JP5087934B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition comprising an aromatic polyester resin and a polylactic acid resin and largely improved in mechanical characteristics, hydrolysis resistance and heat resistance which have been defects of the polylactic acid resin, and a molded product thereof. <P>SOLUTION: The thermoplastic resin composition comprises 15-50 wt.% aromatic polyester resin (a) and 50-85 wt.% polylactic acid resin (b) blended to the same. In the thermoplastic resin, the aromatic polyester resin (a) forms a continuous phase and the polylactic acid resin (b) forms a dispersed phase or a continuous phase in a resin phase-separated structure observed by electron microscope. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention has specific mechanical properties and heat resistance obtained by controlling the resin phase separation structure of a thermoplastic resin composition comprising an aromatic polyester resin and a polylactic acid resin to form a characteristic phase structure. The present invention relates to a thermoplastic resin composition and a molded product obtained by processing the same.

  Conventional polymers are mostly made from petroleum resources, but carbon dioxide that has been stored in the ground since the geological era due to the fact that petroleum resources will be depleted in the future and that large amounts of petroleum resources are consumed. Is released into the atmosphere, and there is concern that global warming will become more serious. However, if a polymer can be synthesized using plant resources that grow by taking in carbon dioxide from the atmosphere, it is possible not only to suppress global warming by carbon dioxide circulation, but also to solve the problem of resource depletion at the same time. . For this reason, attention has been focused on polymers using plant resources as raw materials, that is, polymers using biomass.

  In view of the above, biomass-utilizing polymers are attracting great attention and are expected to replace conventional polymers made from petroleum resources. However, biomass-utilizing polymers generally have problems such as low mechanical properties and heat resistance and high cost. Currently, polylactic acid, which is a kind of aliphatic polyester, has attracted the most attention as a biomass-utilizing polymer that can solve these problems. Polylactic acid is a polymer made from lactic acid obtained by fermenting starch extracted from a plant, and among the biomass-using polymers, it has an excellent balance of mechanical properties, heat resistance, and cost. Development of resin products, fibers, films, sheets, and the like using this has been performed at a rapid pitch.

However, even the most promising polylactic acid has several drawbacks compared to conventional petroleum-based polymers. Among these, a large thing is that mechanical properties and heat resistance are low. For this reason, studies have been made to blend the polylactic acid and a general-purpose resin material to make up for the above drawbacks. Patent Document 1 discloses a polymer alloy of polyester and polylactic acid derived from petroleum resources, but the amount of polylactic acid is small and it cannot be said that it is sufficient from the viewpoint of low environmental load. Patent Documents 2 to 4 disclose resin compositions in which polybutylene terephthalate or polyamide is dispersed in polylactic acid to improve mechanical properties and heat resistance. However, polylactic acid, which is a large component, has a continuous phase. In order to form, it cannot be said that it is sufficient about a mechanical characteristic and heat resistance, and the further improvement is calculated | required.
Japanese Patent Laying-Open No. 2005-200593 (Claims) Japanese Patent Laying-Open No. 2005-42045 (Claims) JP 2003-238775 A (Claims) JP 2004-51835 A (Claims)

  The present invention controls the mechanical properties and resistance of polylactic acid resin by forming the phase structure of the characteristic by controlling the resin phase separation structure of the thermoplastic resin composition comprising an aromatic polyester resin and a polylactic acid resin. The object is to greatly improve the hydrolyzability and heat resistance.

  Therefore, the present inventors have studied to solve the above problems, and as a result, in a thermoplastic resin composition obtained by blending a specific amount of an aromatic polyester resin and a polylactic acid resin, a resin phase separation structure observed with an electron microscope The inventors have found that the above-mentioned problems can be solved by controlling the dispersion structure so that the aromatic polyester resin forms a continuous phase.

That is, the present invention
(1) Aromatic polyester resin (a) 15 to 50% by weight , polylactic acid resin (b) 50 to 85% by weight, and (a) and (b) ) Is a thermoplastic resin composition obtained by blending 0.001 to 2 parts by weight of a catalyst deactivator (c) with respect to a total of 100 parts by weight of : (volume fraction of aromatic polyester resin / polylactic acid resin) Volume fraction) × (melt viscosity of polylactic acid resin / melt viscosity of aromatic polyester resin) is a value greater than 1 and less than or equal to 3.0, and in the resin phase separation structure observed with an electron microscope A thermoplastic resin composition characterized by forming a phase structure in which the group polyester resin (a) is a continuous phase and the polylactic acid resin (b) is a dispersed phase;
(2) The thermoplastic resin composition according to (1), comprising 25 to 45% by weight of an aromatic polyester resin (a) and 55 to 75% by weight of a polylactic acid resin (b),
(3) The thermoplastic resin composition according to any one of (1) and (2) , wherein the intrinsic viscosity of the aromatic polyester resin (a) is in the range of 0.35 to 0.95 ,
(4) 0.01 to 10 parts by weight of the compatibilizing agent (d) is added to 100 parts by weight of the total of (a) and (b). Any of (1) to (3) The thermoplastic resin composition according to
(5) The thermoplastic resin composition according to (4), wherein the compatibilizer (d) is at least one selected from the group consisting of a carbodiimide compound and a polyfunctional epoxy compound,
(6) Any one of (1) to (5), wherein 0.01 to 30 parts by weight of a plasticizer (g) is added to 100 parts by weight of the total of (a) and (b). The thermoplastic resin composition according to claim 1,
(7) The thermoplastic resin composition according to (6), wherein the plasticizer (g) is a polyalkylene glycol plasticizer,
(8) The thermoplastic resin composition according to any one of (1) to (7), wherein a main component of the aromatic polyester resin (a) is a polybutylene terephthalate resin.
(9) It is characterized by being produced by applying a kneading energy of 0.15 kWh / kg or more to a molten mixture of the resin constituting the thermoplastic resin composition while controlling the resin temperature to 260 ° C. or less ( 1) A method for producing a thermoplastic resin composition according to any one of (8),
(10) A molded product obtained by processing the thermoplastic resin composition according to any one of (1) to (8),
(11) The molded article according to (10) obtained by a method selected from injection molding, injection compression molding, and compression molding.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition which consists of an aromatic polyester resin and polylactic acid resin in which the mechanical characteristics, hydrolysis resistance, and heat resistance which were the faults of the polylactic acid resin were significantly improved can be obtained.

  Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

  The aromatic polyester resin (a) used in the present invention is a polymer having an ester bond in the main chain and a thermoplastic polyester having an aromatic ring in the chain unit of the polymer. Specifically, a polymer or copolymer obtained usually by an aromatic dicarboxylic acid (or an ester-forming derivative thereof), a diol (or an ester-forming derivative thereof) and / or a hydroxycarboxylic acid, and obtained by a condensation reaction. Coalescence is mentioned.

  Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl Examples include dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 5-sodium sulfoisophthalic acid and ester-forming derivatives thereof. Two or more of these aromatic dicarboxylic acids can be used in combination. Also used in combination with aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and ester-forming derivatives thereof You can also

  As the diol, an aliphatic diol having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, And cyclohexanedimethanol, cyclohexanediol, and the like, and ester-forming derivatives thereof. Two or more of these diols can be used in combination.

  Specific examples of the polyester preferably used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyalkylene terephthalate such as polyhexylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, Polybutylene-2,6-naphthalene dicarboxylate, polyethylene-1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polybutylene terephthalate / Decane dicarboxylate, poly (ethylene terephthalate / cyclohexanedimethylene terephthalate), polyethylene Non-liquid crystal polyester, and mixtures thereof, such as down-4,4'-dicarboxylate / terephthalate, and the like. In the present invention, a more preferable aromatic polyester resin is an aromatic polyester resin having a melting point of 150 ° C. or higher and excellent in heat resistance and strength, and an aromatic polyester mainly composed of polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate. Resin. When polybutylene terephthalate is selected as the aromatic polyester, it is particularly preferable because molding processability is remarkably improved in addition to improvement in mechanical properties, hydrolysis resistance and heat resistance. These polyester resins are also practically suitable for use as a mixture depending on required properties such as moldability, heat resistance, toughness, and surface properties.

  There is no restriction | limiting in particular in the manufacturing method of aromatic polyester resin (a) used by this invention, It manufactures by the conventionally well-known direct polymerization method or transesterification method.

Although there is no limitation on the degree of polymerization of these polyester resins, for example, 0.5% of o- chlorophenol solution, is intrinsic viscosity measured at 25 ° C., preferably in the range of 0.35 to 0.95, 0.45 The range of ~ 0.95 is more preferable, and the range of 0.50 to 0.95 is particularly preferable.

  In addition, the aromatic polyester resin (a) used in the present invention has a carboxyl end group amount of 10 to 60 eq / t per ton of a polymer obtained by potentiometric titration of an m-cresol solution with an alkaline solution. Is more preferable, and 15 to 50 eq / t is more preferable. If the carboxyl end group amount is less than 10 eq / t, the mechanical properties tend to decrease, and if it exceeds 60 eq / t, the hydrolysis resistance tends to decrease, such being undesirable.

  In general, since the melting point of the polylactic acid resin is about 170 ° C., considering that the blending temperature is lowered as much as possible, the melting point of the aromatic polyester resin is more preferably 250 ° C. or less, particularly preferably 230 ° C. It is as follows. In order to improve the moldability of the blend polymer resin obtained by blending the aromatic polyester resin with the polylactic acid resin and the dimensional stability of the molded body, the blend polymer resin is preferably crystalline. For this reason, it is preferable that the aromatic polyester resin to be blended is also crystalline. If a melting peak can be observed by differential scanning calorimetry (DSC) measurement, the polymer can be judged to be crystalline.

  The polylactic acid resin (b) referred to in the present invention is a polymer containing L-lactic acid and / or D-lactic acid as a main constituent component, but may contain other copolymerization components other than lactic acid. Other copolymerization components include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentaerythritol, Glycol compounds such as bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, Phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid Dicarboxylic acids such as 5-sodium sulfoisophthalic acid and 5-tetrabutylphosphonium isophthalic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid and other hydroxycarboxylic acids, and caprolactone, Examples include lactones such as valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. As such a copolymer component, it is preferable to set it as content of 30 mol% or less normally in all the monomer components, and it is preferable that it is 10 mol% or less. Further, it may contain additives other than polylactic acid, particles, flame retardants, antistatic agents and the like as long as the properties of polylactic acid are not impaired.

  In the present invention, polylactic acid having a high optical purity of the lactic acid component is preferably used as the polylactic acid resin (b) from the viewpoint of compatibility. That is, among the total lactic acid components of polylactic acid, 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 contained at 90% or more. It is particularly preferable that the L-form is contained at 95% or more or the D-form is contained at 95% or more. In addition, in this invention, it is a preferable aspect to use polylactic acid with high optical purity which has L body or D body as a main component, and to use those mixtures individually.

  The molecular weight and molecular weight distribution of the polylactic acid resin (b) are not particularly limited as long as it can be substantially molded, but the weight average molecular weight is usually 10,000 or more, preferably 40,000 or more, Furthermore, it is desirable that it is 80,000 or more. The weight average molecular weight here refers to the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography.

  The melting point of the polylactic acid resin (b) is not particularly limited, but is preferably 120 ° C. or higher, and more preferably 150 ° C. or higher.

  As a method for producing the polylactic acid resin (b), a known polymerization method can be used, and examples thereof include a direct polymerization method from lactic acid and a ring-opening polymerization method via lactide.

  The blending ratio of the aromatic polyester resin (a) and the polylactic acid resin (b) in the thermoplastic resin composition of the present invention is such that the total of (a) and (b) is 100% by weight, and the aromatic polyester resin (a) 15 to 50% by weight, polylactic acid resin (b) 50 to 85% by weight, preferably 25 to 45% by weight of aromatic polyester resin and 55 to 75% by weight of polylactic acid resin. If the polylactic acid resin (b) is less than 50% by weight, it is not preferable because the low environmental load due to the use of the biomass-utilizing polymer, which is a feature of the thermoplastic resin composition of the present invention, becomes poor. When the polylactic acid resin (b) exceeds 85% by weight, it becomes difficult to form a resin phase separation structure in which the aromatic polyester resin, which is a feature of the thermoplastic resin composition of the present invention, forms a continuous phase, Undesirably, mechanical properties and heat resistance are reduced.

  The thermoplastic resin composition of the present invention forms a resin phase separation structure in which the aromatic polyester resin (a) forms a continuous phase. Usually, in the case of a two-component polymer blend, a resin phase separation structure is formed in which a major component is a continuous phase and a minor component is a dispersed phase. In the thermoplastic resin composition of the present invention, (a) and (b) Even if the aromatic polyester resin (a) component is a minor component, such as aromatic polyester resin (a) 15 to 50% by weight and polylactic acid resin (b) 50 to 85% by weight. By appropriately controlling the melt viscosity ratio of the aromatic polyester resin / polylactic acid resin so as to satisfy the formula (1), a resin phase separation structure in which the aromatic polyester resin takes a continuous phase can be formed.

  If the value of (volume fraction of aromatic polyester resin / volume fraction of polylactic acid resin) × (melt viscosity of polylactic acid resin / melt viscosity of aromatic polyester resin) represented by formula (1) is greater than 1 A resin phase separation structure in which a minor component is a continuous phase and a major component is a dispersed phase can be stably formed, but is preferably 1.5 or more. When 1 <(volume fraction of aromatic polyester resin / volume fraction of polylactic acid resin) × (melt viscosity of polylactic acid resin / melt viscosity of aromatic polyester resin) <1.5, melt kneading It is preferable to add the catalyst deactivator (c) in order to prevent the melt viscosity of the aromatic polyester resin or polylactic acid resin from changing and not satisfying the formula (1) at the time and during melt molding.

  Polylactic acid resin is an aliphatic polyester resin, so it has low hydrolysis resistance under constant temperature and high humidity, whereas aromatic polyester resin is more resistant to hydrolysis than aliphatic polyester by introducing an aromatic ring into the molecular chain. It is characterized by excellent properties. In the thermoplastic resin composition of the present invention, since the aromatic polyester resin forms a continuous phase, the hydrolysis resistance is improved more than the composition in which the polylactic acid resin is a continuous phase.

In the aromatic polyester resin (a) and polylactic acid resin (b) used in the present invention, the polymerization catalyst used at the time of polymerization may remain in a small amount, but the remaining polymerization catalyst Due to the action, the melt viscosity of the aromatic polyester resin or polylactic acid resin may change during melt kneading and melt molding. Therefore, even if an aromatic polyester resin and a polylactic acid resin having a melt viscosity ratio satisfying the above formula (1) are selected to produce a thermoplastic resin composition, the aromatic polyester resin and the polylactic acid are melted during melting. In some cases, the melt viscosity ratio of the resin changes and a resin phase separation structure in which the aromatic polyester resin takes a continuous phase cannot be formed. Add the catalyst deactivator (c) in the thermoplastic resin composition of the present invention to prevent this. By adding a catalyst deactivator, the melt viscosity ratio of the aromatic polyester resin / polylactic acid resin can be controlled stably, and the resin phase separation structure in which the aromatic polyester resin, which is a feature of the present invention, takes a continuous phase Can be formed stably. Examples of the catalyst deactivator used in the present invention include phosphorus compounds, hindered phenol compounds, thioether compounds, vitamin compounds, triazole compounds, polyvalent amine compounds, hydrazine derivative compounds, and the like. You may use together. Among these, it is preferable to contain at least one phosphorus compound.

  Specific examples of the hindered phenol compound include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl). -5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexane Diol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-t-butyl- 4-hydroxyphenyl) -propionate], 2,2′-methylenebis- (4-methyl-t-butylphenol), triethylene glycol-bis- [3- (3-t-butyl) 5-methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′-bis-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis-3- (3′-methyl-5) '-T-butyl-4'-hydroxyphenol) propionyldiamine, N, N'-bis- [3- (3,5-di-t-butyl-4-hydroxyphenol) propionyl] Dorazine, N-salicyloyl-N′-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N′-bis [2- {3- (3,5-di- t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylene Bis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like. Preferably, triethylene glycol-bis- [3- (3-t-butyl-5-methyl- 4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate Acid] methane, 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], pentaerythrityl-tetrakis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide). Specific product names of hindered phenol compounds include “Adeka Stub” AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, manufactured by Asahi Denka Kogyo Co., Ltd. AO-330, “Irganox” 245, 259, 565, 1010, 1035, 1076, 1098, 1222, 1330, 1425, 1520, 3114, 5057 manufactured by Ciba Specialty Chemicals, “Sumilyzer” BHT-R manufactured by Sumitomo Chemical Co., Ltd. Examples thereof include MDP-S, BBM-S, WX-R, NW, BP-76, BP-101, GA-80, GM, GS, “Cyanox” CY-1790 manufactured by Cyanamid.

  Specific examples of the thioether compound include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate) Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3- Stearylthiopropionate). Specific product names of thioether compounds include “Adeka Stub” A0-23, AO-412S, AO-503A from Asahi Denka Kogyo Co., Ltd., “Irganox” PS802 from Ciba Specialty Chemicals, and “Sumilyzer” from Sumitomo Chemical Co., Ltd. Examples include TPL-R, TPM, TPS, TP-D, Yoshitomi's DSTP, DLTP, DLTOIB, DMTP, Cypro Kasei's “Sinox” 412S, and Cyamide's “Sianox” 1212.

  Specific examples of the vitamin compound include d-α-tocopherol acetate, d-α-tocopherol succinate, d-α-tocopherol, d-β-tocopherol, d-γ-tocopherol, d-δ-tocopherol, d- Natural products such as α-tocotrienol, d-β-tocofetrienol, d-γ-tocofetrienol, d-δ-tocofetrienol, dl-α-tocopherol, dl-α-tocopherol acetate, succinic acid Synthetic products such as dl-α-tocopherol calcium and dl-α-tocopherol nicotinate can be mentioned. Specific product names of vitamin compounds include “Tocopherol” from Eisai and “Irganox” E201 from Ciba Specialty Chemicals.

  Specific examples of the triazole compound include benzotriazole, 3- (N-salicyloyl) amino-1,2,4-triazole, and the like.

  Specific examples of the polyvalent amine compound include 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro. [5.5] Undecane, ethylenediamine-tetraacetic acid, alkali metal salt (Li, Na, K) salt of ethylenediamine-tetraacetic acid, N, N'-disalicylidene-ethylenediamine, N, N'-disalicylidene-1 , 2-propylenediamine, N, N ″ -disalicylidene-N′-methyl-dipropylenetriamine, 3-salicyloylamino-1,2,4-triazole and the like.

  Specific examples of the hydrazine derivative-based compound include decamethylene dicarboxyl acid-bis (N′-salicyloyl hydrazide), bis (2-phenoxypropionyl hydrazide) isophthalate, N-formyl-N′-salicyloyl hydrazine. 2,2-oxamide bis- [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oxalyl-bis-benzylidene-hydrazide, nickel-bis (1-phenyl-3- Methyl-4-decanoyl-5-pyrazolate), 2-ethoxy-2′-ethyloxanilide, 5-t-butyl-2-ethoxy-2′-ethyloxanilide, N, N-diethyl-N ′, N'-diphenyloxamide, N, N'-diethyl-N, N'-diphenyloxamide, oxalic acid De-bis (benzylidenehydrazide), thiodipropionic acid-bis (benzylidenehydrazide), bis (salicyloylhydrazine), N-salicylidene-N′-salicyloylhydrazone, N, N′-bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, N, N′-bis [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Ethyl] oxamide and the like.

  Examples of phosphorus compounds include phosphite compounds and phosphate compounds. Specific examples of such phosphite compounds include tetrakis [2-t-butyl-4-thio (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -5-methylphenyl] -1, 6-hexamethylene-bis (N-hydroxyethyl-N-methylsemicarbazide) -diphosphite, tetrakis [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-hydroxyethylcarbonylhydrazide-diphosphite, tetrakis [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-) 5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid di-sali Roylhydrazide-diphosphite, tetrakis [2-tert-butyl-4-thio (2′-methyl-4′-hydroxy-5′-tert-butylphenyl) -5-methylphenyl] -di (hydroxyethylcarbonyl) hydrazide— Diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -N, N'-bis (hydroxyethyl) oxamide -Diphosphite and the like are mentioned, and those in which at least one PO bond is bonded to an aromatic group are more preferable. Specific examples include tris (2,4-di-t-butylphenyl) phosphite, Tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene phosphonite, bis (2,4-di-t-butylphenyl) Pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) Octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite— 5-t-butyl-phenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4'-isopropylidenebis (phenyl-dialkyl phosphite) and the like Tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di) t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4, 4′-biphenylenephosphonite and the like can be preferably used. Specific product names of the phosphite compounds include “ADK STAB” PEP-4C, PEP-8, PEP-11C, PEP-24G, PEP-36, HP-10, 2112, 260, 522A manufactured by Asahi Denka Kogyo Co., Ltd. 329A, 1178, 1500, C, 135A, 3010, TPP, “Irgaphos” 168 from Ciba Specialty Chemicals, “Smilizer” P-16 from Sumitomo Chemical, “Sand Stub” from Clariant P-EPQ, GE “Weston” 618, 619G, 624 and the like.

  Specific examples of the phosphate compound include monostearyl acid phosphate, distearyl acid phosphate, methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, isodecyl acid phosphate, etc., among them monostearyl acid phosphate Distearyl acid phosphate is preferred. Specific product names of phosphate compounds include “Irganox” MD1024 from Ciba Specialty Chemicals, “Inhibitor” OABH from Eastman Kodak, “Adekastab” CDA-1, CDA-6 from Asahi Denka Kogyo, AX-71, Mitsui Toatsu Fine's "Quunox", Uniroyal's "Nauguard" XL-1.

The mixing ratio of the catalyst deactivator (c) is 0.001 to 2 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total of (a) and (b). . When the addition amount is less than 0.001 part by weight, a sufficient catalyst deactivation effect cannot be obtained, and when it exceeds 2 parts by weight, the mechanical properties of the thermoplastic resin composition deteriorate, which is not preferable.

  A compatibilizing agent (d) can be added to the thermoplastic resin composition of the present invention for the purpose of improving the compatibility between the thermoplastic resins. It is preferable to add a compatibilizing agent because the resin phase separation structure of the present invention can be stably formed. Here, the compatibilizing agent may be either a low molecular compound or a polymer which is a high molecular compound. Among them, preferred examples include a carboxyl group reactive compound, a carboxyl group, an epoxy group or an acid. Examples thereof include a polymer having an anhydride group.

  In the present invention, the carboxyl group-reactive compound is not particularly limited as long as it is a compound reactive with the carboxyl end group of the polylactic acid resin, but it is generated by thermal decomposition or hydrolysis of the polylactic acid resin. It is more preferable if it is reactive with the carboxyl group of the acidic low molecular compound, and it is more preferable that the compound is also reactive with the hydroxyl group end group of the acidic low molecular compound produced by thermal decomposition.

  Examples of such carboxyl group-reactive compounds include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4 ′. -Bisphenol-glycidyl ether type epoxy compounds such as dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, glycidyl ester type epoxy such as glycidyl phthalate Compounds, glycidylamine epoxy compounds such as N-glycidylaniline, glycidylimide compounds, alicyclic epoxy compounds, polyfunctional epoxy compounds containing two or more epoxy groups, 2 Oxazoline compounds such as 2′-m-phenylenebis (2-oxazoline) and 2,2′-p-phenylenebis (2-oxazoline), oxazine compounds, N, N′-di-2,6-diisopropylphenylcarbodiimide, At least one functional group selected from carbodiimide compounds such as 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide, polycarbodiimide, epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group, and ureido group It is preferable to use at least one kind of compound selected from organic silane compounds such as alkoxysilanes having a polyvalent epoxy compound, an epoxy group, an organic silane compound having an isocyanate group, and a carbodiimide compound. Multifunctional Epoxy compounds, carbodiimide compounds. As the carboxyl group-reactive compound, one or more compounds can be arbitrarily selected and used.

  In the present invention, examples of the polymer having a carboxyl group, an epoxy group, or an acid anhydride group include ethylene / (meth) acrylate glycidyl copolymer, ethylene / (meth) acrylate ethyl-g-maleic anhydride copolymer. ("G" represents a graft, the same shall apply hereinafter), ethylene / glycidyl (meth) acrylate-g- (meth) methyl acrylate copolymer, ethylene / ethyl (meth) acrylate / maleic anhydride copolymer -G- (Meth) acrylic acid methyl copolymer, epoxy group-containing polymer compound obtained by epoxidizing a double bond part of a polymer having a double bond, novolac epoxy resin obtained by reacting novolac phenol resin with epichlorohydrin And so on.

  The blending ratio of the compatibilizing agent (d) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, with respect to 100 parts by weight of the total of (a) and (b). When the addition amount is less than 0.01 parts by weight, a sufficient compatibility improving effect cannot be obtained, and when it exceeds 10 parts by weight, the melt viscosity of the thermoplastic resin composition is remarkably increased and the fluidity is lowered.

  In the present invention, it is preferable to further add a reaction accelerator of the compatibilizer (d). The reaction accelerator here is a compound that has the effect of promoting the reaction between the compatibilizer and the terminal of the resin or the carboxyl group or hydroxyl group of the acidic low molecular weight compound, and the effect of promoting the reaction with a small amount of addition. A certain compound is preferable, for example, an alkali metal compound, an alkaline earth metal compound, and a phosphate ester are preferable. The addition amount of the reaction accelerator is not particularly limited, but is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.2 part by weight with respect to 100 parts by weight of the thermoplastic resin composition. 0.02-0.1 part by weight is most preferable.

  The thermoplastic resin composition obtained by the method of the present invention can be used by blending a filler (e) within the range not impairing the effects of the present invention for the purpose of improving mechanical strength. Specific examples of the filler (e) include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, Asbestos fiber, stone-kow fiber, metal fiber, cotton fiber, hemp fiber, bamboo fiber, wood fiber, kenaf fiber, jute fiber, banana fiber, coconut fiber, fiber such as animal fiber such as silk, wool, Angola, cashmere or camel Swellable layered silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, montmorillonite, synthetic mica, oxidation Silicon, magnesium oxide, aluminum Metal compounds such as sodium, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, calcium hydroxide, magnesium hydroxide and aluminum hydroxide Hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, graphite, paper powder, wood powder, bamboo powder, cellulose powder, rice husk powder, fruit shell powder, chitin powder Non-fibrous fillers such as chitosan powder, protein, starch, rice husk, wood chips, okara, waste paper pulverized material, clothing pulverized material, etc. may be used, and these may be hollow. It is possible to use more than one type together. These fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. In the above filler, PAN-based carbon fibers are preferably used when glass fibers and conductivity are required. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like. Moreover, said filler can also be used in combination of 2 or more types. In addition, the surface of the filler used in the present invention is a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.), other surface treatment agents, and swellable layered silicates. Pretreatment with an organic onium ion is preferable in terms of obtaining a higher mechanical strength. The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

  The blending amount of the filler (e) is preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition of the present invention. More preferably, it is 5 to 80 parts by weight. If the blending amount is less than 0.5 parts by weight, the reinforcing effect is small, which is not preferable. On the other hand, if the blending amount exceeds 100 parts by weight, the fluidity at the time of molding is impaired.

  Moreover, it is preferable that the thermoplastic resin composition of the present invention contains an antioxidant in order to maintain thermal stability. As such a heat-resistant agent and antioxidant, it is preferably used to contain one or more antioxidants selected from phenolic and phosphorus compounds. The blending amount of the antioxidant is preferably 0.01 parts by weight or more, particularly 0.02 parts by weight or more with respect to a total of 100 parts by weight of the thermoplastic resin composition in terms of heat resistance improvement effect, From the viewpoint of the gas component generated sometimes, it is preferably 5 parts by weight or less, particularly 1 part by weight or less. In addition, the combined use of phenolic and phosphorus antioxidants is particularly preferable because of their large heat resistance, thermal stability and fluidity retention effect.

  Furthermore, a resin (f) other than the aromatic polyester resin and polylactic acid resin can be added to the thermoplastic resin composition of the present invention within a range not impairing the effects of the present invention. Specific examples of the resin include polyamide resin, ABS resin, MBS resin, polyolefin resin, polyalkylene oxide resin, modified polyphenylene ether resin, polysulfone resin, polyketone resin, polyphenylene sulfide resin, polyetherimide. Resin, polyarylate resin, polyether sulfone resin, polyether ketone resin, polythioether ketone resin, polyether ether ketone resin, polyimide resin, polyamideimide resin, polytetrafluoroethylene resin, And a multilayer structure polymer having a multilayer structure, and when the blending ratio exceeds 30 parts by weight with respect to 100 parts by weight of the entire thermoplastic resin composition of the present invention, the original characteristics of the thermoplastic resin composition are impaired. Is not preferred, especially 20 The addition of more than the amount portion is preferably used. Of these, olefin resins and multilayer polymers are preferably used for improving impact resistance and toughness.

  Olefin resins include olefin polymer elastomers and / or olefin polymer elastomers and / or conjugated diene-aromatics obtained by graft reaction or copolymerization of unsaturated carboxylic acids and / or their derivatives and vinyl monomers. A hydrogenated block copolymer elastic body in which a part or all of the conjugated diene block portion of the vinyl hydrocarbon block copolymer is hydrogenated is preferable, and an unsaturated carboxylic acid and / or a derivative thereof, which is grafted or copolymerized, The amount of the vinyl monomer is preferably 0.01 to 20% by weight. Examples of the unsaturated carboxylic acid used in the graft reaction or copolymerization include (meth) acrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and butenedicarboxylic acid. In addition, examples of the derivatives include alkyl esters, glycidyl esters, esters having a di- or tri-alkoxysilyl group, acid anhydrides, imides, etc., and glycidyl esters, di- or tri-alkoxysilyl groups having no glycidyl ester. Saturated carboxylic acid esters, acid anhydrides and imides are preferred.

  Preferred examples of the unsaturated carboxylic acid or its derivative include maleic acid, fumaric acid, glycidyl (meth) acrylate, itaconic acid diglycidyl ester, citraconic acid diglycidyl ester, butenedicarboxylic acid diglycidyl ester, butenedicarboxylic acid monoglycidyl Examples thereof include esters, maleic anhydride, itaconic anhydride, citraconic anhydride, maleic imide, itaconic imide, citraconic imide and the like, and glycidyl methacrylate, maleic anhydride, itaconic anhydride and maleic imide are particularly preferred. Examples of vinyl monomers include aromatic vinyl compounds such as styrene, vinyl cyanide compounds such as acrylonitrile, vinylsilane compounds such as vinyltrimethoxysilane, and these unsaturated carboxylic acids or their derivatives or Two or more vinyl monomers may be used in combination. In addition, about the method of grafting these unsaturated carboxylic acid or its derivative (s), or a vinyl monomer, a well-known method can be used. Two or more of these can be used in combination.

  Specific examples include ethylene / methacrylic acid copolymers and those in which some or all of the carboxylic acid moieties in these copolymers are salts with sodium, lithium, potassium, zinc, calcium, ethylene / (meth) acrylic Ethyl acrylate-g-maleic anhydride copolymer, ethylene / ethyl acrylate-g-maleimide copolymer, ethylene / ethyl acrylate-g-N-phenylmaleimide copolymer and partially saponified products of these copolymers, Ethylene / (meth) acrylic acid copolymer, ethylene / vinyl acetate / (meth) acrylic acid copolymer, ethylene / methyl (meth) acrylate / glycidyl (meth) acrylate, ethylene / glycidyl ether copolymer Polymer, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g-none Maleic acid copolymer, ethylene / propylene / 1,4-hexadiene-g-maleic anhydride copolymer, ethylene / propylene / dicyclopentadiene-g-maleic anhydride copolymer, ethylene / propylene / 2,5- Norbornadiene-g-maleic anhydride copolymer, ethylene / propylene-gN-phenylmaleimide copolymer, ethylene / butene-1-gN-phenylmaleimide copolymer, hydrogenated styrene / butadiene / styrene-g -Maleic anhydride copolymer, hydrogenated styrene / isoprene / styrene-g-maleic anhydride copolymer, and the like. Among them, ethylene / methacrylic acid copolymers and some or all of the carboxylic acid moieties in these copolymers as salts with sodium, lithium, potassium, zinc, calcium, ethylene / propylene-g-anhydrous Maleic acid copolymers, ethylene / butene-1-g-maleic anhydride copolymers, hydrogenated styrene / butadiene / styrene-g-maleic anhydride copolymers are preferred, and ethylene / methacrylic acid copolymers and these A part or all of the carboxylic acid moiety in the copolymer made into a salt with sodium, lithium, potassium, zinc, calcium, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g -Maleic anhydride copolymers are preferred.

  The multi-layer structure polymer is composed of an innermost layer (core layer) and one or more layers (shell layer) covering the innermost layer (core layer), and a so-called core-shell type in which adjacent layers are composed of different polymers. The number of layers constituting the multi-layered polymer is not particularly limited, and may be two or more, and may be three or more or four or more. A multilayer structure polymer having at least one rubber layer therein is preferable. 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, a rubber composed of a polymer obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylene propylene component, or the like can be given. Preferred rubbers include, for example, acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, styrene components such as styrene units and α-methylstyrene units, acrylonitrile units, It is a rubber constituted by polymerizing a nitrile component such as a methacrylonitrile unit or a conjugated diene component such as a butanediene unit or an isoprene unit. Further, a rubber composed of a copolymer obtained by combining two or more of these components is also preferable. For example, (1) acrylic components such as ethyl acrylate units and butyl acrylate units, dimethylsiloxane units, and phenylmethylsiloxane Rubber composed of components copolymerized with silicone components such as units, (2) Components copolymerized with acrylic components such as ethyl acrylate units and butyl acrylate units, and styrene components such as styrene units and α-methylstyrene units (3) rubber composed of a component obtained by copolymerizing an acrylic component such as an ethyl acrylate unit or a butyl acrylate unit and a conjugated diene component such as a butanediene unit or an isoprene unit, and (4) ethyl acrylate. Acrylic components such as units and butyl acrylate units and Rubber composed of a styrene component copolymerized with components such as silicone component and styrene units and α- methylstyrene units such as dimethylsiloxane units or phenylmethylsiloxane units and the like. In addition to these components, a rubber obtained by copolymerizing and crosslinking a crosslinkable component such as a divinylbenzene unit, an allyl acrylate unit, or a butylene glycol diacrylate unit is also preferable.

  In the multilayer structure polymer, the type of layer other than the rubber layer is not particularly limited as long as it is composed of a polymer component having thermoplasticity, but a polymer having a glass transition temperature higher than that of the rubber layer. Ingredients are preferred. 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 which unsaturated carboxylic acid alkyl ester units, unsaturated A polymer containing at least one unit selected from glycidyl group-containing units or unsaturated dicarboxylic acid anhydride units is preferred, and at least selected from unsaturated glycidyl group-containing units or unsaturated dicarboxylic acid anhydride units. More preferred are polymers containing one or more units.

  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, etc., from the viewpoint that the effect of improving impact resistance is great ( Methyl methacrylate 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. From the viewpoint that the effect of improving impact resistance is great, glycidyl (meth) acrylate is preferably used. These units can be used alone or in combination of two or more.

  Examples of the unsaturated dicarboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, or aconitic anhydride. From the viewpoint that the effect of improving impact resistance is great, maleic anhydride Acid 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.

  In the multilayer polymer, the type of the outermost 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 vinyl unit, cyanide. Examples include polymers containing vinyl units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic acid anhydride units and / or other vinyl units, among which unsaturated carboxylic acid alkyl ester systems A polymer containing a unit, an unsaturated glycidyl group-containing unit and / or an unsaturated dicarboxylic anhydride-based unit is preferred, and a polymer containing an unsaturated carboxylic acid alkyl ester-based unit is more preferred. The unsaturated carboxylic acid alkyl ester unit is not particularly limited, but (meth) acrylic acid alkyl ester is preferable, and methyl (meth) acrylate is more preferably used.

  As a preferred example of the multilayer structure polymer, the core layer is a dimethylsiloxane / butyl acrylate polymer, the outermost layer is a methyl methacrylate polymer, the core layer is a butanediene / styrene polymer, and the outermost layer is a methyl methacrylate polymer. Examples include a butyl acrylate polymer layer and an outermost methyl methacrylate polymer. Furthermore, it is more preferable that either one or both of the rubber layer and the outermost layer is a polymer containing glycidyl methacrylate units.

  The particle diameter of the multilayer polymer is not particularly limited, but is preferably 0.01 μm or more and 1000 μm or less, more preferably 0.02 μm or more and 100 μm or less, and particularly preferably Most preferably, it is not less than 05 μm and not more than 10 μm.

  In the multilayer structure polymer, the weight ratio of the core and the shell is not particularly limited, but the core layer is preferably 50 parts by weight or more and 90 parts by weight or less with respect to the entire multilayer structure polymer. Further, it is more preferably 60 parts by weight or more and 80 parts by weight or less.

  Examples of the multilayer polymer include “Metablen” manufactured by Mitsubishi Rayon, “Kaneace” manufactured by Kaneka Chemical Industry, “Paraloid” manufactured by Kureha Chemical Industry, “Acryloid” manufactured by Rohm and Haas, “Staffroid” manufactured by Takeda Pharmaceutical Kuraray "parapet SA" and the like can be mentioned, and these can be used alone or in combination of two or more.

  A plasticizer (g) can be added to the thermoplastic resin composition of the present invention. The addition of a plasticizer is preferable because it has the effect of softening and moving the polymer to promote crystal growth, and mechanical properties, moldability and heat resistance are improved. As the plasticizer (g) used in the present invention, generally well-known ones can be used. For example, polyester plasticizer, glycerin plasticizer, polyvalent carboxylic ester plasticizer, phosphate ester. Examples thereof include a plasticizer, a polyalkylene glycol plasticizer, and an epoxy plasticizer.

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

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

  Specific examples of polycarboxylic acid plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, and trimellitic acid. Trimellitic acid esters such as tributyl, trioctyl trimellitic acid, trihexyl trimellitic acid, sebacic acid esters such as diisodecyl adipate, n-octyl-n-decyl adipate adipate, triethyl acetylcitrate, tributyl acetylcitrate, etc. Citrate esters, azelaic acid esters such as di-2-ethylhexyl azelate, sebacic acid esters such as dibutyl sebacate, and di-2-ethylhexyl sebacate.

  Specific examples of the phosphate ester plasticizer include phosphate esters such as tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, tricresyl phosphate, and the like. Mention may be made of aliphatic and aromatic condensed phosphates.

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

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, polycarboxylic acid vinyl esters, silicone oils, and paraffins. be able to.

  The molecular weight of the plasticizer used in the present invention is preferably 100 or more and 30,000 or less, more preferably 500 or more and 20,000 or less, and particularly preferably 1000 or more and 10,000 or less.

  In addition, the above plasticizer obtained by block or graft copolymerization of polylactic acid can be usefully used as a plasticizer.

  Among the plasticizers used in the present invention, at least one selected from polyester plasticizers and polyalkylene glycol plasticizers is preferable among those exemplified above. Also, at least one selected from a copolymer of polylactic acid and an aliphatic polyester plasticizer or a copolymer of polylactic acid and a polyalkylene glycol plasticizer can be preferably used. Only one type of plasticizer may be used in the present invention, or two or more types may be used in combination.

  Moreover, the compounding quantity of a plasticizer has the preferable range of 0.01-30 weight part with respect to a total of 100 weight part of said (a) and (b) of this invention, The range of 0.1-20 weight part Is more preferable, the range of 0.5 to 10 parts by weight is more preferable, and the range of 1 to 5 parts by weight is particularly preferable.

  A crystal nucleating agent that promotes the formation of polymer crystal nuclei can be added to the thermoplastic resin composition of the present invention.

  As the crystal nucleating agent used in the present invention, those generally used as a polymer crystal nucleating agent can be used without particular limitation, and both inorganic crystal nucleating agents and organic crystal nucleating agents can be used. . Specific examples of inorganic crystal nucleating agents include talc, kaolinite, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, Examples thereof include metal salts of barium sulfate, aluminum oxide, neodymium oxide and phenylphosphonate. These inorganic crystal nucleating agents are preferably modified with an organic substance in order to enhance dispersibility in the composition. The average particle size of the inorganic crystal nucleating agent is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 3 μm or less. Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate , Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearic acid Barium, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum Organic carboxylic acid metal salts such as minium dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, lauric acid amide , Stearic acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide), organic carboxylic acid amides such as terephthalic acid dianilide, low Density polyethylene, high density polyethylene, polypropylene, polyisopropylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinyl Sodium or potassium salt of a polymer having a carboxyl group such as a polymer such as loalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid or methacrylic acid copolymer, sodium salt of styrene-maleic anhydride copolymer (So-called ionomers), benzylidene sorbitol and derivatives thereof, phosphorus compound metal salts such as sodium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, and 2,2-methylbis (4,6 -Di-t-butylphenyl) sodium and the like.

  As the crystal nucleating agent used in the present invention, among those exemplified above, at least one selected from talc, organic carboxylic acid metal salts and organic carboxylic acid amides is particularly preferable. Preferable talc includes talc having an average particle size of 0.5 to 7 μm and a ratio of SiO 2 and MgO in the component excluding a loss during combustion of 93% by weight or more. The crystal nucleating agent used in the present invention may be used alone or in combination of two or more.

  Moreover, the compounding amount of the crystal nucleating agent is preferably in the range of 0.01 to 30 parts by weight, and 0.05 to 20 parts by weight with respect to 100 parts by weight of the total of (a) and (b) of the present invention. The range is more preferable, and the range of 0.1 to 15 parts by weight is further preferable.

  In addition, for the purpose of modification, other components such as weathering agents (resorcinol-based, salicylate-based, benzotriazole-based, benzophenone-based, hindered amine-based, etc.), mold release agents and lubricants (Montan) are used as long as the effects of the present invention are not impaired. Acids and their metal salts, their esters, their half esters, stearyl alcohol, stearamide, various bisamides, bisureas, polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (eg, nigrosine), crystal nucleating agents (Talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, polyoxyethylene sorbitan monostearate) Non-io like Antistatic agents, betaine amphoteric antistatic agents, etc.), flame retardants (eg, red phosphorus, melamine cyanurate, magnesium hydroxide, aluminum hydroxide and other hydroxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene) Ethers, brominated polycarbonates, brominated epoxy resins or combinations of these brominated flame retardants and antimony trioxide), and other polymers can be added.

  The kneading machine used for the production of the thermoplastic resin composition of the present invention is supplied to a generally known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll. A representative example is a method of kneading at a processing temperature equal to or higher than the melting point. Among these, an extruder, particularly a twin screw extruder is preferable in terms of productivity. It is also preferred to provide a vent port for the purpose of removing moisture generated during melt kneading and low molecular weight volatile components. In order to control the resin phase separation structure of the thermoplastic resin composition of the present invention as described above using a twin-screw extruder, kneading energy during extrusion (extruder work amount per discharge amount (kW / (kg / H))) needs to be increased. Preferable kneading energy is 0.15 or more and 0.65 or less, and particularly preferably 0.25 or more. As a result, good melt-kneading can be performed, and the intended resin phase separation structure can be formed. However, increasing the kneading energy usually increases the resin temperature due to heat generated by shearing, causing thermal decomposition of polylactic acid resin with poor melt heat resistance, and changing the melt viscosity ratio with the aromatic polyester resin. It becomes difficult to form a structure. The resin temperature here refers to a temperature obtained by measuring, for example, a molten resin discharged from an extruder die with a thermometer. Therefore, the resin temperature at the time of extrusion is preferably not less than the melting point of the resin having the higher melting point of the aromatic polyester resin and the polylactic acid resin and not more than 260 ° C., more preferably not more than 250 ° C. By controlling the kneading energy and the resin temperature in this way, it is possible to form a target resin phase separation structure.

  In melt-kneading using a twin-screw extruder, a method in which the cylinder temperature is set to a low temperature and the screw rotation speed is set to a high rotation speed is preferable because high shear can be obtained and high kneading energy can be achieved. However, in this case, when a conventional kneading disk is used for the screw element of the kneading part, the amount of heat generated by shearing is large, and it is difficult to control the resin temperature during extrusion as described above. On the other hand, it is preferable to use a low exothermic kneading element for the screw element of the kneading part because heat generation due to shearing can be suppressed and a resin temperature of 260 ° C. or less during extrusion can be achieved. The low heat generation element mentioned here includes a screw element or the like in which the flight tip portions arranged in parallel in the conventional kneading disc are inclined within a range of the spiral angle of 0 to 90 degrees or 90 to 180 degrees, By introducing these into the kneading part of the screw, it is possible to obtain the effect of suppressing the temperature rise of the resin which is insufficient in the conventional kneading disk. A method of introducing supercritical carbon dioxide or supercritical nitrogen into the kneading part is also preferable because heat generation due to shearing can be suppressed.

  When the cylinder temperature of the twin screw extruder is divided into a plasticizing part for plasticizing the resin charged in the twin screw extruder and a kneading part for melting and kneading the plasticized molten resin, the plasticizing part is aromatic polyester. Of the resin (a) and the polylactic acid resin (b), the melting point of the resin having a high melting point is preferably from the melting point to the melting point + 20 ° C., and the cylinder temperature of the kneading part is preferably in the range of 100 to 210 ° C. At this time, the mixing order of the raw materials is not particularly limited, and a method in which all raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are blended and melt-kneaded by the above method, and the remaining raw materials are further blended Any method may be used such as a method of melt kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading with a single or twin screw extruder. In addition, as for the small amount additive component, other components may be kneaded and pelletized by the above-described method or the like, and then added before molding and used for molding.

  There is no limitation on the molding method of the thermoplastic resin composition of the present invention, and known methods (injection molding, extrusion molding, blow molding, press molding, etc.) can be used. Molding, injection compression molding, and compression molding. Further, the molding temperature is usually selected from a temperature range 5 to 50 ° C. higher than the melting point of the thermoplastic resin composition, and is generally a single layer, but may be multi-layered by a two-color molding method. . The arrangement of each layer when performing two-color molding is not particularly limited, and all layers may be composed of the thermoplastic resin composition of the present invention, or other layers may be composed of other thermoplastic resins. May be. The thermoplastic resin used as a layer other than the thermoplastic resin composition of the present invention used here is a saturated polyester, polysulfone, tetrafluoropolyethylene, polyetherimide, polyamideimide, polyamide, polyketone copolymer, polyphenylene ether. , Polyimide, polyethersulfone, polyetherketone, polythioetherketone, polyetheretherketone, thermoplastic polyurethane, polyolefin, ABS, polyamide elastomer, polyester elastomer, etc., and if necessary, one or more of these thermoplastic resins These can be used in combination, or various additives can be added to them to impart desired physical properties. Further, the obtained molded products may be bonded or welded to each other or other molded products, and the method is not particularly limited, and a general technique can be used.

  Since the thermoplastic resin composition of the present invention is excellent in mechanical properties and heat resistance, it is an automobile part (interior / exterior part), mechanical part, electrical / electronic part (various housings, gears, gears, etc.), building member, civil engineering. It can be used for various purposes such as materials, agricultural materials, medical care, food, household / office supplies, furniture parts and daily necessities.

  Hereinafter, although an example is given and the present invention is explained in detail, the gist of the present invention is not limited only to the following examples.

(1) Observation of resin phase separation structure The resin phase separation structure was observed as follows. SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd., cylinder temperature 240 ° C. (265 ° C. when the aromatic polyester resin is polyethylene terephthalate), thickness of 500 nm from the molding surface of ASTM No. 1 dumbbell piece molded at a mold temperature of 90 ° C. A 80 nm thin piece was cut and observed with a transmission electron microscope at a magnification of 10,000 times.

(2) Melt viscosity ratio Using a Capillograph type 1C manufactured by Toyo Seiki, the melt viscosity was measured under the conditions of 240 ° C (265 ° C when the aromatic polyester resin is polyethylene terephthalate) and a shear rate of 100 seconds- ¹ ; The melt viscosity ratio was determined from [melt viscosity of lactic acid resin / melt viscosity of aromatic polyester resin].

(3) Resin temperature When melt-kneading in a twin-screw extruder, the molten resin discharged from the extruder die was measured with a thermometer.

(4) Material strength It measured according to the following standard methods.
Tensile strength, tensile elongation: ASTM D638
Flexural modulus: ASTM D790

(5) Formability When SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd. was used, ASTM No. 1 dumbbell piece was molded at a cylinder temperature of 240 ° C. (265 ° C. when the aromatic polyester resin is polyethylene terephthalate) and a mold temperature of 90 ° C. Regarding the moldability, when the tensile test piece 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.

(6) Hydrolysis resistance ASTM No. 1 dumbbell piece molded using SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd., cylinder temperature 240 ° C. (265 ° C. when aromatic polyester resin is polyethylene terephthalate), mold temperature 90 ° C. Tensile strength after treatment for 500 hours under constant temperature and high humidity conditions of 60 ° C. and 95% RH was measured according to ASTM-D638 and determined as follows.
○: Strength reduction rate is 0 to 25%
Δ: Strength reduction rate is 25 to 50%
×: Strength reduction rate is 50% or more

(7) Heat resistance Using a bending test piece (thickness 1/4 inch), the deflection temperature under load (0.45 MPa) was measured according to ASTM method D648.

Examples 3 to 11, Comparative Examples 1 to 6, 10 , 11
After dry blending each component shown below at each ratio shown in Table 1, with a TEX30 type twin screw extruder manufactured by Nippon Steel Works, set the cylinder temperature and screw rotation speed to the conditions shown in Table 1, Examples 3 to 11 and Comparative Examples 2 to 5 , 10, and 11 use a screw with a low exothermic kneading element introduced into the screw kneading part, and Comparative Example 6 uses a screw with a conventional kneading disk introduced into the screw kneading part. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter.

  The pellets obtained were dried for 12 hours at 80 ° C. and injection molded (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 240 ° C. (265 ° C. when the aromatic polyester resin is polyethylene terephthalate), mold temperature 90 )) To prepare test pieces. The results of evaluating the mechanical properties, moldability, and heat resistance of each sample are as shown in Table 1. Comparative Examples 2 to 4 cannot achieve a resin phase separation structure in which the target aromatic polyester resin is a continuous phase, and are inferior in moldability and heat resistance. In Comparative Example 5, melt kneading was performed under the conventional cylinder temperature conditions, but sufficient kneading energy was not obtained, and the target resin phase separation structure could not be achieved, so that the moldability and heat resistance were poor. there were. In Comparative Example 6, melt kneading was performed with the cylinder temperature of the kneading part being low, but since a screw with a conventional kneading disk introduced into the screw kneading part was used, the heat generation was large, the resin temperature increased, and the polylactic acid resin was decomposed. Therefore, the target resin phase separation structure could not be achieved, and the moldability and heat resistance were poor. In this example, compared with Comparative Examples 1-6, it was excellent in balance between mechanical properties, moldability and heat resistance.

Examples 12 and 13, Comparative Example 7
After the components shown below were dry blended with the aromatic polyester resin (a), polylactic acid resin (b), catalyst deactivator (c), and talc in the proportions shown in Table 2, TEX30 type 2 manufactured by Nippon Steel Works Introduce into the main feeder of the shaft extruder, set the cylinder temperature and screw rotation speed to the conditions shown in Table 2, perform melt kneading using a screw with a low exothermic kneading element in the screw kneading section, The gut discharged from was immediately cooled in a water bath and pelletized with a strand cutter. The pellets obtained were dried for 12 hours at 80 ° C., and test pieces were prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 240 ° C., mold temperature 90 ° C.). The results of evaluating the mechanical properties, moldability, and heat resistance of each sample are as shown in Table 2. Compared with the comparative example, the example was excellent in moldability and heat resistance in order to achieve a resin phase separation structure in which the aromatic polyester resin becomes a continuous phase.

Examples 14 to 16, Comparative Example 8
After the components shown below are dry blended with the aromatic polyester resin, polylactic acid resin, and compatibilizing agent in the proportions shown in Table 2, they are introduced into the main feeder of a TEX30 twin screw extruder manufactured by Nippon Steel, Ltd. The temperature and screw rotation speed were set to the conditions shown in Table 2, and melt kneading was performed using a screw having a low exothermic kneading element introduced into the screw kneading section, and glass fibers were introduced from a side feeder downstream of the extruder. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The pellets obtained were dried for 12 hours at 80 ° C. and injection molded (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 240 ° C. (265 ° C. when the aromatic polyester resin is polyethylene terephthalate), mold temperature 90 )) To prepare test pieces. The results of evaluating the mechanical properties, moldability, and heat resistance of each sample are as shown in Table 2. Compared with the comparative example, the example was excellent in moldability and heat resistance in order to achieve a resin phase separation structure in which the aromatic polyester resin becomes a continuous phase.

Examples 17-22, comparative example 9
After dry blending each component shown below at each ratio shown in Table 3, with a TEX30 type twin screw extruder manufactured by Nippon Steel Works, set the cylinder temperature and screw rotation speed to the conditions shown in Table 3, Melting and kneading were performed using a screw having a low exothermic kneading element introduced into the screw kneading section, and the gut discharged from the die was immediately cooled in a water bath and pelletized by a strand cutter. The pellets obtained were dried at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 240 ° C., mold temperature 80 ° C.). The results of evaluating the mechanical properties, moldability, and heat resistance of each sample are as shown in Table 3. Comparative Example 9 cannot achieve the resin phase separation structure in which the target aromatic polyester resin is a continuous phase and is inferior in moldability and heat resistance, while Examples 17 to 22 are mechanical properties. The moldability and heat resistance were particularly excellent.

The aromatic polyester resin (a) used in the examples and comparative examples is as follows.
(A-1): Polybutylene terephthalate resin having a density of 1.31 g / cm ³ , a melting point of 225 ° C., and an intrinsic viscosity of 0.75.
(A-2): Polybutylene terephthalate resin having a density of 1.31 g / cm ³ , a melting point of 225 ° C., and an intrinsic viscosity of 0.85.
(A-3): Polybutylene terephthalate resin having a density of 1.31 g / cm ³ , a melting point of 225 ° C., and an intrinsic viscosity of 1.25.
(A-4): Polypropylene terephthalate resin having a density of 1.33 g / cm ³ , a melting point of 228 ° C., and an intrinsic viscosity of 0.95.
(A-5): Polyethylene terephthalate resin having a density of 1.39 g / cm ³ , a melting point of 258 ° C., and an intrinsic viscosity of 0.70.

Similarly, the polylactic acid resin (b) is as follows.
(B-1): Poly-L lactic acid resin having a density of 1.25 g / cm ³ , a weight average molecular weight (PMMA conversion) of 210,000, and a D-form content of 1.2%.
(B-2): Poly-L lactic acid resin having a density of 1.25 g / cm ³ , a weight average molecular weight (in terms of PMMA) of 160,000, and a D-form content of 1.2%.

Similarly, the catalyst deactivator (c) is as follows.
(C-1): Phosphorus compound, “Adeka Stub” AX-71 from Asahi Denka Kogyo Co., Ltd.
(C-2): Phosphorus compound, “ADK STAB” PEP-36 from Asahi Denka Kogyo Co., Ltd.
(C-3): hindered phenolic compound, “Adeka Stub” AO-330 from Asahi Denka Kogyo Co., Ltd.
Similarly, the compatibilizer (d) is as follows.
(D-1): Polycarbodiimide (Nisshinbo "Carbodilite" LA-1).
(D-2): Polyfunctional epoxy compound (triglycidyl isocyanurate).

Similarly, the filler (d) is as follows.
(E-1): Talc (Nihon Talc SG-200).
(E-2): Glass fiber having an average fiber diameter of 13 μm (T-187 manufactured by Nippon Electric Glass Co., Ltd.).

Similarly, the resin (f) added in addition to the aromatic polyester resin and polylactic acid resin is as follows.
(F-1): A multilayer structure polymer (“METABRENE” S2001 manufactured by Mitsubishi Rayon Co., Ltd.) in which the core layer is a silicone / acrylic polymer and the shell layer is a methyl methacrylate polymer.
(F-2): Copolymer of butadiene, styrene and methyl methacrylate (“Kane Ace” M-511 manufactured by Kaneka Corporation)

Similarly, the plasticizer (g) is as follows.
(G-1): Polyoxyethyleneoxypropylene block copolymer (Asahi Denka Co., Pluronic F68)
(G-2): Polyoxyethyleneoxypropylene block copolymer (Asahi Denka Co., Ltd., Pluronic L101)
(G-3): Polyoxyethyleneoxypropylene block copolymer (Asahi Denka Co., Pluronic P85)
(G-4): Polypropylene glycol (Asahi Denka Co., Adeka Polyether P-3000)
(G-5): Polyethylene glycol-polylactic acid block copolymer The polyethylene glycol-polylactic acid block copolymer of (G-5) was produced by the method of Production Example 1 below.

(Production Example 1)
0.025 parts by weight of tin octylate is mixed with 71 parts by weight of polyethylene glycol having an average molecular weight of 10,000 and 29 parts by weight of L-lactide, and the mixture is stirred at 140 ° C. for 30 minutes in a nitrogen atmosphere in a reaction vessel equipped with a stirrer. For 60 minutes to obtain a block copolymer of polyethylene glycol and polylactic acid having a polylactic acid segment having an average molecular weight of 2,000.

Claims (11)

The total of (a) and (b) is 100% by weight, the aromatic polyester resin (a) 15-50% by weight , the polylactic acid resin (b) 50-85% by weight, and the sum of (a) and (b) It is a thermoplastic resin composition obtained by blending 0.001 to 2 parts by weight of catalyst deactivator (c) with respect to 100 parts by weight , (volume fraction of aromatic polyester resin / volume fraction of polylactic acid resin) Ratio) × (melt viscosity of polylactic acid resin / melt viscosity of aromatic polyester resin) is greater than 1 and 3.0 or less, and the aromatic polyester resin in the resin phase-separated structure observed with an electron microscope A thermoplastic resin composition characterized by forming a phase structure in which (a) is a continuous phase and polylactic acid resin (b) is a dispersed phase. The thermoplastic resin composition according to claim 1, comprising 25 to 45% by weight of the aromatic polyester resin (a) and 55 to 75% by weight of the polylactic acid resin (b). 3. The thermoplastic resin composition according to claim 1 , wherein the aromatic polyester resin (a) has an intrinsic viscosity in the range of 0.35 to 0.95 . The heat according to any one of claims 1 to 3, wherein 0.01 to 10 parts by weight of the compatibilizer (d) is added to 100 parts by weight of the total of (a) and (b). Plastic resin composition. The thermoplastic resin composition according to claim 4, wherein the compatibilizer (d) is at least one selected from the group consisting of a carbodiimide compound and a polyfunctional epoxy compound. The thermoplasticity according to any one of claims 1 to 5, wherein 0.01 to 30 parts by weight of a plasticizer (g) is added to 100 parts by weight of the total of (a) and (b). Resin composition. The thermoplastic resin composition according to claim 6, wherein the plasticizer (g) is a polyalkylene glycol plasticizer. The thermoplastic resin composition according to any one of claims 1 to 7, wherein a main component of the aromatic polyester resin (a) is a polybutylene terephthalate resin. The resin mixture constituting the thermoplastic resin composition is produced by applying kneading energy of 0.15 kWh / kg or more while controlling the resin temperature to 260 ° C or lower. A method for producing a thermoplastic resin composition according to any one of claims 8 to 10. The molded article obtained by processing the thermoplastic resin composition in any one of Claims 1-8. The molded product according to claim 10, obtained by a method selected from injection molding, injection compression molding, and compression molding.