acrylate, methyldimethoxysilylpropyl methacrylate, Acrylic vinyl units having an amino group such as acrylonitrile, methacrylonitrile, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide, α-hydroxymethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc. In particular, acrylic acid, methacrylic acid, methyl acrylate, Methyl crylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-methacrylic acid t- Butyl, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylonitrile, methacrylonitrile are preferred, and acrylic acid, methacrylic acid, methyl acrylate, Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Acrylonitrile, methacrylonitrile is used. These may be used alone or in combination of two or more.

  Specific examples of the raw material monomer that forms the vinyl carboxylate unit include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, Monofunctional aliphatic vinyl carboxylates such as vinyl palmitate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate or vinyl cyclohexanecarboxylate, vinyl benzoate or vinyl cinnamate, etc. And polyfunctional vinyl carboxylates such as vinyl aromatic carboxylate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotonate and vinyl sorbate. Of these, vinyl acetate is preferably used. These may be used alone or in combination of two or more.

  Specific examples of the raw material monomer for forming the aromatic vinyl unit include styrene, α-methylstyrene, p-methylstyrene, α-methyl-p-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2, 4 -Dimethylstyrene, 1-vinylnaphthalene, chlorostyrene, bromostyrene, divinylbenzene, vinyltoluene and the like can be mentioned, among which styrene and α-methylstyrene are preferably used. These may be used alone or in combination of two or more.

  Examples of the raw material monomer that forms the unsaturated dicarboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, or aconitic anhydride, among which maleic anhydride is preferably used. Is done. These may be used alone or in combination of two or more.

  Examples of the raw material monomer for forming the unsaturated dicarboxylic acid unit include maleic acid, maleic acid monoethyl ester, itaconic acid, and phthalic acid. Among these, maleic acid and itaconic acid are preferably used. These may be used alone or in combination of two or more.

  Examples of raw material monomers for forming aliphatic vinyl units include ethylene, propylene, and butadiene. Examples of raw material monomers for forming maleimide units include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- As other raw material monomers for forming vinyl units such as isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, N- (chlorophenyl) maleimide, N-vinyldiethylamine, N- Examples thereof include acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, and the like. These can be used alone or in combination of two or more.

  In the present invention, the glass transition temperature of the polymer containing a glycidyl group-containing vinyl-based unit is not particularly limited. More preferably, it is in the range of ˜70 ° C., most preferably in the range of 50 to 65 ° C. The glass transition temperature here is an intermediate point glass transition temperature measured by DSC at a temperature increase temperature of 20 ° C./min by the method of JIS K7121. In addition, the glass transition temperature of the polymer containing a glycidyl group-containing vinyl-based unit can be controlled by adjusting the composition of the copolymerization component. The glass transition temperature can usually be increased by copolymerizing aromatic vinyl units such as styrene, and can be decreased by copolymerizing acrylic ester units such as butyl acrylate.

  In the present invention, the polymer containing a glycidyl group-containing vinyl-based unit usually contains a volatile component because unreacted raw material monomers and solvents remain. The amount of the non-volatile component that is the balance is not particularly limited, but it is preferable that the non-volatile component amount is large from the viewpoint of suppressing the generation of gas. Specifically, it is preferably 95% by weight or more, more preferably 97% by weight or more, further preferably 98% by weight or more, and most preferably 98.5% by weight or more. preferable. In addition, the non-volatile component here represents the remaining amount ratio when the sample 10g is heated at 110 degreeC for 1 hour in nitrogen atmosphere.

  In the present invention, a polymer containing a glycidyl group-containing vinyl-based unit may use a sulfur compound as a chain transfer agent (molecular weight modifier) in order to obtain a low molecular weight product. Contains sulfur. Here, although sulfur content is not specifically limited, From the viewpoint of suppressing unpleasant odor, it is preferable that the sulfur content is small. Specifically, the sulfur atom is preferably 1000 ppm or less, more preferably 100 ppm or less, further preferably 10 ppm or less, and most preferably 1 ppm or less.

  In the present invention, the method for producing a polymer containing a glycidyl group-containing vinyl-based unit is not particularly limited as long as the conditions specified in the present invention are satisfied. Bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. The known polymerization method can be used. When using these methods, a polymerization initiator, a chain transfer agent, a solvent, or the like may be used, but these remain as impurities in the finally obtained polymer containing a glycidyl group-containing vinyl-based unit. There are things to do. The amount of these impurities is not particularly limited, but it is preferable that the amount of impurities is small from the viewpoint of suppressing a decrease in heat resistance and weather resistance. Specifically, the amount of impurities is preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 3% by weight or less, and particularly preferably 1% by weight or less, with respect to the finally obtained polymer. Most preferred.

  As a method for producing a polymer containing a glycidyl group-containing vinyl-based unit that satisfies the molecular weight, glass transition temperature, nonvolatile component amount, sulfur content, impurity amount, and the like as described above, a high temperature of 150 ° C. or higher is applied. A method of continuous bulk polymerization under a pressure condition (preferably 1 MPa or more) in a short time (preferably 5 to 30 minutes) is a high polymerization rate, a polymerization initiator or a chain transfer agent that causes impurities and sulfur content Alternatively, it is more preferable in that no solvent is used.

  In the present invention, the compounding amount of the reactive compound is excellent in transparency, heat resistance, impact resistance, fluidity, molding processability, durability or bleed-out resistance with respect to 100 parts by weight of the polylactic acid resin. 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 0.5 to 3 parts by weight.

  In the present invention, it is preferable to further mix inorganic particles from the viewpoint of heat resistance, the short axis length of the inorganic particles in the resin composition is 1 to 300 nm, and the long axis length is 1 to 1000 nm. Preferably there is. In terms of transparency, the short axis length of the inorganic particles is more preferably 5 to 200 nm, further preferably 10 to 100 nm, and the long axis length is 10 to 900 nm. More preferably, it is 50-800 nm. In the present invention, the short axis length and the long axis length of the inorganic particles are obtained by observing the resin composition at 20,000 times using an electron microscope, and about 20 arbitrary inorganic particles, preferably 100 particles. The shape is observed and measured, and the shortest length is taken as the minor axis direction, the longest length is taken as the major axis direction, and each is an average value.

  In the present invention, the inorganic particles may be granular, spherical, plate-like, or fibrous, but are preferably plate-like from the viewpoint of heat resistance.

  In the present invention, the granular or spherical inorganic particles include zinc oxide, magnesium oxide, iron oxide, titanium oxide, titania, zirconia, ceria, alumina, silica, calcium carbonate, talc, mica, kaolin, graphite powder, carbon black, etc. Among them, silica is preferable.

  In the present invention, as the plate-like inorganic particles, silicates such as talc, mica, glass flakes, montmorillonite and smectite can be used, and among them, silicates are preferable.

  In the present invention, glass fiber, carbon fiber, zinc oxide, alumina, calcium titanate, potassium titanate, barium titanate, aluminum borate, magnesium borate, magnesium oxysulfate fiber, etc. are used as the fibrous inorganic particles. be able to.

  In the present invention, the inorganic particles are more preferably those containing silicon, and specifically include silica or silicate, among which layered silicates are more preferable, and organically modified layered silicates. More preferably. In the present invention, by performing elemental analysis using an electron microscope-X-ray microanalyzer (XMA), it can be determined that the particles are inorganic particles, and silicon can be detected.

  In the present invention, the silica may be powder, water or an organic solvent dispersed sol (colloidal silica), but colloidal silica is preferable in terms of transparency. Furthermore, in terms of transparency, the surface is treated with at least one functional group selected from a hydroxyl group, amino group, amide group, carboxyl group, glycidyl group, acid anhydride group, carbodiimide group, and oxazoline group. Is preferred. By using the surface-treated silica, the affinity with the matrix resin is improved, which is effective in suppressing aggregation and dispersibility of inorganic particles, and can be uniformly dispersed in the resin composition. A resin composition having excellent transparency can be obtained.

  In the present invention, the organically modified layered silicate is a layered silicate in which an exchangeable cation or anion existing between layers is exchanged with an organic onium ion or an organic anion, and in particular, the exchangeable cation is an organic onium ion. Exchanged layered silicates are preferred.

  A layered silicate having exchangeable ions between layers has a structure in which plate-like materials having a width of 0.05 to 0.5 μm and a thickness of 6 to 15 Å are laminated, and exchangeable ions are provided between the layers of the plate-like materials. have. The ion exchange capacity may be 0.2 to 3 meq / g, and preferably the ion exchange capacity is 0.8 to 1.5 meq / g.

  Specific examples of layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, titanium phosphate, Li Swellable mica, hydrotalcite, etc., such as Na type fluorine teniolite, Na type fluorine teniolite, Na type tetrasilicon fluorine mica, Li type tetrasilicon fluorine mica, etc. There may be. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable.

  Examples of organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. The ammonium ion may be any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium. Examples of the primary ammonium ion include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, and benzyl ammonium. The secondary ammonium ion can include methyldodecylammonium or methyloctadecylammonium, and the tertiary ammonium ion can include dimethyldodecylammonium or dimethyloctadecylammonium. Benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldi Benzyltrialkylammonium ions such as tildodecylammonium, benzyldimethyloctadecylammonium or benzalkonium, alkyltrimethylammonium ions such as trimethyloctylammonium, trimethyldodecylammonium, trimethyloctadecylammonium, dimethyldioctylammonium, dimethyldidodecylammonium or dimethyldioctadecyl Examples thereof include dimethyldialkylammonium ions such as ammonium, trialkylmethylammonium ions such as trioctylmethylammonium or tridodecylmethylammonium, and benzethonium ions having two benzene rings. In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, amino at the terminal Examples also include ammonium ions derived from polyalkylene glycols having a group. Among these ammonium ions, preferred compounds include trioctylmethylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium and the like. These ammonium ions are generally available as a mixture, and the above compound names are representative compound names containing a small amount of analogs. These may be used alone or in combination of two or more. Further, those having a reactive functional group and those having high affinity are preferable, and ammonium ions derived from 12-aminododecanoic acid, polyalkylene glycol having an amino group at the terminal, and the like are also preferable.

  Examples of the organic anion include a long-chain carboxylic acid, and examples thereof include lauric acid, decanoic acid, stearic acid, dodecadicarboxylic acid, and dimer acid.

  In the present invention, the organically modified layered silicate can be produced by reacting a layered silicate having an exchangeable cation or anion between layers, an organic onium ion or an organic anion by a known method. Specifically, a method by ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a layered silicate with a liquid or molten organic salt can be used.

  In the present invention, the amount of organic ions relative to the layered silicate is the cation exchange capacity of the layered silicate in terms of the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, and the suppression of odor generation. In general, it is in the range of 0.4 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents.

  In addition, it is preferable to use the organically modified layered silicate after pretreatment with a coupling agent having a reactive functional group in order to obtain better mechanical strength. Examples of the coupling agent having a reactive functional group include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

  In the present invention, the organically modified layered silicate is preferably uniformly dispersed in the resin composition. Here, uniform dispersion means that the layered silicate is dispersed in a laminated state of 5 layers or less without having a local mass.

  In the present invention, the blending amount of the inorganic particles is 100 parts by weight of the polylactic acid resin in terms of transparency, heat resistance, impact resistance, fluidity, molding processability, durability, surface hardness and gas permeability. 0.1-50 weight part is preferable, 0.5-20 weight part is more preferable, and 1-10 weight part is further more preferable.

  In this invention, it is preferable to mix | blend a lubricant or a mold release agent from the point that the molded article which consists of a resin composition excellent in moldability, heat resistance, or transparency is obtained. As the lubricant or mold release agent, those usually used for the thermoplastic resin lubricant or mold release agent are preferable, and specifically, fatty acids, oxy fatty acids, fatty acid metals not included in the crystallization accelerator used in the present invention. Examples include salts, fatty acid esters, aliphatic partially saponified esters, fatty acid amides, alkylene bis fatty acid amides, paraffins, low molecular weight polyolefins, aliphatic ketones, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acid polyglycol esters or modified silicones. be able to. The blending amount of the lubricant or mold release agent is preferably 0.01 to 3 parts by weight, preferably 0.03 to 2 parts by weight with respect to 100 parts by weight of the polylactic acid resin (A) in terms of moldability, heat resistance and transparency. Part is more preferred.

  In the present invention, a stabilizer is preferably blended from the viewpoint that a molded article made of a resin composition excellent in moldability, durability, transparency or heat resistance can be obtained. As the stabilizer, those usually used as stabilizers for thermoplastic resins are preferred, and among them, at least one selected from an antioxidant, a light stabilizer or an ultraviolet absorber is more preferred. Hindered phenol compounds, phosphite compounds, phosphate compounds, thioether compounds, benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalate anilide compounds not included in the crystallization accelerator used in the invention , Cyanoacrylate compounds or hindered amine compounds. The blending amount of the stabilizer is preferably 0.01 to 3 parts by weight, preferably 0.03 to 2 parts by weight with respect to 100 parts by weight of the polylactic acid resin (A) in terms of moldability, durability, heat resistance and transparency. Part is more preferred.

  For the resin composition used in the present invention, a filler (glass fiber, carbon fiber, metal fiber, natural fiber, organic fiber, glass flake, glass bead, ceramic fiber, ceramic bead is used as long as the object of the present invention is not impaired. , Asbestos, wollastonite, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolinite, finely divided silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, Aluminum oxide, titanium oxide, aluminum silicate, zirconium silicate, silicon oxide, gypsum, novaculite, dawsonite or clay, fluidity improver (branched polymer, liquid crystal polymer, low molecular weight linear polyester, low molecular weight linear polyester) Polycarbonate , Aromatic low molecular weight compounds, acrylic compounds or compounds having a functional group such as three or more hydroxyl groups or amino groups), brominated flame retardants, chlorinated flame retardants, phosphorous flame retardants, nitrogen compound based flame retardants Flame retardants such as flame retardants, silicone flame retardants or other inorganic flame retardants, colorants including dyes or pigments, nucleating agents, antistatic agents and the like can be added.

  In the present invention, other thermoplastic resins (for example, acrylic resins such as polymethylmethacrylate, polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene ( AS) resin, acrylonitrile / styrene / acrylate (ASA) resin, acrylonitrile / ethylene / styrene (AES) resin, methyl methacrylate / styrene (MS) resin, cellulose resin such as cellulose acetate, polyarylate, cyclic olefin resin, nylon 6, nylon 46, nylon 66, aromatic nylon, polyacetal, polycarbonate, polyphenylene oxide, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, polyether Polyimide, polyvinylphenol, fluororesin, polyethylene, polybutylene terephthalate, polybutylene succinate, polybutylene adipate, etc.) or thermosetting resin (eg phenol resin, melamine resin, polyester resin, silicone resin, epoxy resin, etc.) Alternatively, at least one or more kinds of soft thermoplastic resins (for example, ethylene / glycidyl methacrylate copolymer, polyester elastomer, polyamide elastomer, ethylene / propylene terpolymer, ethylene / butene-1 copolymer, etc.) can be blended. .

  The production method of the resin composition used in the present invention is not particularly limited. For example, (A) a polylactic acid resin, a crystallization accelerator and other additives as necessary are blended in advance, and then the melting point In the above, a method of uniformly melting and kneading with a single-screw, twin-screw or multi-screw extruder, a method of removing a solvent after mixing in a solution, a solid-phase kneading method of uniformly kneading while applying a shear in a solid state, etc. are used. However, a method of uniformly melt-kneading with a single-screw or twin-screw extruder is preferable from the viewpoint of productivity, and a method of uniformly melt-kneading with a twin-screw extruder is more preferable from the viewpoint of transparency.

  The temperature for melt kneading is not particularly limited, but is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, further preferably 220 ° C. or higher, and preferably 350 ° C. or lower in terms of heat resistance. ° C or lower is more preferable, and 250 ° C or lower is more preferable.

  The melt flow rate (MFR) of the resin composition used in the present invention is not particularly limited, but the MFR measured at 210 ° C. and 21.2 N load according to JIS K7210 is preferably 0.1 to 40 g / 10 min. 1 to 20 g / 10 min is more preferable, and 1 to 5 g / 10 min is further preferable. If the MFR is 0.1 g / 10 min or less, the load on the melt-kneading apparatus tends to increase, and a stable resin composition tends to be difficult to obtain. If it exceeds 40 g / 10 min, the heat resistance tends to decrease. .

  The deflection temperature under load measured with a load of 1.82 MPa of the resin composition used in the present invention is not particularly limited, but is preferably 65 ° C or higher, more preferably 70 ° C or higher, and 75 ° C or higher. Is more preferable, and 80 ° C. or higher is particularly preferable. Here, the deflection temperature under load is a value measured according to the ASTM D648 standard.

  The molded article of the present invention is characterized by the absence of spherulites. Here, the presence or absence of spherulites can be determined by observing with a polarizing microscope or an electron microscope, and can also be observed in the state of the resin composition.

  The molded article of the present invention is characterized in that the relative crystallinity is 50% or more. Here, the relative crystallinity is the relative crystallinity obtained from the crystal melting enthalpy (ΔHm) derived from polylactic acid resin and the crystallization enthalpy (ΔHcc) at the time of temperature rise [{(ΔHm−ΔHcc) / ΔHm} × 100], preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 93% or more. Here, ΔHcc is the crystallization enthalpy derived from polylactic acid resin measured by a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min, and ΔHm is DSC at a heating rate of 20 ° C./min. The crystal melting enthalpy derived from the polylactic acid resin was measured. In the first measurement (1stRUN), the temperature was increased from 30 ° C. to 200 ° C. at a temperature increase rate of 20 ° C./min, and then the temperature decrease rate was 20 ° C./min. It is preferably a crystal melting enthalpy measured at 2ndRUN when the temperature is increased from 30 ° C to 200 ° C at a temperature increase rate of 20 ° C / min in the second measurement (2ndRUN). It is observable even in the state.

  The molded product of the present invention is preferably observable at the time of cooling crystallization temperature (Tc) derived from the polylactic acid resin in the molded product in that it is excellent in moldability and heat resistance. Here, the temperature-lowering crystallization temperature (Tc) derived from the polylactic acid resin is a crystallization temperature derived from the polylactic acid resin measured by a differential scanning calorimeter (DSC) at a temperature-decreasing rate of 20 ° C./min. The crystallization temperature (Tc) is not particularly limited, but from the viewpoint of moldability, it is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, even in the state of the resin composition. I can observe.

  The molded article of the present invention is characterized in that the total light transmittance is 70% or more. Here, the total light transmittance is a value obtained by measuring a molded product having a thickness of less than 3 mm in accordance with JIS K7105. From the viewpoint of transparency, the total light transmittance is preferably 80% or more, and 85% or more. Is more preferably 90% or more, and particularly preferably 95% or more. The upper limit is 100%.

  The molded product of the present invention preferably has a haze of 50% or less. Here, haze is a value obtained by measuring a molded product having a thickness of less than 3 mm in accordance with JIS K7105. From the viewpoint of transparency, haze is preferably 5% or less, and more preferably 3% or less. . Although a minimum is not specifically limited, If it is 0.1% or more, it can be used practically without a problem.

  The surface hardness (pencil hardness) of the molded product of the present invention is not particularly limited, but the pencil hardness measured in accordance with JIS K5600-5-4 is preferably HB or higher, in terms of excellent scratch resistance, and is H or higher. More preferably. The upper limit is not particularly limited, but is preferably 3H or less, and more preferably 2H or less, in that the molded product is less likely to be destroyed by impact such as dropping. A molded article having such surface hardness (pencil hardness) can be obtained, for example, by using the preferred crystallization accelerator, reactive compound, or thermoplastic resin.

  From the viewpoint of transparency, the molded product of the present invention preferably has a thickness of less than 3 mm, more preferably 2.5 mm or less, further preferably 2 mm or less, and preferably 1.5 mm or less. Particularly preferred is 1 mm or less. From the viewpoint of heat resistance, it is preferably 0.3 mm or more, more preferably 0.4 mm or more, further preferably 0.5 mm or more, and particularly preferably 0.7 mm or more.

  In the present invention, in observation with an electron microscope, it is preferable to contain a particulate matter having a number average particle size in the major axis direction of 300 nm or less. From the viewpoint of transparency and heat resistance, the number average particle size in the major axis direction is preferably 250 nm or less, more preferably 200 nm or less, further preferably 150 nm or less, and 100 nm or less. Is particularly preferable, and most preferably 80 nm or less. Further, in terms of transparency and heat resistance, the number average particle size in the minor axis direction is preferably 200 nm or less, more preferably 100 nm or less, further preferably 70 nm or less, and 50 nm or less. It is particularly preferable that it is 30 nm or less. The number average particle diameter of the particulate matter is preferably 1 nm or more, more preferably 5 nm or more, and particularly preferably 10 nm or more. In terms of transparency and heat resistance, the aspect ratio, which is the ratio of the number average particle diameter in the major axis direction to the number average particle diameter in the minor axis direction, is preferably in the range of 1 to 10, and 2 to 8 More preferably, it is the range. Further, in terms of transparency and heat resistance, the particulate matter preferably contains no metal element, more preferably a component composed of an organic matter, and even more preferably an organic crystal. . In the present invention, the particulate matter having the number average primary particle size is any 10 to 50, preferably 10 to 30 particles that can be detected when observed at 10,000 times using an electron microscope. The particle diameter in the major axis direction or minor axis direction is measured and averaged, and the number average particle diameter is measured. For identification of contained elements such as metal elements, an electron microscope-X-ray microanalyzer (XMA) is used. Can be determined by conducting elemental analysis.

  Examples of the method for producing the molded product of the present invention include known molding methods such as injection molding, extrusion molding, blow molding, vacuum molding or press molding. In terms of transparency and heat resistance, injection molding and extrusion molding are included. Alternatively, blow molding is preferred, and in the case of injection molding, in terms of transparency and heat resistance, the mold temperature is in the temperature range above the glass transition temperature derived from the polylactic acid resin in the resin composition and below the melting point, preferably 60. Set to a temperature range of from 70 ° C. to 150 ° C., more preferably from 70 ° C. to 120 ° C., more preferably from 80 ° C. to 100 ° C., and a molding cycle of 150 seconds or less, preferably Is preferably 90 seconds or less, more preferably 60 seconds or less, and even more preferably 50 seconds or less.

  The molded article of the present invention is a film, sheet, fiber / cloth, non-woven fabric, injection molded article, extruded molded article, vacuum / pressure molded article, blow molded article, or a composite with other materials. Products, extrusion molded products, and blow molded products are preferred.

  The molded article of the present invention can be used for various applications such as electric / electronic parts, building members, automobile parts, various containers, daily necessities, household goods or sanitary goods.

  Specifically, mobile terminals such as relay cases, coil bobbins, optical pickup chassis, motor cases, notebook computer housings or internal parts, CRT display housings or internal parts, printer housings or internal parts, mobile phones, mobile PCs, handheld mobiles, etc. Housing / internal parts, recording medium (CD, DVD, PD, FDD, etc.) drive housing or internal parts, copier housing or internal parts, facsimile housing or internal parts, parabolic antenna Can be mentioned. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera parts, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts Home and office electrical appliance parts represented by Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders , Electrical and electronic parts such as transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, Hot walls, adjusters, plastic bundles, ceiling fishing gear, staircases, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weedproof bags, protection Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dewatering bag, concrete formwork and other civil engineering related parts, air flow meter, air pump, thermostat housing, engine mount, ignition hobbin , Ignition case, clutch bobbin, sensor housing, idle speed control valve, vacuum switching valve, ECU housing, vacuum pump case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base, AB Actuator case, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter, fuel cap, fuel strainer, distributor cap, vapor canister housing, air cleaner housing, Timing belt covers, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes and other automotive underhood parts, torque control levers, safety belt parts, register blades, washer levers, Window regulator handle, knob of window regulator handle, passing light lever, samba Automotive interior parts such as Iser brackets, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Automotive exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors and other automotive connectors, gears, screws, springs, bearings, levers, key stems, cams, ratchets, rollers, water supply parts, toy parts, fans, Tegs, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, bird protection sheets, vegetation protection nonwoven fabrics, seedlings Pot, vegetation pile, seed string tape, germination sheet, house lining sheet, farm-bi fastener, slow-release fertilizer, root-proof sheet, garden net, insect net, young tree net, printed laminate, fertilizer bag, sample Agricultural materials such as bags, sandbags, beast damage prevention nets, inducement strings, windproof nets, disposable diapers, sanitary wrapping materials, cotton swabs, towels, toilet seat wipes, etc., medical non-woven fabrics (stitching reinforcements, adhesion prevention films, Prosthetic repair materials), wound dressing materials, wound tape bandages, sticker base fabric, surgical sutures, fracture reinforcement, medical films and other medical supplies, calendars, stationery, clothing, food packaging films, trays , Blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, baskets and other containers, tableware, hot-fill containers, microwave cooking containers cosmetics , Wrap, foam buffer, paper lami, shampoo bottle, beverage bottle, cup, candy packaging, shrink label, lid material, envelope with window, fruit basket, hand tape, easy peel packaging, egg pack, HDD packaging, Compost bags, recording media packaging, shopping bags, containers and packaging such as wrapping films for electrical and electronic parts, natural fiber composites, polo shirts, T-shirts, inners, uniforms, sweaters, socks, ties, and other clothing, curtains, chairs Paste, carpet, tablecloth, futon, wallpaper, furoshiki interior goods, carrier tape, print lamination, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card , IC card, paper, leather, non-woven Hot melt binders such as cloth, magnetic material, zinc sulfide, powder binders such as electrode materials, optical elements, conductive embossed tape, IC trays, golf tees, garbage bags, plastic bags, various nets, toothbrushes, stationery, draining nets , Body towel, hand towel, tea pack, drainage filter, clear file, coat agent, adhesive, bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel Useful as kitchen cabinets, pen caps, gas lighters, etc.

  Hereinafter, the configuration and effects of the present invention will be described in more detail by way of examples. Here, the compounding ratio in an Example shows weight%. Moreover, the raw material used and the code | symbol in a table | surface are shown below.

(A) Polylactic acid resin (A-1) Poly L lactic acid resin (D-form 1.2%, weight average molecular weight 160,000, melting point 172 ° C.)
(A-2) Poly L lactic acid resin (D-form 0.5%, weight average molecular weight 150,000, melting point 180 ° C.)
(A-3) Poly L-lactic acid resin (D-form 1.2%, weight average molecular weight 200,000, melting point 172 ° C.)
(A-4) Polylactic acid stereocomplex (weight average molecular weight 150,000, melting point 210 ° C.) [Reference Example 1].

(B) Crystal nucleating agent (B-1) Ethylene bis-stearic acid amide (Nippon Kasei "Slipax" E)
(B-2) Ethylenebislauric acid amide (Nippon Kasei "Slipax" L)
(B-3) Ethylene bis-12-hydroxystearic acid amide (Nippon Kasei "Slipax" H)
(B-4) Trimesic acid tricyclohexylamide [Reference Example 2]
(B-5) N, N′-Dibenzoyl sebacic acid dihydrazide [Reference Example 3]
(B-6) Talc ("MICRO ACE" P-6 manufactured by Nippon Talc).

(C) Plasticizer (C-1) Poly (ethylene oxide / propylene oxide) block copolymer (ADEKA "Pluronic" F68)
(C-2) Castor oil fatty acid ester (“Rick Sizer” C401, manufactured by Ito Oil).

(D) Impact resistance improver (D-1) Multi-layer structure polymer ("Parroid" BPM-500 manufactured by Rohm & Haas, core: acrylic polymer, shell: methyl methacrylate copolymer).

(E) Reactive compound (E-1) Glycidyl group-containing acrylic / styrene copolymer (“ARUFON” UG4040 manufactured by Toagosei Co., Ltd., weight average molecular weight 10,000)
(E-2) Polycarbodiimide (Nisshinbo "Carbodilite" HMV-8CA, weight average molecular weight 2000).

(F) Inorganic particles (F-1) Organically modified layered silicate: Montmorillonite exchanged with 12-aminododecanoic acid hydrochloride [Reference Example 4]
(F-2) Colloidal silica (“OSCAL” manufactured by Catalytic Chemical Industry).

[Reference Example 1] (A-4) Production Example of Polylactic Acid Stereocomplex (Stereoblock Polylactic Acid) 100 parts by weight of L-lactide and 0.2 parts by weight of ethylene glycol were added to a nitrogen atmosphere in a reaction vessel equipped with a stirrer. Then, after uniformly dissolving at 170 ° C., 0.01 part by weight of tin octylate was added, followed by polymerization reaction for 2 hours. After completion of the polymerization reaction, the reaction product was dissolved in chloroform and precipitated with stirring in methanol (5 times the amount of chloroform) to completely remove the monomer, and poly-L-lactic acid (P11 having a weight average molecular weight of 40,000). ) The weight average molecular weight of P11 was 50,000.

  Next, 100 parts by weight of the obtained P11 was dissolved in a reaction vessel equipped with a stirrer at 200 ° C. in a nitrogen atmosphere, and then 120 parts by weight of D-lactide was added, and tin octylate 0.01 A part by weight was added and the polymerization reaction was carried out for 3 hours. After completion of the polymerization reaction, the reaction product was dissolved in chloroform, precipitated with stirring in methanol (5 times the amount of chloroform), the monomer was completely removed, and P11 comprising L-lactic acid units was converted into D11 from D-lactic acid units. A stereoblock polylactic acid (P12) having 3 segments to which the following segments were bonded was obtained. P12 had a weight average molecular weight of 150,000 and a melting point of 210 ° C.

[Reference Example 2] (B-4) Production Example of Trimesic Acid Tricyclohexylamide 42 g (0.2 mol) trimesic acid, 70 g (0.7 mol) cyclohexylamine, 217 g (0.7 mol) triphenyl phosphite , 70 g (0.9 mol) of pyridine and 350 g (3.5 mol) of N-methylpyrrolidone were placed in a reaction vessel, reacted at 100 ° C. for 5 hours under a nitrogen stream, cooled to room temperature, and then poured into 2500 mL of methanol. The precipitate was filtered to obtain 39 g of a white solid (43% yield, melting point 383 ° C.).

[Reference Example 3] (B-5) Production example of N, N'-dibenzoyl sebacic acid dihydrazide 27.2 g (0.2 mol) of benzoic acid hydrazide and 38.3 g (0.1 mol) of dibenzyl sebacate and pyridine 15.8 g (0.2 mol) and 53 g (0.6 mol) of dioxane were put in a reaction vessel, reacted at 100 ° C. for 20 hours in a nitrogen stream, cooled to room temperature, then poured into 500 mL of methanol, and a precipitate. Was filtered to obtain 13 g of white solid (yield 30%, melting point 208 ° C.).

[Reference Example 4] (F-1) Production Example of Organically Modified Layered Silicate 100 g of Na-type montmorillonite (Kunimine Industries: “Kunimine F”, cation exchange capacity 120 m equivalent / 100 g) was stirred and dispersed in 10 liters of warm water. 2L of warm water in which 30.2 g of 12-aminododecanoic acid hydrochloride (equivalent to the cation exchange capacity) was dissolved was added and stirred for 1 hour, and the resulting precipitate was filtered and washed with warm water three times. F-1 was obtained by vacuum-drying the obtained solid at 80 degreeC.

  The measurement method and determination method used in the present invention are shown below.

(1) Formability When the molded product was taken out from the mold, the shortest time for obtaining a solid molded product without deformation was measured as the molding cycle time. It can be said that the shorter the molding cycle time, the better the moldability.

(2) Relative crystallinity A part is cut out from the center part of the square plate molded product, and the temperature-induced crystallization temperature (Tcc) and temperature-induced crystallization enthalpy (ΔHcc), melting point (Tm) and crystal melting enthalpy derived from polylactic acid resin (ΔHm) was measured. The measurement was carried out using a Perkin Elmer DSC7 in a 10 mg sample under a nitrogen atmosphere at a heating rate of 20 ° C./min. Using the measured ΔHm and ΔHcc, the relative crystallinity [{(ΔHm−ΔHcc) / ΔHm } × 100] (%).

(3) Transparency Using the Nippon Denshoku Industries haze meter NDH-300A, the total light transmittance and haze of the square plate molded product were measured according to JIS-K7105.

(4) Observation of spherulite A part was cut out from the central part of a square plate molded article, an ultrathin section was prepared using a microtome, and observed with a polarizing microscope at a magnification of 500 to examine the presence or absence of spherulites.

(5) Particulate matter A part was cut out from the central part of the square plate molded article, an ultrathin section was prepared using a microtome, and observed with a transmission electron microscope (TEM) manufactured by Hitachi, Ltd. at a magnification of 10,000 times. The primary particle size was measured for any 15 particles, and the average value was taken as the number average particle size. In addition, the presence or absence of a metal element was examined using an energy dispersive X-ray analyzer (EDX).

(6) Heat resistance: Heat sag test In a state where an 80 mm x 80 mm square plate molded product was cantilevered, the amount of deformation when held at 60 ° C for 30 minutes was measured. It can be said that the smaller the amount of deformation, the better the heat resistance.

(7) Heat resistance: deflection temperature under load In accordance with ASTM D648, a deflection temperature under load (load 0.45 MPa) was measured using a molded product of 12.7 mm × 127 mm × 3 mm.

(8) Tensile strength According to ASTM D638, a tensile test was performed using a 3 mm thick ASTM No. 1 dumbbell molded product.

(9) Impact strength According to ASTM D256, Izod impact strength was measured using a 3 mm thick notched strip-shaped molded product.

(10) Weight average molecular weight (Mw)
It is a value of weight average molecular weight in terms of standard PMMA measured by gel permeation chromatography (GPC). Hexafluoroisopropanol was used as a solvent, the flow rate was 0.5 mL / min, and 0.1 mL of a solution having a sample concentration of 1 mg / mL was injected and measured.

[Reference Comparative Example 1-5, Example 6-14, Comparative Example 1]
As shown in Tables 1 and 2, the raw materials were blended, melt-kneaded under the conditions of a cylinder temperature of 200 ° C. and a rotation speed of 200 rpm using a 30 mm diameter twin screw extruder (TEX-30α manufactured by Nippon Steel), and pellets A resin composition was obtained.

  The obtained pellet-shaped resin composition was injection-molded at an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 200 ° C. and a mold temperature of 90 ° C. to obtain molded products for various evaluations. .

  Tables 1 and 2 show the results of various evaluations using the obtained molded product.

From the examples, comparative examples , and reference comparative examples in Tables 1 and 2, the following is clear.

From the comparison between Reference Comparative Examples 1 to 5, Examples 6 to 14, and Comparative Example 1, a molded article made of a resin composition formed by blending a polylactic acid resin and a crystallization accelerator is excellent in transparency and heat resistance. I understand that. Moreover, it turns out that it is excellent in transparency and heat resistance especially when a plasticizer contains 2 or more types from Examples 6-14.

[ Reference Comparative Examples 15 to 18, Example 19 and Comparative Example 2]
As shown in Table 3, the raw materials were blended and melt-kneaded under the conditions of a cylinder temperature of 200 ° C. and a rotation speed of 200 rpm using a 30 mm diameter twin screw extruder (TEX-30α manufactured by Nippon Steel), and a pellet-shaped resin A composition was obtained.

  The obtained pellet-shaped resin composition was subjected to injection molding at an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C., and then at 100 ° C. for 5 minutes. A crystallization treatment was carried out to obtain molded products for various evaluations.

  Table 3 shows the results of various evaluations using the obtained molded product.

The following is clear from the reference comparative examples, examples and comparative examples in Table 3.

From Reference Comparative Examples 15 to 18, Example 19 and Comparative Example 2, it can be seen that a molded product made of a resin composition containing polylactic acid and a crystallization accelerator is excellent in transparency and heat resistance. Moreover, from Example 19, when a plasticizer contains 2 or more types, it turns out that it is excellent in transparency and heat resistance especially.

[Examples 20 to 28, Comparative Example 3]
As shown in Table 4 and Table 5, the raw materials were blended, and melt-kneaded under the conditions of a cylinder temperature of 200 ° C. and a rotation speed of 200 rpm using a 30 mm diameter twin screw extruder (TEX-30α manufactured by Nippon Steel), and pellets A resin composition was obtained.

  The obtained pellet-shaped resin composition was injection-molded at an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 200 ° C. and a mold temperature of 90 ° C. to obtain molded products for various evaluations. .

  Tables 4 and 5 show the results of various evaluations using the obtained molded product.

  From the examples and comparative examples in Tables 4 and 5, the following is clear.

  From a comparison between Examples 20 to 28 and Comparative Example 3, it can be seen that a molded article made of a resin composition containing polylactic acid and a crystallization accelerator is excellent in transparency and heat resistance. Moreover, it turns out that it is excellent in impact resistance, when Examples 20-26 mix | blends an impact-resistance improving agent, and it is excellent in heat resistance especially when it mix | blends inorganic particles from Examples 27-28.

Claims (6)

(A) A resin composition comprising 0.5 to 50 parts by weight of a crystallization accelerator based on 100 parts by weight of a polylactic acid resin, and (A) the polylactic acid resin is a total of (a) the polylactic acid resin. Among the lactic acid components, a polylactic acid resin containing 80% or more of L-form or 80% or more of D-form, and / or (b) a polylactic acid stereocomplex, wherein the crystallization accelerator is (B) It comprises a crystal nucleating agent and (C) a plasticizer, (B) the crystal nucleating agent is at least one selected from an amide compound and a hydrazide compound, and (C) the plasticizer includes two or more plasticizers. The molded article has no spherulites, a relative crystallinity of 50% or more, a total light transmittance of 70% or more, and the number average particle diameter in the major axis direction when observed with an electron microscope. Containing particles of 300 nm or less Shaped product. The molded article according to claim 1 , wherein at least one of the (C) plasticizers is a polyalkylene glycol plasticizer. The molded article according to any one of claims 1 to 2 , wherein the thickness of the molded article is less than 3 mm. The polylactic acid resin composition comprises (D) 0.1 to 200 parts by weight of an impact modifier, (E) 0.01 to 30 parts by weight of a reactive compound, and (A) 100 parts by weight of a polylactic acid resin. F) The molded article according to any one of claims 1 to 3 , which is a composition comprising at least one selected from 0.1 to 50 parts by weight of inorganic particles. (A) 0.5 to 50 parts by weight of a crystallization accelerator is blended with 100 parts by weight of a polylactic acid resin, and the (A) polylactic acid resin is (a) of the total lactic acid components of the polylactic acid resin. A polylactic acid resin containing 80% or more of the L isomer or 80% or more of the D isomer, and / or (b) a polylactic acid stereocomplex, wherein the crystallization accelerator comprises (B) a crystal nucleating agent and (C) consisting of a plasticizer, (B) the crystal nucleating agent is at least one selected from amide compounds and hydrazide compounds, (C) the plasticizer includes two or more plasticizers, The resin composition is a resin composition containing a particulate matter having a number average particle size in the major axis direction of 300 nm or less as observed with an electron microscope. The mold temperature was set to the glass transition temperature or higher and a temperature range below the melting point of from polylactic acid resin in the resin composition, according to claim 1-4, characterized by being obtained by injection molding under the following molding cycle 150 seconds The manufacturing method of the molded article of any one of Claims 1.