JP5326232B2 - Resin composition and molded article comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in impact resistance and antistatic performance and having an appearance excellent in surface gloss without pearlescent gloss, further a resin composition excellent in heat resistance, flame retardance and hydrolyzability, and molded products made therefrom. <P>SOLUTION: The resin composition comprises 15-85 wt.% (A) polylactic acid resin, 85-15 wt.% (B) aromatic polycarbonate resin and (C) a polyether-ester block copolymer and/or a polyether-ester-amide block copolymer in 1-50 pts.wt. based on 100 pts.wt. sum total of the components (A) and (B), and has &ge;50 J/m impact strength by Izod impact test of ASTM specification D256. The resin composition may further comprise (D) an inorganic filler having &gt;3 &mu;m average particle size in 0-1 pts.wt. based on 100 pts.wt. sum total of the components (A) and (B). The molded products made thereof are also provided. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention provides a resin composition having an excellent impact strength and antistatic property, having a molded article appearance having no pearly luster and excellent surface gloss, and further a resin composition excellent in heat resistance, flame retardancy and hydrolyzability, and The present invention relates to a molded product comprising the same.

  Polylactic acid resin is expected as a practically excellent biodegradable polymer because it has a high melting point and can be melt-molded. In addition, in the future, it is expected to be used as a general-purpose polymer made from bio raw materials, and various molded products are formed by injection molding, extrusion molding, and the like.

  However, polylactic acid resins have the disadvantage of being inferior in impact resistance and heat resistance, and it has been proposed to blend an aromatic polycarbonate resin excellent in impact resistance and heat resistance.

  Patent Document 1 proposes blending polylactic acid as a method for modifying the fluidity of an aromatic polycarbonate resin. However, since the obtained material has a pearly luster, its application is limited, and there is a problem that the ballast effect is easily caused during melt-kneading and the productivity is poor.

  Patent Document 2 proposes blending an aromatic polycarbonate resin in order to improve the by-cut softening point of polylactic acid resin.

  Patent Document 3 proposes blending polycarbonate to improve the impact resistance of polylactic acid resin.

  However, the compositions of Patent Documents 1 to 3 have a problem inferior in any of the performances of impact strength, electrostatic property, and appearance of a molded product.

  Here, pearl gloss and surface gloss of the molded product appearance will be explained. Melting and mixing two or more different polymers such as polylactic acid resin and aromatic polycarbonate resin is widely used as a polymer blend or a polymer alloy. It is known and widely used as a method for modifying the defects of individual polymers. However, due to differences in viscosity, molecular weight, molecular structure, etc., it is separated into individual phases and has a coarse dispersion structure, and the resulting injection molded product may have a matte appearance that is inferior to pearly luster and surface gloss. is there.

  As a method for improving such phase separation, Patent Document 4 proposes melt mixing a polylactic acid resin and a polycarbonate with a radical reaction initiator in a nitrogen atmosphere.

  In addition, the polylactic acid resin and the aromatic polycarbonate resin composition have a property of being easily charged due to low electrical conductivity and difficult to discharge, and the resulting molded product is easily dusty. There is a problem that the more wiping is done, the more charged the material becomes and the more difficult it is to remove dust, and a molded product with antistatic properties has been desired.

  As a method for suppressing such charging, Patent Document 5 proposes that a migratory antistatic agent is blended with a polylactic acid resin together with a polyether ester amide. There has been a problem that decomposition is reduced, and a material excellent in antistatic properties without containing an antistatic agent has been desired.

  Moreover, since the polylactic acid resin itself is easily combusted, it cannot be used for a member that needs to be flame retardant. On the other hand, the aromatic polycarbonate resin is known as a material that is less flammable than the polylactic acid resin, but the polylactic acid resin and the aromatic polycarbonate resin composition are easily flammable. Could not be used.

Patent Document 1 discloses that a flame retardant can be blended, but there is no disclosure of specific means for obtaining high flame retardancy.
Japanese Patent No. 3279768 (page 1-2), (paragraph number [0008]) US Pat. No. 5,300,576 (EXAMPLE1) JP-A-11-140292 (page 1-2) JP 2002-371172 A (page 1-2) JP-T-2006-51329 (page 1-2)

  The present invention has been achieved as a result of examining the solution of the problems in the above-described prior art as an object.

  Therefore, the object of the present invention is to blend the polylactic acid resin, the aromatic polycarbonate resin and the polyether ester block copolymer and / or the polyether ester amide block copolymer, and has excellent impact strength and antistatic property, It is an object of the present invention to provide a resin composition having an appearance of a molded article having no pearly luster and excellent surface gloss, a resin composition excellent in heat resistance, flame retardancy and hydrolyzability, and a molded article comprising the same.

  The present inventors have developed a resin composition comprising a polylactic acid resin, an aromatic polycarbonate resin, a polyether ester block copolymer and / or a polyether ester amide block copolymer, a dicarboxylic acid anhydride, The present inventors have found that a resin composition containing a flame retardant and a hydrolysis improving agent has excellent characteristics that meet the above-mentioned purpose, and has reached the present invention.

That is, the present invention is as follows.
1. The total of (A) and (B) is 100% by weight, with respect to 100 parts by weight of a resin composition consisting of 15 to 85% by weight of (A) polylactic acid resin and 85 to 15% by weight of (B) aromatic polycarbonate resin. (C) 1 to 50 parts by weight of a polyetherester block copolymer and / or a polyetheresteramide block copolymer and (I) at least one hydrolysis improver selected from carbodiimide compounds and epoxy compounds. A resin composition comprising 0.01 to 10 parts by weight , wherein the impact strength in an Izod impact test of ASTM standard D256 of a molded article made of the resin composition is 50 J / m or more.
2. 2. The resin composition according to 1, wherein (D) 0 to 1 part by weight of an inorganic filler having an average particle diameter exceeding 3 μm is blended with 100 parts by weight of the total of (A) polylactic acid resin and (B) aromatic polycarbonate resin. object.
3. (F) (F) a modified compound or polymer of (f-3) dicarboxylic acid anhydride, (f-2) dicarboxylic acid anhydride, and (A) polylactic acid resin and (B) aromatic polycarbonate resin in total of 100 parts by weight (F-1) The resin composition according to 1 or 2, comprising 0.05 to 5 parts by weight of any one or more selected from dicarboxylic acids.
4). (E) (e) (e-1) hindered phenol antioxidant and (e-2) phosphite antioxidant with respect to a total of 100 parts by weight of (A) polylactic acid resin and (B) aromatic polycarbonate resin And (e-3) The resin composition according to any one of 1 to 3, comprising 0.05 to 5 parts by weight of at least one selected from thioether-based antioxidants.
5. (A) Phosphoric flame retardant, nitrogen compound flame retardant, silicone flame retardant, bromine flame retardant, and other inorganic materials with respect to 100 parts by weight of the total of polylactic acid resin and (B) aromatic polycarbonate resin The resin composition according to any one of 1 to 4, comprising 1 to 100 parts by weight of at least one flame retardant selected from flame retardants.
6). (A) The total of 100 parts by weight of the polylactic acid resin and (B) the aromatic polycarbonate resin, The resin composition as described.
7. (A) 0.01-10 weight part of 2 or more types of hydrolysis improving agents chosen from a carbodiimide compound and an epoxy compound with respect to a total of 100 weight part of (A) polylactic acid resin and (B) aromatic polycarbonate resin The resin composition according to any one of 1 to 6, wherein
8). (A) The total amount of 100 parts by weight of the polylactic acid resin and (B) the aromatic polycarbonate resin, wherein (J) 0.01 to 20 parts by weight of a plasticizer is blended. Resin composition.
9. A molded article comprising the resin composition according to any one of 1 to 8.

  The resin composition of the present invention has excellent impact strength and antistatic properties, a resin composition having a molded product appearance with no pearly luster and excellent surface gloss, and further excellent in heat resistance, flame retardancy and hydrolyzability. The molded article of the present invention, which is a resin plastic material and is made of this resin composition, is effectively used in various applications such as mechanical mechanism parts, electrical / electronic parts, building parts, automobile parts, and daily necessities, taking advantage of the above-mentioned characteristics. be able to.

  The present invention will be described in detail below.

  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. Other monomer units include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentane. Glycol compounds such as erythritol, 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 dicarbohydrate Acids, dicarboxylic acids such as 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, and caprolactone And lactones such as valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Such other copolymerization component is preferably 0 to 30 mol%, and preferably 0 to 10 mol%, based on all monomer components.

  In the present invention, it is preferable to use a polylactic acid resin (A) in which the optical purity of the lactic acid component is high from the viewpoint of compatibility. That is, (A) Of the total lactic acid components of the polylactic acid resin, it is preferable that the L-form is contained in 80% or more, or the D-form is contained in 80% or more, and the L-form is contained in 90% or more or It is particularly preferably 90% or more, more preferably 95% or more of L isomer or 95% or more of D isomer, 98% or more of L isomer, or 98% or more of D isomer. More preferably.

  It is also preferable to use a polylactic acid containing 80% or more of L-form and a polylactic acid containing 80% or more of D-form. It contains 90% or more of polylactic acid containing 90% or more of L-form and D-form. It is more preferable to use polylactic acid in combination.

  (A) The polylactic acid resin may be modified, for example, by using maleic anhydride-modified polylactic acid resin, epoxy-modified polylactic acid resin, amine-modified polylactic acid resin, etc., not only heat resistance, The mechanical properties tend to be improved, which is preferable.

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

  (A) The molecular weight and molecular weight distribution of the polylactic acid resin is not particularly limited as long as it can be practically processed, 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 upper limit is preferably 350,000 or less from the viewpoint of fluidity during molding. The weight average molecular weight here refers to the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography.

  (A) Although it does not restrict | limit especially about melting | fusing point of a polylactic acid resin, It is preferable that it is 120 degreeC or more, and also it is preferable that it is 150 degreeC or more. (A) Since the melting point of the polylactic acid resin tends to increase as the optical purity increases, the polylactic acid resin having a high melting point may be a polylactic acid resin having a high optical purity.

  Moreover, cellulose ester can be mix | blended up to 50 weight part with respect to 100 weight part of (A) polylactic acid resin, and it can use as (A) component.

  In this case, the cellulose ester (A) has a glass transition temperature higher than that of the polylactic acid resin, and when combined, heat resistance can be expected to be improved, and the hydroxyl group of cellulose is blocked with an esterifying agent. Say. Specific esterifying agents include acid bases such as acetyl chloride and propionyl chloride, acid anhydrides such as acetic anhydride, pyropionic acid and butyric anhydride, carboxylic acid compound derivatives such as amide compounds and ester compounds, and ε- Specific examples of cellulose esters include cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate phthalate. ) From the viewpoint of compatibility or miscibility with polylactic acid resin, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate And cellulose triacetate and cellulose acetate propionate are more preferred. Moreover, it is preferable that the substitution degree of the hydroxyl group in cellulose (average number of hydroxyl groups substituted by cellulose ester) is 0.5 to 2.9 per glucose unit. In addition, from the viewpoint of better compatibility or miscibility with (A) polylactic acid resin, the degree of substitution is preferably 1.5 to 2.9, and more preferably 2.0 to 2.8. More preferred. Moreover, said substitution degree can be calculated | required by using and esterifying the esterifying agent produced | generated by alkaline hydrolysis to a high performance liquid chromatography.

  Examples of the aromatic polycarbonate resin (B) in the present invention include aromatic polycarbonates such as aromatic homo- or copolycarbonates obtained by reacting aromatic dihydric phenol compounds with phosgene or diester carbonate.

  Examples of the aromatic dihydric phenol compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4- Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane or the like can be used, and these can be used alone or as a mixture.

  The blending amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin is (A) polylactic acid resin 15 to 85% by weight, (B) aromatic It is preferably 85 to 15% by weight of an aromatic polycarbonate resin, (A) 20 to 80% by weight of a polylactic acid resin, (B) 80 to 20% by weight of an aromatic polycarbonate resin, and (A) 30 to 70% of a polylactic acid resin. Particularly preferred are 70% by weight and 70% by weight of (B) aromatic polycarbonate resin.

  In the present invention, the impact strength and heat resistance of (A) polylactic acid resin can be modified by blending (B) aromatic polycarbonate resin, and (B) the blending amount of aromatic polycarbonate resin is 15 wt. If it is less than%, the above-mentioned modification effect is insufficient, and if the blending amount of the (B) aromatic polycarbonate resin exceeds 85% by weight, the transparency of the molded product becomes too strong.

  The (C) polyether ester block copolymer and / or the polyether ester amide block copolymer in the present invention has high impact strength and antistatic property to the resin composition comprising the component (A) and the component (B). The amount of component (C) is preferably 1 to 50 parts by weight, more preferably 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. Is 2 to 40 parts by weight, particularly preferably 3 to 30 parts by weight. If it is less than 1 part by weight, the impact strength and the antistatic effect are small, and if it exceeds 50 parts by weight, the mechanical properties deteriorate. Therefore, it is not preferable.

With the resin composition of the present invention, a molded product having an impact strength of 50 J / m or more and a volume resistivity of 10 ¹⁴ Ωcm or less can be obtained in an Izod impact test of ASTM standard D256.

  The (C) component polyether ester block copolymer is a polyether ester block copolymer containing a poly (alkylene oxide) glycol having a number average molecular weight of 600 to 10,000, but is not limited thereto. Specific examples of polyether ester block copolymers containing poly (alkylene oxide) glycol include block copolymers of polyesters such as polybutylene terephthalate and poly (alkylene oxide) glycols such as polyethylene glycol. A polyether ester copolymer containing at least 20 to 90% by weight of poly (alkylene oxide) glycol such as polyethylene glycol is preferable, and the degree of polymerization of the polyether ester copolymer is not particularly limited. Mechanical properties of the final resin composition in which a relative viscosity (ηr) measured at 25 ° C. in a concentration of orthochlorophenol solution is 1.1 to 5.0, preferably 1.3 to 4.0. It is preferable from the viewpoint of characteristics and moldability.

  The (C) component polyetheresteramide block copolymer is a polyetheresteramide block copolymer containing an alkylene oxide residue having a number average molecular weight of 200 to 10,000, but is not limited thereto. Examples of specific polyetheresteramide block copolymers include (a-1) a polyamide-forming component, (a-2) a polyester-forming component, and (a-3) an alkylene having a number average molecular weight of 200 to 10,000. It is a block copolymer obtained from a reaction with a diol containing an oxide residue.

  Examples of the (a-1) polyamide-forming component include aminocarboxylic acids having 6 or more carbon atoms or lactams or diamines having 6 or more carbon atoms and dicarboxylic acid salts such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, aminocarboxylic acids such as 2-aminododecanoic acid or lactols such as caprolactam, enanthractam, capryllactam and laurolactam and hexamethylene Diamine-dicarboxylic acid salts such as diamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate, especially caprolactam, 12-aminododecanoic acid, and hexamethylenediamine-adipate Is preferably used.

  Moreover, as said (a-2) polyester formation component, as a dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4 Aromatic dicarboxylic acids such as' -dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1 Of alicyclic dicarboxylic acids such as 1,3-dicarboxymethylcyclohexyl, 1,4-dicarboxymethylcyclohexyl and dicyclohexyl-4,4′-dicarboxylic acid and succinic acid, oxalic acid, adipic acid, sebacic acid and decanedicarboxylic acid Aliphatic dicarboxylic acid and fat Ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3-, 2,3-, or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol as diol In particular, dicarboxylic acids include terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, and decanedicarboxylic acid and aliphatic diol as ethylene glycol, 1,2- or 1,3-propylene glycol. 1,4-butanediol is preferably used in view of polymerizability, color tone and physical properties.

  Examples of the diol containing an alkylene oxide residue having a number average molecular weight of 200 to 10,000 (a-3) include poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, and poly (1,3 -Propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, block or random copolymer of ethylene oxide and propylene oxide and block or random copolymer of ethylene oxide and tetrahydrofuran. Among these, poly (ethylene oxide) glycol is particularly preferably used in terms of excellent antistatic properties.

  Diols containing alkylene oxide residues having a number average molecular weight of 200 to 10,000 include those added to both ends, such as hydroquinone, bisphenol A, and naphthalene, and further dicarboxylic acids and diamines. Three components can be used.

  (A-3) The number average molecular weight of the diol containing an alkylene oxide residue is preferably in the range of 200 to 10,000, preferably 400 to 6,000, from the viewpoints of polymerizability and antistatic properties.

  (C-3) Component unit of the polyetheresteramide block copolymer (a-3) The diol containing an alkylene oxide residue having a number average molecular weight of 200 to 10,000 is 20 to 90% by weight, preferably 30 to 80% by weight is preferable from the viewpoint of antistatic properties, and the degree of polymerization of the polyetheresteramide block copolymer is not particularly limited, but the relative viscosity (measured at 25 ° C. in a 0.5% orthochlorophenol solution) ηr) is preferably 1.0 to 5.0, preferably from the viewpoint of mechanical properties and moldability of the final resin composition obtained in the range of 1.3 to 4.0. 6 / Polyethylene glycol resin is commercially available under the trade name “Pelestat” manufactured by Sanyo Chemical Industries.

  In the present invention, the resin composition having an impact strength of 50 J / m or more in the Izod impact test of ASTM standard D256 is 1/8 inch (about 3.17 mm) in thickness according to the shape of ASTM standard D256, V Using 10 injection-molded products processed into notches, an impact test was performed with an Izod impact tester model CIT-1201 manufactured by Toyo Seimitsu Kogyo Co., Ltd., and 10 impact energies were obtained. J / m), and a resin composition blended at a specific ratio of the present invention is a resin composition having an impact strength of 50 J / m or more in the ASTM standard D256 Izod impact test.

  In the present invention, the (D) inorganic filler having an average particle diameter exceeding 3 μm includes a plate-like, needle-like or granular inorganic filler, and the average particle diameter is measured by a laser diffraction scattering method. The cumulative distribution is 50% average particle size. The blending amount of the inorganic filler (D) having an average particle size exceeding 3 μm is 1 part by weight from the viewpoint of impact strength with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. In the following, it is more preferable that it is less than 0.5 parts by weight, and it is particularly preferable not to blend. (D) It is preferable that the blending amount of the inorganic filler exceeding the average particle size of 3 μm is 1 part by weight or less because the impact resistance of the molded product made of the resin composition can be improved.

  As said inorganic filler, what pulverized the silicate mineral, the silicate mineral, and various minerals by processes, such as a grinding | pulverization, is used preferably. Specific examples include bentonite, dolomite, barlite, finely divided silicic acid, aluminum silicate, silicon oxide, dosonite, shirasu balloon, clay, sericite, feldspar powder, kaolin, zeolite (including synthetic zeolite), talc, mica and Wollastonite (including synthetic wollastonite), glass flakes, glass beads, hydrotalcite, calcium carbonate, silica and the like can be mentioned, and they are blended for improving heat resistance.

  Among the inorganic fillers, an inorganic filler having an average particle diameter of 3 μm or less is preferable from the viewpoint of improving heat resistance while maintaining impact strength, and more preferably in the range of an average particle diameter of 0.1 to 2.5 μm. Preferably, an inorganic filler having an average particle size of less than 0.1 μm is not preferable from the viewpoint of handleability at the time of manufacture, and adding a large amount of an inorganic filler having an average particle size exceeding 3 μm can reduce the impact strength of the molded product. Since it lowers, it is not preferable. The measuring method of the average particle diameter is the 50% average particle diameter of the cumulative distribution measured by the laser diffraction scattering method as in the previous period.

  The blending amount of the inorganic filler having an average particle size of 0.1 to 3 μm is 0.1 to 15 weights with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. Part is preferable, particularly preferably 0.5 to 10 parts by weight. If it is less than 1 part by weight, the effect of improving heat resistance is small, and if it exceeds 15 parts by weight, even if the inorganic filler has a small average particle diameter, This is not preferable because the strength is lowered.

  In the present invention, (E) (e-1) a hindered phenol antioxidant and (e-2) a phosphite antioxidant and (e-3) a thioether antioxidant are blended. By doing so, it is preferable because the heat deterioration deterioration characteristics of the molded product can be improved. (E) The resin composition which mix | blends (A) polylactic acid resin, (B) aromatic polycarbonate, and (C) polyetherester block copolymer and / or polyetheresteramide block copolymer by the mixing | blending of a component. When an object is injection-molded, it has the effect of suppressing the appearance of burnt streaks, silver, etc. in the molded product, not only improving the heat deterioration characteristics such as heat aging resistance, but also a product with a stable molded product appearance. This has the effect of reducing the defective rate. These effects are obtained by using (e-2) a phosphite antioxidant and / or (e-3) a thioether antioxidant rather than using (E) (e-1) a hindered phenol antioxidant alone. Use in combination is preferable because the improvement effect is high.

  The amount of component (E) is preferably 0.05 to 5 parts by weight, more preferably 0, per 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. .1 part by weight to 4 parts by weight, and by adding 0.05 part by weight or more, improvement effects such as burnt streaks and silver can be expressed, and by making the part 5 parts by weight or less, the mechanical properties are deteriorated. Is preferable. The combined ratio of (e-2) and / or (e-3) to (e-1) is (e-1) 20 to 80% by weight, (e) -2) or (e-3) in a total amount of 80 to 20% by weight has a high effect of improving burnt lines, silver and the like.

  Specific examples of the (E) (e-1) hindered phenol antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], Pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1.6-hexanediol-bis [3- (3,5-di-tert-butyl-4) -Hydroxyphenyl) propionate, octadodecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4- Hydroxy-hydrocinnamamide, 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester and 1,3,5-trimethyl Etc. Le-2,4,6-tris (3,5-di -t- butyl-4-hydroxybenzyl) benzene.

  Specific examples of the (e-2) phosphite antioxidant include 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 examples of the (e-3) thioether-based antioxidant include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol. -Tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopro) Pionate), pentaerythritol-tetrakis (3-stearylthiopropionate) and the like.

  Further, a light stabilizer benzophenone compound, benzotriazole compound, aromatic benzoate compound, oxalic acid anilide compound, cyanoacrylate compound, hindered amine compound, and the like may be used in combination.

  In the present invention, by blending at least one selected from (F) (f-1) dicarboxylic acid, (f-2) dicarboxylic acid anhydride and (f-3) dicarboxylic acid anhydride modified compound or polymer. In order to influence the phase structure of the resin composition obtained from (A) polylactic acid resin, (B) aromatic polycarbonate and (C) polyetherester block copolymer and / or polyetheresteramide block copolymer In addition, properties such as impact resistance, heat resistance and moldability are greatly improved, which is preferable.

  The (f-1) dicarboxylic acid is a compound having two carboxylic acids in the molecule. For example, maleic acid, itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, 1-cyclohexene -1,2-dicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, succinic acid, adipic acid, cyclohexanedicarboxylic acid, phthalic acid and the like, and maleic acid in terms of impact resistance and heat resistance Any one or more of succinic acid is preferable, and maleic acid is more preferable in terms of impact resistance. In addition, (f-1) dicarboxylic acid may exist alone as a compound in the resin composition of the present invention, and any one or more of components (A), (B) and (C) May be present without retaining the structure of the dicarboxylic acid.

  The (f-2) dicarboxylic acid anhydride is a compound having a structure in which water molecules are eliminated from the dicarboxylic acid in the molecule. For example, maleic acid anhydride, itaconic acid anhydride, Citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, succinic anhydride , Adipic acid anhydride, cyclohexanedicarboxylic acid anhydride, phthalic acid anhydride, etc., and any one or more of maleic acid anhydride and succinic acid anhydride in terms of impact resistance, heat resistance, and moldability In view of impact resistance and heat resistance, maleic anhydride is more preferable. The (f-2) dicarboxylic acid anhydride may be present alone as a compound in the resin composition of the present invention, and any one of the components (A), (B) and (C). It may react with more than the species and be present without retaining the structure of the dicarboxylic anhydride.

  The modified compound or polymer of (f-3) dicarboxylic anhydride is a polyolefin resin such as high density polyethylene, low density polyethylene, ultra low density polyethylene and polypropylene, ethylene / ethyl acrylate, ethylene / propylene, ethylene / A compound or polymer in which an acid anhydride such as maleic anhydride is grafted or copolymerized to an ethylene copolymer such as butene-1 by a known method. In the present invention, the decalin solvent A product having a molecular weight of 30000 or less measured by a viscosity method converted from an intrinsic viscosity at 135 ° C. to a molecular weight is defined as a modified compound of a dicarboxylic anhydride, and a product having a molecular weight exceeding 30000 is defined as a modified polymer of a dicarboxylic anhydride.

  As commercially available products of the modified compound (f-3) dicarboxylic anhydride, “Mitsui High Wax” acid-modified polyethylene wax and acid-modified polypropylene wax manufactured by Mitsui Chemicals, Inc. are commercially available. Further, as commercial products of (f-3) a modified polymer of dicarboxylic acid anhydride, “Admer” “N-Tuffmer” manufactured by Mitsui Chemicals, Inc. are known.

  In the present invention, the modified compound or polymer of (f-1) dicarboxylic acid, (f-2) dicarboxylic anhydride and (f-3) dicarboxylic anhydride may be used alone or in combination of two or more. You may use together.

  Moreover, the compounding quantity of the modified compound of (F) (f-1) dicarboxylic acid, (f-2) dicarboxylic acid anhydride, (f-3) dicarboxylic acid anhydride is (A) polylactic acid resin and (B) 0.05 weight part-5 weight part is preferable with respect to 100 weight part of total amounts of aromatic polycarbonate resin, More preferably, it is 0.1 weight part-4 weight part, By mix | blending 0.05 weight part or more. It is preferable to improve the impact resistance, heat resistance, molding processability and the like, and to blend 5 parts by weight or less can prevent deterioration of mechanical properties.

  The blending amount of the modified polymer of (F) (f-3) dicarboxylic anhydride is 0.5 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. -30 parts by weight is preferable, more preferably 1 part by weight to 20 parts by weight. By blending 0.5 parts by weight or more, improvement effects such as impact resistance, heat resistance and molding processability appear, and 30 parts by weight. It is preferable to add less than or equal to a part because the cloth properties can be reduced in mechanical properties.

  In this invention, since a flame retardance can be provided to a composition by mix | blending (G) a flame retardant, it is preferable. (G) A flame retardant is not particularly limited as long as it is a substance added for the purpose of imparting flame retardancy to a resin. Specifically, a brominated flame retardant, a phosphorus flame retardant, a nitrogen compound. -Based flame retardants, silicone-based flame retardants, other inorganic flame retardants and the like, and at least one of them can be selected and used.

  Specific examples of the brominated flame retardant used in the present invention include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromo). Phenoxy) ethane, ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, Tris (2,3-dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobis Enol-A, tetrabromobisphenol-A derivative, tetrabromobisphenol-A-epoxy oligomer or polymer, tetrabromobisphenol-A-carbonate oligomer or polymer, brominated epoxy resin such as brominated phenol novolac epoxy, tetrabromobisphenol-A -Bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, Tris (tribromoneopentyl) phosphate, poly (pentabromobenzylpolyacrylate), octabromotrimethylphenylindane, dibromoneope Chill glycol, pentabromobenzyl polyacrylate, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo phthalic imide. Of these, tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, and brominated epoxy resin are preferable.

  The phosphorus-based flame retardant used in the present invention is not particularly limited, and a generally used phosphorus-based flame retardant can be used. Typically, an organic phosphorus compound such as a phosphate ester or a polyphosphate, , Red phosphorus.

  Specific examples of the phosphoric acid ester in the above organic phosphorus compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl. Phosphate, tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl Phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acetate Phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid Examples include condensed phosphate esters such as diethyl, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and condensates thereof. be able to. Examples of commercially available condensed phosphate esters include PX-200, PX-201, PX-202, CR-733S, CR-741, CR747 manufactured by Daihachi Chemical Co., Ltd. and FP-600 and T-1317F manufactured by Adeka Corporation. be able to.

  Moreover, the phosphate and polyphosphate which consist of a salt with phosphoric acid, polyphosphoric acid, a metal of group IA-IVB of the periodic table, ammonia, an aliphatic amine, and an aromatic amine can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts and the like as metal salts, methylamine salts as aliphatic amine salts, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts, triazine salts, melamine salts, and ammonium salts.

  In addition to the above, halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris (β-chloropropyl) phosphate), and a structure in which a phosphorus atom and a nitrogen atom are connected by a double bond. Examples thereof include phosphazene compounds and phosphoric ester amides.

  Further, as red phosphorus, not only untreated red phosphorus but also red phosphorus treated with one or more compound films selected from the group consisting of thermosetting resin coatings, metal hydroxide coatings, and metal plating coatings. It can be preferably used. The thermosetting resin of the thermosetting resin film is not particularly limited as long as it is a resin capable of coating red phosphorus. For example, phenol-formalin resin, urea-formalin resin, melamine-formalin resin, alkyd resin Etc. The metal hydroxide coating is not particularly limited as long as it can coat red phosphorus, and examples thereof include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. . The metal of the metal plating film is not particularly limited as long as it can coat red phosphorus, and examples thereof include Fe, Ni, Co, Cu, Zn, Mn, Ti, Zr, Al, and alloys thereof. Furthermore, these coatings may be laminated in combination of two or more or in combination of two or more.

  Examples of the nitrogen compound-based flame retardant used in the present invention include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides, aromatic amides, urea, thiourea and the like. . In addition, nitrogen-containing phosphorus flame retardants such as ammonium polyphosphate as exemplified in the above phosphorus flame retardant are not included in the nitrogen compound flame retardant referred to herein. Examples of the aliphatic amine include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane, 1,2-diaminocyclooctane and the like. Examples of the aromatic amine include aniline and phenylenediamine. Examples of nitrogen-containing heterocyclic compounds include uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, and triazine compounds. Examples of the cyan compound include dicyandiamide. Examples of the aliphatic amide include N, N-dimethylacetamide. Examples of aromatic amides include N, N-diphenylacetamide.

  The triazine compounds exemplified above are nitrogen-containing heterocyclic compounds having a triazine skeleton, and are triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, triphenyltriazine, amelin, and amelide. And thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoisopropoxytriazine and the like.

  As melamine cyanurate or melamine isocyanurate, an addition product of cyanuric acid or isocyanuric acid and a triazine compound is preferable, usually an addition having a composition of 1 to 1 (molar ratio) and optionally 1 to 2 (molar ratio). You can list things. Although it is produced by a known method, for example, a mixture of melamine and cyanuric acid or isocyanuric acid is made into a water slurry and mixed well to form both salts into fine particles, and then the slurry is filtered and dried. Later it is generally obtained in powder form. The salt does not need to be completely pure, and some unreacted melamine, cyanuric acid or isocyanuric acid may remain. Moreover, the average particle diameter before blending with the resin is preferably 100 to 0.01 μm, more preferably 80 to 1 μm from the viewpoint of flame retardancy, mechanical strength, and surface property of the molded product.

  Of the nitrogen compound-based flame retardants, nitrogen-containing heterocyclic compounds are preferable, among which triazine compounds are preferable, and melamine cyanurate is more preferable.

  When the dispersibility of the nitrogen compound flame retardant is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent such as polyvinyl alcohol or metal oxide may be used in combination. Good.

Examples of the silicone flame retardant used in the present invention include silicone resins and silicone oils. Examples of the silicone resin include a resin having a three-dimensional network structure formed by combining structural units of SiO ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. In the silicone oil, polydimethylsiloxane, and at least one methyl group at the side chain or terminal of polydimethylsiloxane is a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, or a polyether group. , A modified polysiloxane modified with at least one group selected from a carboxyl group, a mercapto group, a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group, or a mixture thereof Can be mentioned.

  Other inorganic flame retardants used in the present invention include magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, oxidation Metal of tin salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, calcium borate, ammonium borate, ammonium octamolybdate, tungstic acid Examples thereof include salts, complex oxide acids of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, graphite, and swellable graphite. Of these, aluminum hydroxide, zinc borate, and swellable graphite are preferable.

  The (G) flame retardant may be used alone or in combination of two or more. In addition, when using aluminum hydroxide, it is preferable to knead | mix previously (A) polylactic acid resin and (B) aromatic polycarbonate resin, and to melt-mix and use it at the kneading | mixing temperature of 210 degrees C or less.

  The blending amount of the (G) flame retardant is preferably 1 to 100 parts by weight, more preferably 2 to 70 parts by weight, with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. Is preferred.

  Among the flame retardants (G), at least one or two or more selected from phosphorus-based flame retardants, nitrogen compound-based flame retardants, silicone-based flame retardants, and other inorganic flame retardants that do not contain any halogen. Are preferably used in combination. In the above, when two or more flame retardants are used in combination, it is preferable to use a phosphorus-based flame retardant together with another flame retardant. The nitrogen compound-based flame retardant used in combination with the phosphorus-based flame retardant is preferably a nitrogen-containing heterocyclic compound, more preferably a triazine compound, and further preferably melamine cyanurate. Moreover, as a silicone type flame retardant used together with a phosphorus type flame retardant, a silicone resin is preferable. Moreover, as other inorganic flame retardants used in combination with phosphorus flame retardants, aluminum hydroxide, zinc borate and swellable graphite are preferable. Further, the blending ratio with the phosphorus-based flame retardant can be combined with any amount, and the amount of the phosphorus-based flame retardant in 100% by weight of the flame retardant is particularly preferably 5% by weight or more, and 5 to 95% by weight. It is more preferable that

  The (H) fluorine-based resin in the present invention is a resin containing fluorine in a substance molecule, specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, Tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, hexafluoropropylene / propylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer, etc. Polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene Fluoride is preferred, polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymer are particularly preferred, polytetrafluoroethylene is more preferred, and polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer The body is also preferably used. The molecular weight of the fluororesin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, particularly for the extrudability and flame retardancy of the present invention. effective. Commercially available products of polytetrafluoroethylene include “Teflon (registered trademark)” 6-J, “Teflon (registered trademark)” 6C-J, and “Teflon (registered trademark)” 62 manufactured by Mitsui DuPont Fluorochemical Co., Ltd. -J, “Full-on” CD1 and CD076 manufactured by Asahi IC Fluoropolymers Co., Ltd. are commercially available. In addition, as a commercial product of a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, it is commercially available as “Metabrene (registered trademark)” A series from Mitsubishi Rayon Co., Ltd. METABLEN (registered trademark) “A-3000”, “METABBRENE (registered trademark)” A-3800, and the like are commercially available. In addition, polytetrafluoroethylene “Teflon (registered trademark)” 6-J and the like are prone to agglomerate, so if they are mechanically strongly mixed with other resin compositions using a Henschel mixer or the like, agglomeration may occur due to aggregation. There are problems in handling and dispersibility depending on conditions. On the other hand, a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is excellent in handling properties and dispersibility, and is particularly preferably used. The polytetrafluoroethylene-containing mixed powder composed of the polytetrafluoroethylene particles and the organic polymer is not limited, but polytetrafluoroethylene disclosed in Japanese Patent Application Laid-Open No. 2000-226523. Polytetrafluoroethylene-containing mixed powder composed of particles and an organic polymer, and the like. Examples of the organic polymer include aromatic vinyl monomers, acrylate monomers, and vinyl cyanide. An organic polymer containing 10% by weight or more of a monomer, and a mixture thereof may be used. The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder is from 0.1% by weight to 90%. It is preferable that it is weight%.

  Moreover, the compounding quantity of (H) fluorine-type resin is 0.01-3 weight part with respect to 100 weight part of total amounts of (A) polylactic acid resin and (B) aromatic polycarbonate resin, Preferably it is 0.8. 02 to 2 parts by weight is preferable, and 0.03 to 1 part by weight is more preferable. If the blending amount of the fluorine-based resin exceeds 3 parts by weight, the flame retardancy is decreased, and if it is less than 0.01, no effect is found in improving the flame retardancy.

  In the present invention, (I) one kind of hydrolysis improver selected from an epoxy compound and a carbodiimide compound improves the hydrolyzability of the resin composition of the present invention, and the durability of the resin composition of the present invention such as wet heat characteristics. Is used, and one or two or more of them are used in combination.

  One kind of hydrolysis improver selected from the above (I) epoxy compound and carbodiimide compound is (A) a compound capable of blocking the carboxyl terminal, such as polylactic acid resin, and has a carboxyl terminal group at the time of melt-kneading or wet heat. It is blocked to improve hydrolyzability.

  The epoxy compound may be a monofunctional epoxy compound or a bifunctional or higher functional epoxy compound, but is preferably an epoxy compound having a glycidyl group, such as a glycidyl ester compound, a glycidyl ether compound, And glycidyl ester ether compounds. One or more of these epoxy compounds can be used.

  As an epoxy compound that is preferably used, an epoxy compound in which a monofunctional glycidyl ester compound and a glycidyl ether compound are used in combination or a composition from which a monofunctional glycidyl ester compound is obtained has an excellent balance between viscosity stability and hydrolysis resistance. . The epoxy compound may be a polymer compound grafted or copolymerized with a glycidyl compound. The polymer compound grafted or copolymerized with a glycidyl compound or acid anhydride is not limited, but acrylonitrile. / A polymer compound containing the above glycidyl compound by grafting or copolymerization with styrene, ethylene copolymer, polyamide resin, or the like, and one or more selected from among them are used. Examples of the above ethylene copolymers include ethylene as a monomer, and copolymerizable monomers include propylene, butene-1, vinyl acetate, isoprene, butadiene, monocarboxylic acids such as acrylic acid and methacrylic acid, or the like. Examples include copolymers prepared from the following ester acids, and polymer compounds grafted with methyl methacrylate are also preferably used. Acrylonitrile / styrene / glycidyl methacrylate, ethylene / glycidyl methacrylate, ethylene / glycidyl methacrylate-g-methacrylic acid Examples of specific examples include methyl ("-/-" represents copolymerization, "-g-" represents grafting, the same applies hereinafter), and commercially available products such as "Bond" manufactured by Sumitomo Chemical Co., Ltd. “First” or “Modipa” manufactured by Nippon Oil & Fats Co., Ltd. "There is such.

  The carbodiimide compound is a compound having a carbodiimide group represented by (—N═C═N—) in the molecule. For example, the organic isocyanate is heated in the presence of a suitable catalyst to remove the carbodiimide compound. It can be produced by a carbonic acid reaction.

  Specific examples of the carbodiimide compound include diphenylcarbodiimide, di-cyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, and 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-phenyle -Bis-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 Nitrophenylcarbodiimide, N, N′-di-p-aminophenylcarbodiimide, N, N′-di-p-hydroxyphenylcarbodiimide, N, N′-di-cyclohexylcarbodiimide, N, N′-di-p-toluyl Carbodiimide, 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-isopropylphenylcarbodiimi N, 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 Mono- or dicarbodiimide compounds such as N, N'-di-2,4,6-triisopropylphenylcarbodiimide, N, N'-di-2,4,6-triisobutylphenylcarbodiimide, Poly (1,6-hexamethylenecarbodiimide), poly (4,4′-methylenebiscyclohexyl) Rubodiimide), 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 ( And polycarbodiimides such as triethylphenylenecarbodiimide) and poly (triisopropylphenylenecarbodiimide). Of these, N, N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide and carbodiimide-modified isocyanate compounds are preferred. Furthermore, there may be a mixture of the carbodiimide compound and the thermoplastic resin, a mixture of the carbodiimide compound and the end of the thermoplastic resin, or one or more of them.

  Furthermore, at least one compound selected from an oxazoline compound, an oxazine compound, and an isocyanate compound that can be used as a carboxyl group-reactive terminal blocking agent other than an epoxy compound and a carbodiimide compound can be used in combination.

  In addition, the blending amount of one kind of hydrolysis improver selected from (I) epoxy compound and carbodiimide compound is the sum of (A) polylactic acid resin and (B) aromatic polycarbonate resin from the viewpoint of viscosity stability and hydrolyzability. The amount is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight.

  As the plasticizer (J) in the present invention, known ones generally used as polymer plasticizers can be used without any particular limitation. For example, polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers And polyalkylene glycol plasticizers and epoxy plasticizers. Moreover, in this invention, there exists an effect which improves injection moldability, without reducing impact strength by mix | blending (J) plasticizer.

  Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, 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, 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, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, adipic acid Adipic acid esters such as benzylbutyl diglycol, citrate esters such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebacin Dibutyl, and sebacic acid esters such as di-2-ethylhexyl sebacate and the like.

  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 thereof include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, polyacrylic acid esters, and paraffins. The (K) plasticizer used in the present invention is preferably at least one selected from polyester-based plasticizers and polyalkylene glycol-based plasticizers, among those exemplified above, and may be used in combination of two or more. Good.

  Moreover, the blending amount of the plasticizer (J) is preferably 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin (B) aromatic polycarbonate resin. Part is more preferable, and the range of 0.5 to 10 parts by weight is particularly preferable. If the amount is less than 0.01 part by weight, there is no effect of improving injection moldability, and if it exceeds 20 parts by weight, impact strength and heat resistance are decreased. Absent.

  In the present invention, a thermoplastic resin other than (A) a polylactic acid resin, a cellulose ester, (B) an aromatic polycarbonate resin, and (C) a polyetherester block copolymer and / or a polyetheresteramide block copolymer Specific examples of thermoplastic resins that can be blended include polyolefin resins such as low-density polyethylene resins, high-density polyethylene resins, and polypropylene resins, polyester resins, polyamide resins, polystyrene resins, polyacetal resins, polyurethane resins, and aromatic resins. Aliphatic and aliphatic polyketone resins, polyphenylene sulfide resins, polyether ether ketone resins, polyimide resins, thermoplastic starch resins, polystyrene resins, acrylic resins such as polymethyl methacrylate, polyvinyl chloride resins Polyvinylidene chloride resin, vinyl ester resin, polyurethane resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene oxide resin, poly-4-methylpentene-1, polyetherimide resin, and polyvinyl alcohol resin And so on.

  In addition, ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers and alkali metal salts thereof (so-called ionomers) , Ethylene-acrylic acid alkyl ester copolymer (for example, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer), acid-modified ethylene-propylene copolymer, diene rubber (for example, polybutadiene, polyisoprene, poly Chloroprene), polyisobutylene, copolymers of isobutylene and butadiene or isoprene, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber, etc. Degree A layer composed of a core layer and one or more shell layers covering the core layer, and a layer adjacent to each other. A so-called core-shell rubber called a so-called core-shell rubber composed of different polymers can also be used, and a core-shell rubber containing a silicone compound or a silicone / acrylic composite core-shell rubber can also be used.

  The various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers and graft copolymers, and may be used alone. Two or more types may be used in combination.

  Among the above thermoplastic resins, polyester resins, acrylic resins such as polymethyl methacrylate, styrene resins, and core shell rubbers are more preferably used.

  Moreover, the compounding quantity of said thermoplastic resin is 1-100 weight part with respect to 100 weight part of total amounts of (A) polylactic acid resin and (B) polycarbonate resin, Furthermore, it is 2-80 weight part. Is preferred.

  In the present invention, a fibrous reinforcing material can be further blended to improve heat resistance, particularly heat distortion temperature. As the fibrous reinforcing material, those usually used for reinforcing thermoplastic resins are used. be able to. Specifically, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, sepiolite, asbestos, slag fiber, zonolite, elestite, plaster Fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber and other inorganic fibrous reinforcements, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie And organic fibrous reinforcing materials such as cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, bamboo fiber, banana fiber, sugar cane, wood pulp, paper waste, waste paper and wool. Among these fiber reinforcing materials, glass fiber, bamboo fiber and kenaf are particularly preferable. The fibrous reinforcing material may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or a cup such as aminosilane or epoxysilane. It may be treated with a ring agent or the like.

  The amount of the fibrous reinforcing material is preferably 1 to 200 parts by weight, more preferably 2 to 100 parts by weight, with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. .

  In the present invention, a layered silicate can be further blended, and the formability can be improved. The layered silicate is more preferably blended with a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions. In the present invention, the layered silicate in which the exchangeable cation existing between the layers is exchanged with the organic onium ion is the exchange of the exchangeable cation of the layered silicate having the exchangeable cation between the layers with the organic onium ion. Inclusion compound.

  A layered silicate having an exchangeable cation 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 angstroms are laminated. Has a cation. The cation exchange capacity is 0.2 to 3 meq / g, and preferably the cation exchange capacity is 0.8 to 1.5 meq / g.

  Specific examples of the layered silicate include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate. Examples thereof include swelling mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, and the like, which may be natural or synthesized. 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, and examples of the primary ammonium ion include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, and benzyl ammonium. Examples of secondary ammonium ions include methyldodecylammonium and methyloctadecylammonium. Examples of tertiary ammonium ions include dimethyldodecylammonium and dimethyloctadecylammonium. Examples of quaternary ammonium ions include benzyltrimethylammonium, benzyltriethylammonium, Benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyl Benzyltrialkylammonium ions such as utadecylammonium and benzalkonium, alkyltrimethylammonium ions such as trimethyloctylammonium, trimethyldodecylammonium, and trimethyloctadecylammonium, dimethyldialkyl such as dimethyldioctylammonium, dimethyldidodecylammonium, and dimethyldioctadecylammonium Examples thereof include ammonium ions, trialkylmethylammonium ions such as trioctylmethylammonium and 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.
The layered silicate in which the exchangeable cation existing in the interlayer used in the present invention is exchanged with the organic onium ion is obtained by reacting the layered silicate having the exchangeable cation between the layer and the organic onium ion by a known method. Can be manufactured. Specifically, a method by an 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 melted ammonium salt may be used.

  In the present invention, the amount of the organic onium ion relative to the layered silicate is such that the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, the suppression of odor generation, and the like (J) Usually, it is in the range of 0.4 to 2.0 equivalents with respect to the cation exchange capacity, but preferably 0.8 to 1.2 equivalents.

  In addition to the above organic onium salts, these layered silicates are preferably pretreated 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.

  The amount of layered silicate is preferably 0.1 to 50 parts by weight, and 0.5 to 30 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. Is more preferable, and 1 to 10 parts by weight is particularly preferable.

  In the present invention, a crystal nucleating agent can be further blended for the purpose of improving the injection moldability and heat resistance of the resin composition of the present invention. As the crystal nucleating agent, known inorganic nucleating agents such as nitrides are used. , Organic nucleating agents such as organic carboxylic acid metal salts, sorbitols, and (A) polymer nucleating agents having a melting point higher than that of polylactic acid resin, etc., may be used alone or in combination of two or more. If it is used in combination with (J) a plasticizer, it is further effective in improving injection moldability.

  The compounding amount of the crystal nucleating agent is preferably 0.01 to 20 parts by weight, and 0.05 to 10 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin. Further preferred.

  In the present invention, for the purpose of obtaining a colored molded product of the resin composition of the present invention, one or more kinds of carbon black, titanium oxide, dial, ultramarine blue, calcined yellow, and various pigments and dyes are further blended. It is also possible to improve the toning, weather resistance (light) resistance, and conductivity of the resin in various colors, and the blending amount of the pigment or dye can be (A) polylactic acid resin and (B) aromatic It is 0.1-5 weight part with respect to 100 weight part of total amounts of polycarbonate resin, Preferably it is 0.2-4 weight part, More preferably, it is 0.3-3 weight part.

  Examples of the carbon black include, but are not limited to, channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. The average particle diameter is 500 nm or less, and dibutyl phthalate. Carbon black having an oil absorption of 50 to 400 cm 3/100 g is preferably used, and may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like as a treatment agent.

  Further, as the titanium oxide, titanium oxide having a rutile form or anatase form and having an average particle diameter of 5 μm or less is preferably used, and aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, It may be treated with a polyol, a silane coupling agent or the like. In addition, the above-described carbon black, titanium oxide, and various color pigments and dyes may be used in various thermoplastic resins in order to improve dispersibility with the flame retardant resin composition of the present invention and to improve handling during production. And may be used as a blended material that is melt blended or simply blended. In particular, the thermoplastic resin is preferably a polyester resin such as a polylactic acid resin, and a polylactic acid resin is particularly preferably used.

  For the resin composition of the present invention, an amine antioxidant, a light-resistant agent, an ultraviolet absorber, a copper damage inhibitor, a release agent (fatty acid, fatty acid metal salt, Fatty acid, fatty acid ester, aliphatic partially saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, modified silicone), etc. It can be added as necessary.

  Although the manufacturing method of the resin composition of this invention is not specifically limited as long as the requirements prescribed | regulated by this invention are satisfy | filled, For example, (A), (B) and (C) component, as needed (D ) To (J) component, and after further blending other additives as necessary, (A) a method of uniformly kneading with a single screw or twin screw extruder above the melting point of the polylactic acid resin, A method of removing the solvent after mixing in the solution is preferably used.

  When the resin composition of the present invention is produced, the melt-kneading temperature is preferably 170 to 240 ° C, more preferably 175 to 230 ° C, and particularly preferably 180 to 220 ° C.

  The resin composition of the present invention is a general-purpose polymer excellent in impact strength and antistatic properties, and is formed by injection molding, blow molding, extrusion molding, sheet molding, film molding and spinning into various fibers such as undrawn yarn, drawn yarn, and superdrawn yarn. Can be used as molded products for various purposes such as mechanical mechanism parts, electrical / electronic parts, automobile parts, optical equipment, building materials, and daily necessities. Useful for goods.

  Moreover, since the molded article of the present invention has a plant-derived (A) polylactic acid resin as a main component, it can be suitably used as a useful molded article from the viewpoint of protecting the natural environment as compared with petroleum-derived resins.

  In addition, since the resin composition further blended with (G) a flame retardant can satisfy the standard of the vertical combustion test of US UL standard subject 94 (UL94), a housing in which flame retardancy is essential It can be suitably used as a molded product such as a casing of an electric product.

  The present invention will be described in more detail below by way of examples, but these examples do not limit the present invention.

[Examples 26 to 29 , 36 to 41 , Comparative Examples 1 to 40 ]
(A) Poly-L lactic acid resin, aromatic polycarbonate resin shown below, polyether ester block copolymer, polyether having a D-form content of 1.2% and a weight average molecular weight in terms of PMMA of 160,000 Esteramide block copolymers, inorganic fillers with an average particle size exceeding 3 μm, hindered phenol antioxidants, phosphite antioxidants, thioether antioxidants, dicarboxylic acids, dicarboxylic anhydrides, and dicarboxylic anhydrides The modified compounds or polymers of the product, various flame retardants, fluororesins, epoxy compounds, carbodiimide compounds, plasticizers and other additives to be blended as necessary are mixed in the proportions shown in Tables 1 to 6, respectively. Melting and kneading is performed with a 30mm diameter twin screw extruder under conditions of a cylinder temperature of 250 ° C and a rotation speed of 150rpm. Pull the molten GATT from the die into strands, cooled with water in a cooling bath, to obtain a resin composition pelletized by a strand cutter.

  In Tables 1 to 6, (B) aromatic polycarbonate resin, (C) polyether ester block copolymer and / or polyether ester amide block copolymer, (D) inorganic filler having an average particle size exceeding 3 μm , (E) hindered phenolic antioxidants, phosphite antioxidants, thioether antioxidants, (F) dicarboxylic acids, dicarboxylic anhydrides and modified compounds or polymers of dicarboxylic anhydrides (G) various difficulties The signs of the flame retardant, (H) fluorine-based resin, (I) epoxy compound, carbodiimide compound (J) plasticizer, (K) other additives indicate the following contents ("-/-" is common Represents polymerization or graft copolymerization, the same shall apply hereinafter). In addition, the compounding quantity of (C)-(K) component is a compounding quantity with respect to 100 weight part of total amounts of (A) polylactic acid resin and (B) aromatic polycarbonate resin.

    B-1: (B) Aromatic polycarbonate resin (“A-1900” manufactured by Idemitsu Petrochemical Co., Ltd.)

C-1: Polyetherester block copolymer: 12 parts by weight of terephthalic acid, 11 parts by weight of 1,4 butanediol, 77 parts by weight of polyethylene glycol having a number average molecular weight of 8000, 0.2 parts by weight of an antioxidant (Irganox 1098) And 0.1 part by weight of titanium catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, and the mixture was purged with nitrogen and stirred at 90 ° C for 90 minutes while flowing a small amount of nitrogen, and 0.1 part by weight of titanium catalyst was added. Thereafter, polymerization was carried out for 5 hours under the conditions of 250 ° C. and 0.5 mmHg or less to obtain a transparent polymer. The polymer was discharged in a gut shape and pelletized to prepare a pellet-like polyetherester block copolymer <C-1>. The obtained polyetherester block copolymer has a relative viscosity (ηr) measured at 25 ° C. in a 0.5% concentration of orthochlorophenol solution at 2.9, and has a volume resistivity value that is an index of antistatic properties. Was 1 × 10 ⁹ Ω · cm.

C-2: Polyetheresteramide block copolymer: 40 parts of caprolactam, 56.3 parts of polyethylene glycol having a number average molecular weight of 2000, and 4.8 parts of terephthalic acid, 0.2 parts by weight of an antioxidant (Irganox 1098) The mixture was charged into a reaction vessel equipped with a helical ribbon stirring blade together with 0.1 part by weight of antimony trioxide, and purged with nitrogen. The mixture was heated and stirred for 50 minutes while flowing a small amount of nitrogen at 260 ° C. to obtain a transparent homogeneous solution. Was polymerized for 3 hours under the condition of 0.5 mmHg or less to obtain a transparent polymer. The polymer was discharged onto a cooling belt in a gut shape and pelletized to prepare a pellet-like polyetheresteramide block copolymer <C-2>. The obtained polyetheresteramide block copolymer has a relative viscosity (ηr) of 2.01 measured at 25 ° C. in a 0.5% concentration of orthochlorophenol solution, and has a volume resistivity which is an index of antistatic property. The value was 1 × 10 ⁹ Ω · cm.

  D-1: Inorganic filler: (D) Talc (“P-6” manufactured by Nippon Talc Co., Ltd., average particle size of about 4 μm).

  E-1: (E) (e-1) Hindered phenol antioxidant: pentaerythrityl-tetrakis {3- (3,5-t-butyl-4-hydroxyphenyl) propionate} (Nippon Ciba-Geigy Co., Ltd.) “IRGANOX (registered trademark)” 1010).

  E-2: (E) (e-2) Phosphite antioxidant: Tris (2,4-di-t-butylphenyl) phosphite (“IRGAFOS (registered trademark)” 168, manufactured by Ciba Geigy Japan, Inc.) .

  E-3: (E) (e-3) Thioether-based antioxidant: pentaerythritol-tetrakis (3-laurylthiopropionate) (“MARK” AO-412S manufactured by ADEKA CORPORATION).

  F-1: (F) (f-2) Dicarboxylic anhydride: maleic anhydride (reagent grade 1).

  F-2: (F) (f-3) Polyethylene / maleic anhydride wax (“Mitsui High Wax” 1105A manufactured by Mitsui Chemicals, Inc.).

  F-3: (F) (f-3) Ethylene / ethyl acrylate / maleic anhydride (“Bondyne” HX8290 manufactured by Sumitomo Chemical Co., Ltd.).

  G-1: condensed phosphate ester (“PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.).

  G-2: Triphenyl phosphate (“TPP” manufactured by Daihachi Chemical Industry Co., Ltd.).

  G-3: Melamine cyanurate (“MC-440” manufactured by Nissan Chemical Industries, Ltd.).

  G-4: Ammonium polyphosphate (“Fire Cut” FCP730, manufactured by Suzuhiro Chemical Co., Ltd.).

  G-5: Melamine polyphosphate (“Melpua” 200 manufactured by DSM).

  G-6: Zinc borate ("Firebreak" ZB manufactured by Borax).

  H-1: Tetrafluoroethylene (“Teflon (registered trademark)” 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd.).

  H-2: Acrylic-modified tetrafluoroethylene (Mitsubrene (registered trademark) A-3800 manufactured by Mitsubishi Rayon Co., Ltd.).

  I-1: Epoxy compound: Bisphenol A diglycidyl ether (“Epicoat” 828 manufactured by Japan Epoxy Resin Co., Ltd.).

  I-2: Epoxy compound: ethylene / methyl acrylate / glycidyl methacrylate (“Bond First” 7M, manufactured by Sumitomo Chemical Co., Ltd.).

  I-3: Carbodiimide compound: (Nisshinbo Co., Ltd. “Carbodilite” HMV-8CA)

  J-1: Plasticizer: Polyethylene propylene glycol ("Pluronic" F68 manufactured by Adeka Corporation).

  K-1: Cellulose ester: cellulose acetate propionate (Eastman Chemical Co., “CAP”, acetate substitution degree 0.1, propionate substitution degree 2.93).

  K-2: Inorganic filler having an average particle size of less than 3 μm: Talc (“SG-2000” manufactured by Nippon Talc Co., Ltd., average particle size of about 1 μm).

  K-3: Styrene resin: Styrene / ethylene / butadiene / styrene (“Clayton” 1650 manufactured by Shell Chemical Co., Ltd.).

K- 4 : Core shell rubber: Silicone-acrylic composite core shell rubber ("Maybrene" SX-005 manufactured by Mitsubishi Rayon Co., Ltd.).

K- 5 : Layered silicate: Organized layered silicate ("MTE" manufactured by Coop Chemical Co., Ltd.).

  Further, the obtained resin composition was subjected to injection molding at a cylinder temperature of 240 ° C. and a mold temperature of 50 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd. to obtain various molded products. ) To (6) to evaluate the characteristics.

(1) Impact strength Using a V-notch impact test piece having a thickness of 1/8 inch (about 3.17 mm) produced by injection molding, according to ASTM method D256, using the 10 impact test pieces described above, Toyo Seimitsu Industry Co., Ltd. ) Izod impact tester made by impact test using model CIT-1201, 10 impact energies were determined, and the average value was defined as impact strength (unit: J / m).

(2) Appearance of molded product (2.1) Pearl luster The surface appearance of a 80 mm × 80 mm × 3 mm thick square plate produced by injection molding was visually observed, and a sample in which pearl-like pearl luster was observed was determined to be x. .

(2.2) Surface Gloss Furthermore, surface gloss was measured at an incident angle of 60 ° using a digital variable angle gloss meter UGV-5M manufactured by Suga Test Instruments Co., Ltd. The larger the gloss value, the better the surface gloss.

(2.3) Molded Product Defect Rate The surface appearance of 100 square plates was visually observed, a square plate with burnt streaks and silver was determined to be defective, and the defect rate (%) was determined from the number of defective products.

(3) Antistatic property Using a square plate of 80 mm × 80 mm × 3 mm thickness produced by injection molding, volume resistivity was determined using Toa Denpa Kogyo Co., Ltd. Ultra Megaohmmeter Model SM-10E. In addition, it is electroconductivity and is excellent in antistaticity, so that resistance value is small.

(4) Heat resistance Using a 3 mm-thick test piece produced by injection molding, a thermal deformation test was performed under a load condition of 0.45 MPa according to ASTM method D648.

(5) Flame retardance Using a 127 mm × 12.7 mm × 0.8 mm (5 inch × 1/2 inch × 1/32 inch) test piece produced by injection molding, the UL UL Subject 94 (UL94) Combustion test is performed in accordance with the vertical combustion test method, flame retardancy is evaluated, and the evaluation rank is indicated by V-0, V-1, V-2 in the order of excellent flame retardancy, and corresponds to the above rank Those that did not do so were out of specification.

(6) Hydrolyzability A 3 mm-thick ASTM No. 1 dumbbell test piece produced by injection molding was placed in a constant temperature and high humidity container of “Humidy Cabinet” LHL-112 manufactured by Tabay Espec. The conditions of the temperature and humidity of the constant temperature and high humidity and the treatment time are 60 ° C. × 95% RH × 200 h, a tensile test is performed according to ASTM method D638, the tensile strength retention is obtained from the following formula, and hydrolyzability is obtained. It was used as an index.

Tensile strength retention rate (%) = (Tensile strength after treatment ÷ Tensile strength of untreated product) × 100
These results are also shown in Tables 1 to 6.

  From Table 1, the resin composition containing the components (A) to (D) of the present invention within the scope of the invention is excellent in impact strength and antistatic properties, without pearl luster, excellent in surface gloss, and excellent in surface appearance. It can be said that it is a product.

  Also, from Table 2, the resin composition containing the components (A) to (D) of the present invention outside the scope of the invention or the resin composition not containing any of the components (A) to (C) is It was a molded article made of a resin composition inferior in either the antistatic property or the surface appearance.

    Further, from Tables 3 to 6, (E) hindered phenol antioxidant, phosphite antioxidant, thioether antioxidant, (F) modification of dicarboxylic acid, dicarboxylic acid anhydride and dicarboxylic acid anhydride Compound or polymer (G) Various flame retardants, (H) Fluororesin, (I) Epoxy compound, Carbodiimide compound (J) Plasticizer, (K) Resin composition containing other additives has excellent impact strength Resin composition that is excellent in appearance of molded products while maintaining anti-static properties, and has excellent performance in any of the following, such as reduced defective rate, further improved impact strength, imparted flame retardancy, improved hydrolyzability It can be said that it is a molded product consisting of

Claims (9)

The total of (A) and (B) is 100% by weight, with respect to 100 parts by weight of a resin composition consisting of 15 to 85% by weight of (A) polylactic acid resin and 85 to 15% by weight of (B) aromatic polycarbonate resin. (C) 1 to 50 parts by weight of a polyetherester block copolymer and / or a polyetheresteramide block copolymer and (I) at least one hydrolysis improver selected from carbodiimide compounds and epoxy compounds. A resin composition comprising 0.01 to 10 parts by weight , wherein the impact strength in an Izod impact test of ASTM standard D256 of a molded article made of the resin composition is 50 J / m or more. The total amount of (A) polylactic acid resin and (B) aromatic polycarbonate resin is 100 parts by weight, and (D) an inorganic filler having an average particle size exceeding 3 μm is blended in an amount of 0 to 1 part by weight. Resin composition. (F) (F) a modified compound or polymer of (f-3) dicarboxylic acid anhydride, (f-2) dicarboxylic acid anhydride, and (A) polylactic acid resin and (B) aromatic polycarbonate resin in total of 100 parts by weight (F-1) The resin composition according to claim 1 or 2, wherein 0.05 to 5 parts by weight of any one or more selected from dicarboxylic acids are blended. (E) (e) (e-1) hindered phenol antioxidant and (e-2) phosphite antioxidant with respect to a total of 100 parts by weight of (A) polylactic acid resin and (B) aromatic polycarbonate resin The resin composition according to any one of claims 1 to 3, wherein 0.05 to 5 parts by weight of at least one selected from (e-3) a thioether-based antioxidant is blended. (A) Phosphoric flame retardant, nitrogen compound flame retardant, silicone flame retardant, bromine flame retardant, and other inorganic materials with respect to 100 parts by weight of the total of polylactic acid resin and (B) aromatic polycarbonate resin The resin composition according to any one of claims 1 to 4, comprising 1 to 100 parts by weight of at least one flame retardant selected from flame retardants. 6. The composition according to claim 1, wherein (A) 0.01 to 3 parts by weight of (H) fluorine-based resin is blended with respect to a total of 100 parts by weight of (A) polylactic acid resin and (B) aromatic polycarbonate resin. The resin composition according to item. (A) 0.01-10 weight part of 2 or more types of hydrolysis improving agents chosen from a carbodiimide compound and an epoxy compound with respect to a total of 100 weight part of (A) polylactic acid resin and (B) aromatic polycarbonate resin The resin composition according to any one of claims 1 to 6. In any one of Claims 1-7 formed by mix | blending 0.01-20 weight part of (J) plasticizer with respect to a total of 100 weight part of (A) polylactic acid resin and (B) aromatic polycarbonate resin. The resin composition as described. The molded article which consists of a resin composition of any one of Claims 1-8.