JP2011195815A - Thermoplastic resin composition, method for producing the same and article molded out of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in heat resistance, impact resistance and peeling resistance, a method for producing the thermoplastic resin composition and an article molded out of the thermoplastic resin composition.SOLUTION: The thermoplastic resin composition is obtained by blending 1-99 wt.% of a polylactic acid-based resin (A) with 99-1 wt.% of a polyolefin-based resin (B). The polylactic acid-based resin (A) is obtained by reacting 100 parts weight of a polylactic acid-based resin precursor (A') with 0.01-3 parts weight of a chain extender (C). The ratio (MFR/MFR) (wherein MFRis the melt flow rate of the polylactic acid resin (A) at 190°C under 21.2 N load condition; MFRis that of the polyolefin resin (B) at 190°C under 21.2 N load condition) is ≥0.01 and <0.1.

Description

  The present invention is a thermoplastic resin composition comprising (A) a polylactic acid resin and (B) a polyolefin resin, wherein (A) the polylactic acid resin is (A ′) a polylactic acid resin precursor. (A) polylactic acid in which the ratio of the melt flow rate of (A) polylactic acid resin and (B) polyolefin resin is controlled. The present invention relates to a thermoplastic resin composition excellent in heat resistance, impact resistance, and peel resistance, which is obtained by blending a polyolefin resin and (B) a polyolefin resin, a method for producing the same, and a molded article comprising the same.

  Polylactic acid-based resin can be produced at low cost by the fermentation method using microorganisms such as corn as a raw material, and the melting point is as high as about 170 ° C. For this reason, it is expected to be a biopolymer that can replace resin produced from fossil raw materials such as petroleum, and research and application development are being actively promoted.

  However, since the polylactic acid-based resin has a low crystallization rate, there is a limit to use it as a molded product after crystallization. For example, when polylactic acid resin is injection-molded, it not only requires a long molding cycle time and heat treatment after molding, but is also practical in terms of moldability and heat resistance, such as large deformation during molding and heat treatment. There was a big problem. Moreover, it is inferior to impact resistance, and the improvement was desired.

  On the other hand, a technique of blending a plurality of resins is widely known as a polymer alloy technique, and is widely used for the purpose of improving the defects of individual polymers. Regarding polylactic acid-based resins, polymer alloys with various resins are being studied. For example, as a development for general-purpose resin replacement applications, studies are being actively conducted on alloying with polyolefin-based resins. .

  For example, Patent Document 1 discloses a resin composition composed of a biodegradable aliphatic polyester resin typified by a polylactic acid resin and a polyolefin resin, a molded product thereof, and a method for producing the same. In the patent document, as a preferred embodiment, when the biodegradable aliphatic polyester resin and the polyolefin resin are melt-kneaded, the melt flow index of the biodegradable aliphatic polyester under a certain condition and the melt of the polyolefin resin under the same condition are melted. A production method for obtaining a resin composition using a biodegradable aliphatic polyester and polyolefin resin having a flow index ratio in the range of 0.1 to 10 is disclosed, and the heat resistance and impact resistance obtained thereby are disclosed. A resin composition excellent in durability, moldability, and appearance is disclosed. However, although the physical properties such as heat resistance and impact resistance are improved to some extent by the invention of the patent document, the improvement effect is insufficient from a practical viewpoint, and in terms of practical characteristics such as peeling resistance. There was a problem.

  Patent Document 2 discloses a resin composition comprising a polylactic acid-based resin, a polyolefin-based resin, and a compatibilizing agent, and a resin composition excellent in moldability, impact resistance, and heat resistance is disclosed. Has been. However, although the physical properties such as impact resistance and heat resistance are improved to some extent by the invention of the patent document, the improvement effect is insufficient from the practical viewpoint, and in terms of practical characteristics such as peeling resistance. However, the improvement effect was insufficient.

  Patent Document 3 discloses a method for producing a resin composition containing a biodegradable resin typified by a polylactic acid resin and a polyolefin resin, and a molded product. It is disclosed that a resin composition excellent in properties and the like can be obtained. However, although the impact resistance is improved to some extent by the invention of this patent document, the improvement effect is insufficient from a practical viewpoint, and there are problems in terms of practical characteristics such as heat resistance and peel resistance. It was.

  Patent Document 4 discloses a thermoplastic resin composition comprising a lactic acid resin, a polypropylene resin, and an aromatic vinyl / conjugated diene block copolymer modified with a polar functional group. A thermoplastic resin composition excellent in appearance and peel resistance is disclosed. However, although the peel resistance is improved to some extent by the invention of the patent document, the improvement effect is insufficient from the practical point of view, and in terms of practical characteristics such as heat resistance and impact resistance, The improvement effect was insufficient.

  As described above, it is very difficult to obtain a thermoplastic resin composition that is excellent in any of the characteristics such as heat resistance, impact resistance, and peel resistance by using any known method. There have been many requests for materials that can be used practically without problems, and further improvements have been demanded.

International Publication No. 2005/035656 (Page 1-2, Examples) JP 2008-38142 A (page 1-3, Examples) JP 2009-155644 A (page 1-2, Examples) JP-A-2006-241445 (page 1-2, Examples)

  The present invention provides a thermoplastic resin composition excellent in all of the characteristics such as heat resistance, impact resistance, and peel resistance, which has been difficult in the above-described prior art, a method for producing the same, and a molded article comprising the same. Is an issue.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a thermoplastic resin composition comprising (A) a polylactic acid resin and (B) a polyolefin resin, and (A) a polylactic acid resin. The resin is obtained by reacting (A ′) a polylactic acid resin precursor with (C) a chain extender, and (A) a melt flow rate of the polylactic acid resin and (B) a melt of the polyolefin resin. The inventors have found that the above problems can be solved by blending (A) a polylactic acid resin and (B) a polyolefin resin in which the flow rate ratio is controlled, and the present invention has been achieved.

That is, the present invention
(1) (A) A thermoplastic resin composition comprising 1 to 99% by weight of a polylactic acid resin and (B) 99 to 1% by weight of a polyolefin resin, wherein (A) the polylactic acid resin is (A ′) a polylactic acid resin precursor and (A ′) 100 parts by weight of a polylactic acid resin precursor are reacted with 0.01 to 3 parts by weight of (C) a chain extender, the ratio of 190 ° C. of a) polylactic acid resin, the melt flow rate at 21.2N load conditions (MFR _a) and (B) 190 ° C. of the polyolefin resin, the melt flow rate at 21.2N load conditions (MFR _B) ( (MFR _A / MFR _B ) is 0.01 or more and less than 0.1 (A) a polylactic acid resin and (B) a polyolefin resin,
(2) The thermoplastic resin composition as described in (1) above, wherein the (C) chain extender is a polymer containing an epoxy group and / or a polymer containing a carbodiimide group,
(3) The heat according to (2) above, wherein the epoxy equivalent of the polymer containing the epoxy group and the carbodiimide equivalent of the polymer containing the carbodiimide group are 50 to 800 g / mol. A plastic resin composition,
(4) The (C) chain extender is at least one selected from a styrene polymer containing an epoxy group, an acrylic polymer containing an epoxy group, and a copolymer thereof. The thermoplastic resin composition according to any one of (1) to (3) above,
(5) Further, (D) a conjugated diene polymer is blended in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) polyolefin resin. The thermoplastic resin composition according to any one of (1) to (4) above,
(6) (D) The conjugated diene polymer includes (D-1) a conjugated diene polymer having a melt flow rate of more than 30 g / 10 minutes at 230 ° C. and a 21.2N load condition. The thermoplastic resin composition according to item (5),
(7) The heat described in (5) or (6) above, wherein (D) the conjugated diene polymer includes (D-2) a conjugated diene polymer modified with a polar functional group. A plastic resin composition,
(8) (D) The conjugated diene polymer is a block copolymer containing a block mainly containing a conjugated diene and a block mainly containing an aromatic vinyl unit, or a hydrogenated block copolymer thereof. The thermoplastic resin composition as described in any one of (5) to (7) above, wherein
(9) (D) The conjugated diene polymer is not modified with a polar functional group. (D-1) A conjugated diene polymer having a melt flow rate of more than 30 g / 10 min at 230 ° C. and 21.2 N load condition. And (D-2) a conjugated diene polymer modified with a polar functional group having an MFR of 30 g / 10 min or less at 230 ° C. and a 21.2N load condition, (5) to (8) above The thermoplastic resin composition according to any one of the items,
(10) The polar functional group is any one or more of an acid anhydride group, a carboxyl group, an amino group, an imino group, an alkoxysilyl group, a silanol group, a silyl ether group, a hydroxyl group, and an epoxy group. The thermoplastic resin composition according to (7) or (9) above,
(11) The thermoplastic resin composition according to the above (10), wherein the polar functional group is an amino group and / or an imino group,
(12) Further, (E) a phosphorus compound is blended in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) polyolefin resin. The thermoplastic resin composition according to any one of (1) to (11) above,
(13) Further, (B) an ethylene / α-olefin copolymer different from (B) the polyolefin resin is used in an amount of 1 to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) polyolefin resin. 50 parts by weight of the thermoplastic resin composition according to any one of (1) to (12) above,
(14) (A ′) Polylactic acid resin precursor and (A ′) 0.01 to 3 parts by weight of (C) chain extender are melt-kneaded with 100 parts by weight of polylactic acid resin precursor (A ) After obtaining a polylactic acid-based resin, the MFR _A / MFR _B is 0.01 or more and less than 0.1 (A) polylactic acid-based resin and (B) polyolefin-based resin are melt-kneaded. The method for producing a thermoplastic resin composition according to any one of (1) to (13) above,
(15) A thermoplastic resin composition obtained by the production method described in (14) above,
(16) A molded article comprising the thermoplastic resin composition according to any one of (1) to (13) and (15) above.

  The thermoplastic resin composition of the present invention is excellent in impact resistance, heat resistance, and peel resistance. A molded article made of this thermoplastic resin composition can be used in various applications such as automobile parts, electrical / electronic parts, home appliance parts, and various daily necessities taking advantage of the above characteristics.

  In the present invention, (A) a polylactic acid-based resin means (A ′) a polylactic acid-based resin precursor and (A ′) 100 parts by weight of the polylactic acid-based resin precursor. -3 parts by weight are reacted.

  In the present invention, the (A ′) polylactic acid-based resin precursor is a polymer containing L-lactic acid and / or D-lactic acid as a main constituent component, but may contain a copolymer component other than lactic acid. Good. Examples of such other copolymer component units include polyvalent carboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, and the like. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Azelaic acid, sebacic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutyl Polycarboxylic acids such as phosphonium sulfoisophthalic acid, ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglyco Glycerin, pentaerythritol, bisphenol A, aromatic polyhydric alcohol obtained by addition reaction of bisphenol with ethylene oxide, polyhydric alcohols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycolic acid, Hydroxycarboxylic acids such as 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, hydroxybenzoic acid, and glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ -Units generated from lactones such as butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone. Such a copolymerized unit usually preferably has a content of 0 to 30 mol%, preferably 0 to 10 mol%, when the total monomer units are 100 mol%.

  In the present invention, it is preferable to use a polylactic acid resin precursor (A ′) having a high optical purity of the lactic acid component from the viewpoint of heat resistance. That is, (A ′) Among the total lactic acid components of the polylactic acid-based resin precursor, it is preferable that the L isomer is contained in 80% or more, or the D isomer is contained in 80% or more, and the L isomer is contained in 90% or more. It is more preferable that 90% or more of the D isomer is contained, 95% or more of the L isomer is contained or 95% or more of the D isomer is contained, and 98% or more of the L isomer is contained or the D isomer is contained. Most preferably, it is contained at 98% or more. Moreover, the upper limit of the content of L-form or D-form is usually 100% or less.

  In the present invention, as the (A ′) polylactic acid resin precursor, it is preferable to use a polylactic acid stereocomplex in terms of heat resistance and moldability. As a method for forming a polylactic acid stereocomplex, for example, L-form is 90% or more, and in terms of heat resistance, preferably 95%, more preferably 98% or more poly-L-lactic acid, and D-form is 90%. From the viewpoint of heat resistance, preferably, 95%, more preferably 98% or more of poly-D-lactic acid can be mixed using a method such as melt kneading, solid phase kneading, or solution mixing. In addition, as another method, a method of forming a block copolymer composed of a poly-L-lactic acid segment and a poly-D-lactic acid segment can also be mentioned, and a polylactic acid stereocomplex can be easily formed. A method of preparing a block copolymer comprising a poly-L-lactic acid segment and a poly-D-lactic acid segment is preferred. In addition, the polylactic acid stereocomplex may be used alone, but the polylactic acid stereocomplex and poly-L-lactic acid or poly-D-lactic acid may be used in combination.

  In the present invention, as a method for producing the (A ′) polylactic acid resin precursor, a known polymerization method can be used, and a direct polymerization method from lactic acid or a ring-opening polymerization method via lactide can be used. .

  In the present invention, the molecular weight and molecular weight distribution of the (A ′) polylactic acid-based resin precursor are not particularly limited as long as they can be substantially molded, but the phase structure can be easily controlled, The weight average molecular weight (Mw) is preferably 50,000 or more, more preferably 100,000 or more, further preferably 150,000 or more, and particularly preferably 200,000 or more in terms of improving impact properties. The upper limit is not particularly limited, but is preferably 800,000 or less, more preferably 600,000 or less, and more preferably 400,000 or less. The weight average molecular weight (Mw) here is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  In the present invention, the melting point of the (A ′) polylactic acid resin precursor is not particularly limited, but is preferably 140 ° C. or higher, and more preferably 150 ° C. or higher.

  In the present invention, (C) the chain extender is a compound containing (A ′) two or more functional groups having reactivity with the carboxyl group and / or hydroxy group of the polylactic acid resin precursor in the skeleton molecular chain. If it is, there will be no restriction | limiting in particular, Preferably, it is a compound containing an epoxy group, a carbodiimide group, an oxazoline group, an oxazine group, an acid anhydride, and an isocyanate group as a functional group, and these can use 1 or more types. . Among them, from the viewpoint of reactivity, a compound containing an epoxy group and / or a carbodiimide group is preferred, more preferably a polymer containing an epoxy group and / or a polymer containing a carbodiimide group, most preferably an epoxy group. It is a polymer to contain.

  In the present invention, when the chain extender (C) is a polymer containing an epoxy group and / or a polymer containing a carbodiimide group, the epoxy equivalent of the epoxy group and the carbodiimide equivalent of the carbodiimide group are reactive. And from a viewpoint of a moldability, 50-800 g / mol is preferable, More preferably, it is 100-700 g / mol, Most preferably, it is 150-600 g / mol. Here, the epoxy equivalent and the carbodiimide equivalent represent the gram number of a polymer containing 1 equivalent of an epoxy group and the gram number of a polymer containing 1 equivalent of a carbodiimide group.

  In the present invention, when the chain extender (C) is a polymer containing an epoxy group, the skeleton portion of the polymer is not particularly limited. For example, polyethylene, polypropylene, polybutene, polybutadiene, polybutadiene hydrogenated polymer, Those having structures such as olefin polymers such as polyethylene butylene, polyisobutylene, cycloolefin, or vinyl polymers, styrene polymers, acrylic polymers, ester polymers, amide polymers, etc. are preferred. May be one or more types copolymerized. The skeleton of the polymer is more preferably an olefin polymer, a styrene polymer, an acrylic polymer, and one or more copolymers thereof, most preferably a styrene polymer or an acrylic polymer. And one or more copolymers thereof. The epoxy group may be added directly to the polymer, or may have a structure obtained by grafting an epoxy group-containing polymer onto the polymer.

  The styrenic monomer constituting the styrenic polymer here is preferably one or more of styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, t-butylstyrene, o-chlorostyrene, vinylpyridine and the like. More preferably, it is at least one of styrene and α-methylstyrene.

  Moreover, as an acrylic monomer which comprises an acrylic polymer here, Preferably, 1 or more types, such as acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester, are mentioned. For example, as acrylate ester, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, acrylic Examples thereof include one or more of n-octyl acid, n-decyl acrylate, cyclohexyl acrylate, methyl cyclohexyl acrylate, cyclopentyl acrylate, and the like. Further, for example, as methacrylate ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, isobornyl methacrylate, n-hexyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate , N-octyl methacrylate, n-decyl methacrylate, cyclohexyl methacrylate, methyl cyclohexyl methacrylate, cyclopentyl methacrylate and the like. The acrylic monomer constituting the acrylic polymer is more preferably acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate. 1 or more types, such as butyl methacrylate.

  In the present invention, when the chain extender (C) is a polymer containing an epoxy group, the weight average molecular weight (Mw) of the polymer is preferably 1 from the viewpoint of reactivity and compatibility with the resin. 4,000 to 40,000, more preferably 1,500 to 30,000, and most preferably 2,000 to 20,000. The weight average molecular weight (Mw) here is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  In the present invention, when the chain extender (C) is a polymer containing an epoxy group, it can be produced and used by a known technique, but a commercially available product can also be used. Specific examples of products include the NOF "Modiper" series, Sumitomo Chemical "Bond First" series, Toagosei "ARUFON" and "RESEDA" series, BASF "JONCRYL" series, etc. However, from the viewpoint of reactivity, the “ARUFON” series manufactured by Toagosei Co., Ltd. and the “JONCRYL” series manufactured by BASF can be used more suitably.

  In the present invention, (A) a polylactic acid-based resin means (A ′) a polylactic acid-based resin precursor and (A ′) 100 parts by weight of the polylactic acid-based resin precursor. -3 parts by weight, more preferably (C) a chain extender 0.05-2.5 parts by weight, most preferably (C) a chain extender 0.1 to 2.0 parts by weight is reacted.

  In the present invention, the method of reacting (A ′) the polylactic acid resin precursor and (C) the chain extender is not particularly limited, and (A ′) the polylactic acid resin precursor and (C) the chain extender And (A ′) a method in which a polylactic acid resin precursor and (C) a chain extender are kneaded and reacted in a heated and melted state. From the viewpoint of promoting the reaction over time, a method of kneading and reacting (A ′) a polylactic acid-based resin precursor and (C) a chain extender while being heated and melted can be preferably used.

  In the present invention, the method of kneading and reacting (A ′) the polylactic acid resin precursor and (C) the chain extender in a heated and melted state is not particularly limited, but is preferably heated by an extruder or a kneader. A reaction method is used by using a melt kneader, and a reaction method is more preferable by using an extruder. Examples of the extruder include a single-screw extruder, a twin-screw extruder, a multi-screw extruder of three or more axes, a twin-screw / single-screw composite extruder, etc., preferably from the viewpoint of kneadability and convenience. A single screw extruder or a twin screw extruder can be preferably used.

  In the present invention, the melt kneading temperature when (A ′) polylactic acid resin precursor and (C) chain extender are heated, melted and kneaded and reacted is (A ′) polylactic acid resin precursor and (C). There is no particular limitation as long as it is the melting point of the chain extender, but from the viewpoint of reactivity and moldability, it is preferably 150 ° C to 270 ° C, more preferably 160 ° C to 260 ° C, most preferably 170 ° C to 250 ° C. is there.

  In the present invention, the reaction time when the (A ′) polylactic acid resin precursor and the (C) chain extender are heated, melted and kneaded and reacted is not particularly limited. From 5 seconds to 1800 seconds, more preferably from 10 seconds to 1200 seconds, and most preferably from 20 seconds to 600 seconds.

In the present invention, the melt flow rate (MFR _A ) of (A) polylactic acid-based resin at 190 ° C. and 21.2N load condition is (B) the melt flow of polyolefin-based resin at 190 ° C. and 21.2N load condition described later. If the ratio (MFR _A / MFR _B ) to the rate (MFR _B ) is 0.01 or more and less than 0.1, there is no particular limitation, but the moldability, heat resistance, impact resistance, peel resistance, etc. Is preferably 0.1 to 10 g / 10 minutes, more preferably 0.2 to 8 g / 10 minutes, still more preferably 0.3 to 5 g / 10 minutes, Most preferably, it is 0.4-3 g / 10min. The melt flow rate here is a value measured at 190 ° C. under a 21.2N load condition according to JIS K7210 using a “melt indexer” manufactured by Toyo Seiki.

  In the present invention, the melting point of the (A) polylactic acid resin is not particularly limited, but is preferably 140 ° C. or higher, more preferably 150 ° C. or higher.

  In the present invention, the (B) polyolefin resin is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1 -Unmodified olefin resin obtained by polymerizing or copolymerizing olefins such as olefins such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and vinyl alcohol or derivatives thereof, and unsaturated A modified polyolefin resin modified with a compound such as a carboxylic acid or a derivative thereof and a carboxylic acid vinyl ester is not included.

  Specific examples include homopolymers such as polyethylene resin, polypropylene resin, poly 1-butene resin, poly 1-pentene resin, poly 4-methyl-1-pentene resin, and copolymers thereof.

  In the present invention, polyethylene resin, polypropylene resin, and poly-4-methyl-1-pentene resin are preferable in that the phase structure is easily controlled and heat resistance or impact resistance is improved. From the viewpoint of balance, polypropylene resin is most preferable.

  In the present invention, the method for producing the (B) polyolefin-based resin is not particularly limited, and a known method can be used. For example, in the (B) polyolefin-based resin, radical polymerization, Ziegler-Natta catalyst is used. Any method such as coordination polymerization, anion polymerization, or coordination polymerization using a metallocene catalyst may be used.

In the present invention, when the (B) polyolefin resin is a polypropylene resin, it is preferable to use a polypropylene resin with high stereoregularity. When a polypropylene resin with high isotacticity is used, moldability and heat resistance are improved. An excellent resin composition can be obtained. When a high syndiotactic polypropylene resin is used, a resin composition excellent in impact resistance and transparency can be obtained. As stereoregularity, isotacticity or syndiotacticity is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. Syndiotacticity here means deuterated o-dichlorobenzene as a solvent and is observed as syndiotacticity, heterotacticity, and isotacticity in ¹³ C-NMR measurement at 110 ° C. 20.2 ppm, 20.8 ppm, 21.5 ppm, and the sum of the integrated intensities of the methyl-branched peaks of the straight chain are 100%, and can be calculated by expressing the percentage of the integrated intensity of each peak as a percentage. .

  In the present invention, polypropylene resins having different stereoregularity may be used in combination. For example, it is preferable to use two or more types of polypropylene resins having an isotacticity as a main structure, because it is easy to obtain a resin composition excellent in fluidity, moldability, and heat resistance. It is preferable to use one or more high syndiotactic polypropylene resins because a resin composition excellent in moldability, heat resistance and impact resistance can be easily obtained.

  In the present invention, a high isotacticity polypropylene resin is easily obtained by coordination polymerization using a Ziegler-Natta catalyst as a catalyst, and a high syndiotactic polypropylene resin is a coordination polymerization using a metallocene catalyst as a catalyst. It is easy to obtain by.

In the present invention, (B) the melt flow rate (MFR _B ) of the polyolefin resin at 190 ° C. and 21.2N load condition is the melt flow rate of the (A) polylactic acid resin at 190 ° C. and 21.2N load condition. (MFR _a) and the ratio of _(MFR a / MFR _B) is 0.01 or more is not particularly limited as long as it is less than 0.1, the moldability, heat resistance, being excellent in impact resistance and peel resistance In this respect, it is preferably 5 to 50 g / 10 minutes, more preferably 8 to 40 g / 10 minutes, and further preferably 10 to 30 g / 10 minutes. The melt flow rate here is a value measured at 190 ° C. under a 21.2N load condition according to JIS K7210 using a “melt indexer” manufactured by Toyo Seiki.

The thermoplastic resin composition of the present invention, (A) 190 ° C. of the polylactic acid-based resin, melt flow rate at 21.2N load conditions _{(MFR A) (B) 190} ℃ polyolefin resin, 21.2N load conditions The ratio (MFR _A / MFR _B ) of the melt flow rate (MFR _B ) is 0.01 or more and less than 0.1, and (A) a polylactic acid resin and (B) a polyolefin resin are blended. However, MFR _A / MFR _B is preferably 0.02 or more and less than 0.1, and more preferably 0.03 or more and less than 0.1.

In the present invention, as the phase structure of the resin composition, a phase structure in which either (A) a polylactic acid resin or (B) a polyolefin resin is a dispersed phase and the other is a continuous phase (matrix phase). However, from the viewpoint of moldability, heat resistance, impact resistance and peel resistance, it is preferable that (A) the polylactic acid-based resin forms a dispersed phase and (B) the polyolefin-based resin forms a continuous phase. . In the present invention, by setting the above MFR _A / MFR _B to 0.01 or more and less than 0.1, (A) a polylactic acid resin forms a dispersed phase, and (B) a polyolefin resin forms a continuous phase. This facilitates the moldability, heat resistance, impact resistance, and peel resistance. The average particle size of the dispersed phase is preferably 1 μm or less, more preferably 700 nm or less, further preferably 500 nm or less, particularly preferably 100 nm or less, and most preferably 70 nm or less. This phase structure can be confirmed by observation using a scanning electron microscope (SEM) or transmission electron microscope (TEM). In the present invention, the phase structure should be confirmed at a magnification of 10,000 using a TEM. Is preferred. In addition, as a method of observing the phase structure with an electron microscope, in order to clearly observe the phase structure, it is possible to perform pretreatment using various known methods such as an ultrathin section method, an ion etching method, and an electron staining method. Good.

  In the present invention, the blending ratio of (A) polylactic acid resin and (B) polyolefin resin is not particularly limited, but the total amount of (A) polylactic acid resin and (B) polyolefin resin is 100 parts by weight. The (A) polylactic acid-based resin is 1 to 99 parts by weight, preferably 1 to 80 parts by weight, and 1 to 60 parts by weight from the viewpoints of moldability, heat resistance, impact resistance and peel resistance. 1 to 40 parts by weight is more preferred, and (B) the polyolefin-based resin is 99 to 1 part by weight, from the viewpoint of moldability, heat resistance, impact resistance and peel resistance, 99 to 20 parts by weight. Part is preferable, 99 to 40 parts by weight is more preferable, and 99 to 60 parts by weight is further preferable.

  In the present invention, it is preferable to blend 1 to 50 parts by weight of (D) conjugated diene polymer, with the total amount of (A) polylactic acid resin and (B) polyolefin resin being 100 parts by weight. (D) By adding a conjugated diene polymer, the compatibility of (A) polylactic acid resin and (B) polyolefin resin can be improved, and moldability, peel resistance, and impact resistance are improved. A resin composition having excellent heat resistance can be obtained.

  In the present invention, the (D) conjugated diene polymer includes a conjugated diene homopolymer, a copolymer of a conjugated diene and a compound copolymerizable with the conjugated diene, or a hydrogenated copolymer thereof. Either may be used, but in terms of excellent moldability, heat resistance, impact resistance, peel resistance, paintability and surface hardness, a copolymer of a conjugated diene and a compound copolymerizable with conjugated diene, or Those hydrogenated copolymers are preferred, and block and conjugated diene copolymerized with conjugated diene as the main component in terms of excellent moldability, heat resistance, impact resistance, peel resistance, paintability and surface hardness. A block copolymer containing a block mainly composed of a possible compound or a hydrogenated block copolymer thereof is more preferable, in that it is particularly excellent in moldability, heat resistance, impact resistance and peel resistance. , Conjugate It is a block copolymer in which a block containing ene as a main component exists on the inside and a block containing a compound copolymerizable with a conjugated diene as a main component on the outside, or a hydrogenated block copolymer thereof. Is more preferable.

  In the present invention, conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl- Examples include 1,3-octadiene, 1,3-hexadiene, 1,3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene, and chloroprene. These can be used alone or in combination of two or more, and in general, 1,3-butadiene, isoprene or a combination thereof is preferably used.

  In the present invention, the compound copolymerizable with the conjugated diene is preferably a compound having a vinyl unit, and preferably a compound having an aromatic vinyl unit in terms of moldability and heat resistance, such as styrene, o- Methylstyrene, p-methylstyrene, p-ethylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine, and the like can be used, and one or more of these can be used. Generally, styrene or p-tert-butylstyrene, α- Methylstyrene or a combination thereof is preferably used.

  In the present invention, the (D) conjugated diene polymer is preferably a copolymer of a conjugated diene unit and a vinyl unit or a hydrogenated copolymer thereof in terms of moldability and heat resistance. More preferred are copolymers of system units and aromatic vinyl units or hydrogenated copolymers thereof. Specific examples include styrene / butadiene random copolymers, styrene / butadiene block copolymers, styrene / butadiene / Styrene block copolymer (SBS), styrene / isoprene random copolymer, styrene / isoprene block copolymer, styrene / isoprene / styrene block copolymer (SIS), polybutadiene grafted with styrene, butadiene / Acrylonitrile copolymer, styrene / butadiene / butylene / styrene Lock copolymer (SBBS), Styrene / ethylene / butylene / styrene block copolymer (SEBS), Styrene / ethylene / propylene block copolymer (SEP), Styrene / ethylene / propylene / styrene block copolymer (SEPS) And styrene / ethylene / ethylene / propylene / styrene block copolymer (SEEPS). Especially, it is preferable that it is 1 or more types selected from SBS, SIS, SBBS, SEBS, SEP, SEPS, and SEEPS at the point which is excellent in a moldability, heat resistance, impact resistance, and peeling resistance, SBBS, SEBS More preferably, one or more selected from SEPS, SEEPS, more preferably one or more selected from SBBS, SEBS, SEPS, and most preferably SBBS and / or SEBS.

  In the present invention, when the (D) conjugated diene polymer is a copolymer of a conjugated diene unit and a vinyl unit, or a hydrogenated copolymer thereof, moldability, heat resistance, impact resistance In terms of excellent peeling resistance, the vinyl unit is preferably an aromatic vinyl unit, and more preferably styrene. In addition, the vinyl unit is preferably 1 to 50% by weight in terms of particularly excellent balance of moldability, heat resistance, impact resistance and peel resistance, and 5 to 40% by weight in terms of excellent peelability. Is more preferable, and is more preferably 10 to 35% by weight in terms of excellent moldability and heat resistance.

  In the present invention, the (D) conjugated diene polymer preferably includes (D-1) a conjugated diene polymer having an MFR of more than 30 g / 10 min at 230 ° C. and a 21.2N load condition. In terms of excellent heat resistance, impact resistance and peel resistance, the MFR is preferably 50 g / 10 min or more, more preferably 100 g / 10 min or more, and 125 g / 10 min or more. More preferably, it is most preferably 150 g / 10 min or more. A preferable upper limit of MFR is 300 g / 10 minutes.

  In the present invention, the (D) conjugated diene polymer preferably includes (D-1) a conjugated diene polymer having an MFR of more than 30 g / 10 min at 230 ° C. and a 21.2N load condition. -1) alone, or as other components, a conjugated diene polymer having an MFR of 30 g / 10 min or less may be used in combination.

  In the present invention, it is also preferable to include (D-2) a conjugated diene polymer modified with a polar functional group as the (D) conjugated diene polymer. Examples of polar functional groups include acid anhydride groups, carboxyl groups, amino groups, imino groups, alkoxysilyl groups, silanol groups, silyl ether groups, hydroxyl groups, and epoxy groups. An amino group and / or an imino group are preferable from the viewpoint of excellent impact resistance and peel resistance, and an imino group is more preferable from the viewpoint of excellent peel resistance. One or more of these functional groups can be used. (D-2) Although there is no restriction | limiting in particular in MFR of the conjugated diene polymer modified by the polar functional group, MFR in 230 degreeC and 21.2N load conditions is moldability, heat resistance, impact resistance, and peeling resistance. In terms of excellent properties, it is preferably more than 1 g / 10 minutes, more preferably 2 g / 10 minutes or more, and most preferably 3 g / 10 minutes or more. A preferable upper limit of MFR is 30 g / 10 minutes.

  In the present invention, (D-1) a conjugated diene polymer modified with the above-mentioned polar functional group may be used as the conjugated diene polymer having an MFR of more than 30 g / 10 minutes at 230 ° C. and 21.2 N load. Is possible.

  Thus, in the present invention, (D-1) it is preferable to include a conjugated diene polymer having an MFR of more than 30 g / 10 minutes at 230 ° C. and a 21.2N load condition. A conjugated diene polymer of 10 minutes or less and (D-2) a conjugated diene polymer modified with a polar functional group can be used in any combination.

  In the present invention, when (D) a conjugated diene polymer is blended, the most preferable combination is (D-1) not modified with a polar functional group (D-1) MFR at 230 ° C. and 21.2 N load condition is 30 g / 10. It is a combination of a conjugated diene polymer exceeding 20 minutes and a conjugated diene polymer modified with a polar functional group (D-2) having an MFR of 30 g / 10 minutes or less at 230 ° C. and a 21.2N load condition.

  In the present invention, the blending amount of the (D) conjugated diene polymer is excellent in moldability, heat resistance, impact resistance and peel resistance, and (A) a polylactic acid resin and (B) a polyolefin resin. 1 to 50 parts by weight is preferable, 3 to 30 parts by weight is more preferable, and 5 to 20 parts by weight is most preferable with respect to 100 parts by weight. (D) The proportion of the conjugated diene polymer in the conjugated diene polymer (D-1) having an MFR of more than 30 g / 10 min at 230 ° C. and 21.2N load may be 100% by weight. Any ratio may be used. Preferably, the component (D-1) in the (D) conjugated diene polymer is 10% by weight or more, and more preferably 30% by weight or more.

  In the present invention, (D-2) the conjugated diene polymer modified with a polar functional group may be in an arbitrary ratio, and preferably (D) occupies the conjugated diene polymer (D-2). ) Component is 10% by weight or more, more preferably 30% by weight or more.

  In the present invention, as a preferred embodiment, (D-1) a conjugated diene polymer that is not modified with a polar functional group (D-1) at 230 ° C. and 21.2N load condition exceeds 30 g / 10 minutes, and 230 ° C. When using in combination with (D-2) a conjugated diene polymer modified with a polar functional group having an MFR of 30 g / 10 min or less under a 21.2N load condition, the respective blending amounts are: (D) conjugated diene heavy Component (D-2) having an MFR of 20 to 80% by weight, 230 ° C., and 21.2N load condition, wherein the component (D-1) not modified with a polar functional group is 30 g / 10 min or less, based on the entire union Is preferably 80 to 20% by weight, more preferably 30 to 70% by weight of the component (D-1) not modified with a polar functional group, and an MFR of 30 at 230 ° C. and a 21.2N load condition of 30. / 10 minutes or less (D-2) component is 70 to 30 wt%.

  In the present invention, it is preferable to add (E) a phosphorus compound from the viewpoint of excellent thermal stability. (A) Polylactic acid resin may be thermally decomposed by heat history during melt kneading and melt molding. (E) Addition of phosphorus compound can suppress thermal decomposition and improve thermal stability. can do.

  In the present invention, the phosphorus compound (E) is not particularly limited, and examples thereof 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 phosphite compounds include “ADEKA STAB” C, PEP-4C, PEP-8, PEP-11C, PEP-24G, PEP-36, HP-10, 2112, 260, 522A, manufactured by ADEKA, 329A, 1178, 1500, C, 135A, 3010, TPP, “Irgaphos” 168, manufactured by Ciba Specialty Chemicals, “Sumilyzer” P-16, manufactured by Sumitomo Chemical, “Sand Stub” manufactured by Clariant, P-EPQ, “Weston” manufactured by GE 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. Acid phosphate and distearyl acid phosphate are preferred.

  Specific product names of phosphate compounds include “Irganox” MD1024 manufactured by Ciba Specialty Chemicals, “Inhibitor” OABH manufactured by Eastman Kodak, “Adeka Stub” AX-71 manufactured by ADEKA, and the like.

  In the present invention, the (E) phosphorus compound is preferably “ADEKA STAB” AX-71 (dioctadecyl phosphate), PEP-8 (distearyl pentaerythritol diphosphite), PEP-36 (cyclic neodylate) manufactured by ADEKA. Pentatetrayl bis (2,6-t-butyl-4-methylphenyl) phosphite), most preferably "ADK STAB" AX-71.

  In the present invention, the amount of the (E) phosphorus compound is not particularly limited, but (A) a polylactic acid resin and (B) in that it is excellent in moldability, heat resistance, impact resistance and peel resistance. It is preferable that it is 0.01-10 weight part with respect to 100 weight part of total amounts of polyolefin resin, More preferably, it is 0.05-8 weight part, More preferably, it is 0.1-5 weight part.

  In the present invention, the method of blending the (E) phosphorus compound is not particularly limited, and it can be used as a melt kneading method or a solvent above the melting point of the (A ′) polylactic acid resin precursor or the (A) polylactic acid resin. Although the method of removing a solvent after dissolving and mixing can be mentioned, (A ′) a polylactic acid resin precursor or (A) a polylactic acid resin in that it can be produced efficiently A method of melt kneading at or above the melting point is preferred. The melt-kneading method may be a batch method or a continuous method. As the apparatus, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a plastmill, a kneader, a stirring reactor equipped with a decompression device, or the like is used. It is preferable to use a single screw extruder or a twin screw extruder in that it can be kneaded efficiently and uniformly.

  In the present invention, (E) a method of blending a phosphorus compound includes (A ′) a method of blending together a polylactic acid resin precursor and (C) a chain extender, and (A) poly A method of blending together the lactic acid resin and the (B) polyolefin resin can be used.

  In the present invention, the kneading temperature in the case of blending (E) a phosphorus compound by a method of melt kneading at or above the melting point of (A ′) polylactic acid resin precursor or (A) polylactic acid resin is 150 to 270 ° C. The temperature is preferably 160 to 260 ° C, and most preferably 170 to 250 ° C.

  In the present invention, the pressure for compounding the (E) phosphorus compound may be any of reduced pressure, normal pressure and increased pressure, and the (E) phosphorus compound is converted into (A ′) polylactic acid resin precursor or (A) poly When blending by a method of melt-kneading at a melting point or higher of the lactic acid-based resin, it is preferable to reduce the pressure in that the generated gas at the time of melt-kneading can be removed.

  In this invention, when mixing in a solvent as a method of mix | blending (E) phosphorus type compound, the solvent in which a polymer and a monomer melt | dissolve is used. As the solvent, for example, chloroform, methylene chloride, tetrahydrofuran, hexafluoroisopropanol, acetonitrile and the like can be used. The method for removing the solvent when it is necessary to remove the solvent after mixing is not particularly limited. For example, the solvent is volatilized at room temperature and the solvent is volatilized at a temperature equal to or higher than the boiling point of the solvent under reduced pressure. Or the like can be used.

  In the present invention, (E) a phosphorus compound is blended, and (A) the molecular weight of the polylactic acid resin due to residence during melt kneading or injection molding is improved by improving the thermal stability of the polylactic acid resin. A thermoplastic resin composition having a favorable phase structure and excellent moldability, heat resistance, impact resistance and peel resistance can be obtained.

  Further, in the present invention, a polymer other than (D) a conjugated diene polymer may be contained. For example, an ethylene / vinyl acetate copolymer, an ethylene / (meth) acrylate copolymer, an acid anhydride An olefin resin containing at least one functional group selected from a physical group, a carboxyl group, an amino group, an imino group, an alkoxysilyl group, a silanol group, a silyl ether group, a hydroxyl group and an epoxy group, an acid anhydride group, Acrylic resin, ionomer resin, (B) polyolefin-based resin containing at least one functional group selected from a carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group Different from resin (F) ethylene / α-olefin copolymer and other thermoplastic resins, etc. From the viewpoint of effective impact resistance improvement, it is preferable to blend (F) an ethylene / α-olefin copolymer different from (B) the polyolefin-based resin.

  In the present invention, the (F) ethylene / α-olefin copolymer is a copolymer of ethylene and at least one of α-olefins having 3 or more carbon atoms, preferably 3 to 20 carbon atoms, Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1 -Pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl 1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof Can be mentioned. Among these α-olefins, copolymers using α-olefins having 3 to 12 carbon atoms are preferable from the viewpoint of improving mechanical strength, and in particular, from the viewpoint of excellent impact resistance, 1-butene and 1-hexene. Is preferred.

In the present invention, the density of (F) an ethylene / alpha-olefin copolymers, moldability, heat resistance, balance of impact resistance, preferably 860~900kg / ^{m 3,} more preferably 870~900kg / ^{m 3} Most preferably, it is 880 to 900 kg / m ³ .

  In the present invention, the MFR of the (F) ethylene / α-olefin copolymer has a MFR at 190 ° C. and 21.2 N of preferably 0.5 to 50 g / m 2 from the balance of moldability, heat resistance and impact resistance. 10 minutes, more preferably 1 to 40 g / 10 minutes, most preferably 2 to 30 g / 10 minutes.

  In the present invention, when blending (F) ethylene / α-olefin copolymer different from (B) polyolefin resin, the total amount of (A) polylactic acid resin and (B) polyolefin resin is 100 wt. As a part, 1-50 weight part is preferable, 3-40 weight part is more preferable, and 5-30 weight part is the most preferable.

  In the present invention, fillers, plasticizers, carboxyl group-reactive compounds different from (C) chain extenders, stabilizers (antioxidants, ultraviolet absorbers, etc.), lubricants, as long as the object of the present invention is not impaired. Release agents, flame retardants, colorants including dyes and pigments, crystal nucleating agents, antistatic agents, other thermoplastic resins, and the like can be added.

  In this invention, it is preferable to mix | blend a filler from the point that the thermoplastic resin composition excellent in mechanical characteristics, a moldability, heat resistance, etc. is obtained. As the filler, there can be used those in the form of fibers, plates, granules, and powders that are usually used as fillers for thermoplastic resins. Specifically, glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, calcium carbonate whisker, wollastonite, sepiolite, asbestos, slag fiber, Zonolite, elestadite, gypsum fiber, silica fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber and other inorganic fillers, glass flakes, non-swellable mica, graphite, metal foil, ceramic beads, Talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine powder silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, oxidation Luminium, titanium oxide, aluminum silicate, silicon oxide, plaster, novaculite, doughnite, white clay, and other inorganic fillers, polyester fiber, nylon fiber, acrylic fiber, cotton fiber, hemp fiber, bamboo fiber, wood fiber , Kenaf fiber, jute fiber, banana fiber, coconut fiber, animal fiber such as silk, wool, Angola, cashmere or camel, paper powder, wood powder, bamboo powder, cellulose powder, rice husk powder, fruit shell powder, chitin powder, chitosan Examples thereof include organic fillers in the form of fibers, powders or chips, such as powder, protein, starch, rice husk, wood chips, okara, waste paper pulverized material, and clothing pulverized material. Among these fillers, fibrous inorganic fillers, plate-like inorganic fillers, and organic fillers are preferable. In particular, glass fiber, wollastonite, aluminum borate whisker, potassium titanate whisker, calcium carbonate whisker, and talc. Mica, kaolin, hemp fiber, bamboo fiber, kenaf fiber, jute fiber, paper powder and wood powder are preferred. The aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more. These fillers can be used alone or in combination of two or more. The filler 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, and may be a coupling agent such as aminosilane or epoxysilane. It may be processed.

  In the present invention, the blending amount of the filler is preferably 0.5 to 300 parts by weight, preferably 1 to 150 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) polyolefin resin. Is more preferable.

  In the present invention, a plasticizer can also be blended from the viewpoint that a thermoplastic resin composition excellent in mechanical properties, moldability, heat resistance and the like can be obtained. As the plasticizer, generally well-known ones can be used. For example, polyalkylene glycol plasticizer, polyester plasticizer, polyvalent carboxylate plasticizer, glycerin plasticizer, phosphate ester Can include plasticizers, epoxy plasticizers, fatty acid amides such as stearamide, ethylenebisstearic acid amide, pentaerythritol, various sorbitols, polyacrylic esters, silicone oils and paraffins, and bleed-out resistance From the viewpoint of polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenol, bisphenol Polyalkylene glycols such as propylene oxide addition polymers of diols, tetrahydrofuran addition polymers of bisphenols, or terminal-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds. Plasticizers, polyvalent carboxylic acid esters such as bis (butyl diglycol) adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, acetyl tributyl citrate, methoxycarbonylmethyl dibutyl citrate, ethoxycarbonylmethyl dibutyl citrate Plasticizer, glycerol monoacetomonolaurate, glycerol diacetomonolaurate, glycerol monoacetomonostearate, glycerol Glycerin-based plasticizers such as acetoacetic monooleate and glycerol mono acetonate monomontanate are preferred. These plasticizers can be used alone or in combination of two or more.

  In the present invention, the blending amount of the plasticizer is preferably in the range of 0.01 to 50 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) polyolefin resin, A range of ˜20 parts by weight is more preferred.

  In the present invention, it is also preferable to add a carboxyl group-reactive compound different from the chain extender (C) from the viewpoint that the durability and toughness of the resulting thermoplastic resin composition can be further improved. (C) The carboxyl group-reactive compound different from the chain extender may be a compound having a structure different from that of the (C) chain extender and (A) a compound reactive with the carboxyl end group of the polylactic acid resin. Although not particularly limited, (A) it is more preferable if it is reactive with the carboxyl group of an acidic low molecular weight compound such as lactic acid or formic acid produced by thermal decomposition or hydrolysis of a polylactic acid resin. More preferably, the compound is also reactive with a hydroxyl group end group of an acidic low molecular weight compound produced by thermal decomposition. Examples of the carboxyl group-reactive compound different from the chain extender (C) include glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, glycidyl imide compounds, alicyclic epoxy compounds, epoxy group-containing compounds, 2, 2 Oxazoline compounds such as' -m-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), oxazine compounds, N, N'-di-2,6-diisopropylphenylcarbodiimide, 2 , 6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide, polycarbodiimide and other carbodiimide compounds are preferably used, and epoxy group-containing compounds and / or carbodiimide compounds are particularly preferable. For example, when the (C) chain extender is a polymer containing an epoxy group, a carbodiimide compound can be preferably used as a carboxyl group-reactive compound different from the (C) chain extender. As the carboxyl group-reactive compound different from (C) the chain extender, one or more compounds can be arbitrarily selected and used.

  In the present invention, the compounding amount of the carboxyl group-reactive compound different from (C) the chain extender is 0.01 with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) polyolefin resin. Is preferably 10 to 10 parts by weight, and more preferably 0.05 to 5 parts by weight.

  In the present invention, it is preferable to further add a reaction catalyst of a carboxyl group-reactive compound different from (C) the chain extender. The reaction catalyst here has an effect of promoting the reaction between a carboxyl group-reactive compound different from (C) the chain extender and (A) the terminal of the polylactic acid-based resin or the carboxyl group of the acidic low-molecular compound. Preferably, the compound is a compound that has the effect of accelerating the reaction with a small amount of addition, and (C) the reaction catalyst of the carboxyl group-reactive compound different from the chain extender is an acidic low-molecular compound produced by thermal decomposition. It is also preferable to have an effect of promoting a reaction with a hydroxyl group. As such a reaction catalyst, for example, an alkali metal compound, an alkaline earth metal compound, and a phosphate ester are preferable. The addition amount of the reaction catalyst is not particularly limited, but is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) polyolefin resin, 0.01-0.2 weight part is more preferable, and 0.02-0.1 weight part is the most preferable.

In the present invention, it may be appropriately reacted with a carboxyl end group or an acidic low molecular weight compound depending on the application to be used. Specific (A) the terminal of the polylactic acid resin or the carboxyl group of the acidic low molecular weight compound or The degree of reactivity with the hydroxyl group is preferably such that the acid concentration in the resin composition is 10 equivalents / 10 ⁶ g or less from the viewpoint of hydrolysis resistance, and 5 equivalents / 10 ⁶ g. The reaction is more preferably carried out so that it is less than or equal to 1 equivalent / 10 ⁶ g or less. The acid concentration in the resin composition can be measured by dissolving the resin composition in an appropriate solvent and then titrating with an alkaline compound solution with a known concentration such as sodium hydroxide or nuclear magnetic resonance (NMR). it can.

  The method for producing the thermoplastic resin composition of the present invention is not particularly limited as long as it satisfies the requirements specified in the present invention. For example, (A) polylactic acid resin, (B) polyolefin resin and necessary Depending on the conditions, other additives may be preferably used, such as a method of uniformly melting and kneading using a single screw or twin screw extruder or a method of volatilizing and removing the solvent after mixing in a solution. A method of uniformly melting and kneading using a screw or twin screw extruder can be more preferably used.

In the present invention, as a method of melt-kneading using a single-screw or twin-screw extruder, in order to obtain a thermoplastic resin composition having a preferred phase structure, (A ′) a polylactic acid-based resin precursor, A ′) 0.01-3 parts by weight of (C) chain extender was melt-kneaded with 100 parts by weight of polylactic acid resin precursor (A) to obtain a polylactic acid resin, and then MFR _A / MFR _B However, a method of melt kneading (A) a polylactic acid resin and (B) a polyolefin resin that are 0.01 or more and less than 0.1 is preferable. As a specific production method, for example, (A ′) a polylactic acid resin precursor and (A ′) 100 parts by weight of a polylactic acid resin precursor are preliminarily provided with 0.01 to 3 parts by weight of (C) a chain extender. (A) polylactic acid-based resin pellets obtained by melting and kneading with an extruder (A), wherein the MFR _A / MFR _B is 0.01 or more and less than 0.1. B) Method of supplying polyolefin resin from the main feeder of the extruder and melt-kneading, (A ′) polylactic acid resin precursor and (A ′) 100 parts by weight of polylactic acid resin precursor from the main feeder of the extruder (C) 0.01-3 parts by weight of a chain extender is supplied, (B) a polyolefin-based resin is supplied from a side feeder installed in the middle of the extruder, and the MFR _A / MFR _B is 0.01 Above, it becomes less than 0.1 (A) polylactic acid type Examples thereof include a method of melt-kneading a resin and (B) a polyolefin-based resin.

In the present invention, when producing a thermoplastic resin composition by a melt kneading method using a single screw or twin screw extruder, (D) a conjugated diene polymer, (E) a phosphorus compound, ( F) When blending an ethylene / α-olefin copolymer and other additives, they can be blended at any location, but preferably (A ′) a polylactic acid resin precursor and (A ′) poly after obtaining the pellets of the lactic acid based on the resin precursor 100 parts by weight of (C) a chain extender 0.01-3 parts by weight melt-kneaded in advance to the extruder (a) polylactic acid resin, the MFR _a / MFR _B is 0.01 or more and less than 0.1 (A) polylactic acid resin and (B) polyolefin resin, optionally (D) conjugated diene polymer, (E) phosphorus compound, ( F) Ethylene / α-olefin copolymer and its A method of supplying an additive from a main feeder of an extruder and melt-kneading (two-stage kneading method 1), (A ′) a polylactic acid resin precursor, and (A ′) 100 parts by weight of a polylactic acid resin precursor On the other hand, (C) 0.01 to 3 parts by weight of a chain extender and optionally (E) a phosphorus compound was previously melt-kneaded with an extruder to obtain (A) a polylactic acid resin pellet, and then the MFR _A / MFR _B is 0.01 or more and less than 0.1 (A) polylactic acid resin and (B) polyolefin resin, optionally (D) conjugated diene polymer, (F) ethylene / α-olefin A method in which a copolymer and other additives are supplied from a main feeder of an extruder and melt-kneaded (two-stage kneading method 2), (A ') a polylactic acid resin precursor and (A') from the main feeder of the extruder For 100 parts by weight of polylactic acid resin precursor C) 0.01 to 3 parts by weight of a chain extender and optionally (E) a phosphorus compound, (B) a polyolefin resin, optionally (D) a conjugated diene polymer, (F) ethylene / α- The olefin copolymer and other additives are supplied from a side feeder installed in the middle of the extruder, and the MFR _A / MFR _B is 0.01 or more and less than 0.1 (A) a polylactic acid resin and ( B) Method of melt kneading polyolefin resin (side feed kneading method 1), from main feeder of extruder (A ′) polylactic acid resin precursor and (A ′) 100 parts by weight of polylactic acid resin precursor (C) Supplying 0.01 to 3 parts by weight of a chain extender and optionally (D) a conjugated diene polymer, (E) a phosphorus compound, (B) a polyolefin resin, optionally (F) ethylene / α -I A fin copolymer and other additives are supplied from a side feeder installed in the middle of the extruder, and the MFR _A / MFR _B is 0.01 or more and less than 0.1 (A) a polylactic acid resin and ( B) A thermoplastic resin composition can be produced by a method of melt-kneading polyolefin resin (side feed kneading method 2).

In the present invention, when the thermoplastic resin composition is produced by the side feed kneading method 1 or the side feed kneading method 2, the MFR _A is supplied from a side feeder installed in the middle of the extruder (B ) Melt flow rate at 190 ° C. and 21.2N load condition of (A) polylactic acid resin before being kneaded with polyolefin resin. As a measuring method thereof, for example, (B) polyolefin resin is used. Using an extruder equipped with a sampling valve in front of the side feeder to be supplied (main feeder side), (A) measuring the melt flow rate of polylactic acid resin sampled from the sampling valve at 190 ° C and 21.2N load From the main feeder that supplies the polylactic acid resin precursor (A ′) and (B ′) Using another extruder with equal L / D (L: Extruder screw length, D: Extruder screw diameter) to the side feeder that supplies the olefin resin, (A) Polylactic acid resin is manufactured in advance. A method for measuring the melt flow rate of the produced (A) polylactic acid-based resin at 190 ° C. under a 21.2N load condition may be used. In the side feed kneading method 2, (C) chain extender 0.01 with respect to 100 parts by weight of (A ′) polylactic acid resin precursor and (A ′) polylactic acid resin precursor from the main feeder of the extruder. Since -3 parts by weight and optionally (D) a conjugated diene polymer is supplied, it is necessary to remove (D) the conjugated diene polymer when measuring MFR _A. In this case, as a method of removing (D) the conjugated diene polymer, for example, (A) a solvent in which the polylactic acid resin is soluble and (D) the conjugated diene polymer is unnecessary (for example, hexafluoroisopropanol). Etc.), (A) Melt flow rate of polylactic acid resin obtained by dissolving only polylactic acid resin and volatilizing the solvent from the solution at 190 ° C. and 21.2 N load condition Measure.

  In the present invention, when a thermoplastic resin composition is produced by a melt kneading method using a single-screw or twin-screw extruder, the L / D of the extruder is as long as the requirements specified in the present invention are satisfied. Although there is no restriction | limiting in particular, Preferably it is 20-100, More preferably, it is 25-80, Most preferably, it is 30-70. In addition, when manufacturing a thermoplastic resin composition by the side feed kneading method 1 or the side feed kneading method 2, the position of the side feeder installed in the middle of the extruder is not particularly limited as long as it satisfies the requirements specified in the present invention. Although the L / D of the extruder is 100%, the position is preferably 30% to 95% from the main feeder, more preferably 40% to 92% from the main feeder, most preferably 50% to 90%. Position.

  In the present invention, when a thermoplastic resin composition is produced by a melt kneading method using a single screw or twin screw extruder, the melt kneading temperature is (A) a polylactic acid resin and (B) a polyolefin resin. Although there will be no restriction | limiting in particular if it is more than melting | fusing point of resin, 170-270 degreeC is preferable, 180 degreeC-260 degreeC is more preferable, 190-250 degreeC is especially preferable.

  The thermoplastic resin composition of the present invention can be formed into a molded product by various known molding methods. As the molding method, injection molding, extrusion molding, press molding, blow molding and the like are preferable, and particularly useful by processing into various molded products such as injection molded products, extrusion molded products, press molded products and blow molded products. It can also be used as a sheet, film, fiber, or the like.

  In the present invention, when injection molding is selected as the molding method, the mold temperature is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and more preferably 70 ° C. or higher in terms of heat resistance, moldability and appearance. Is more preferable, and is preferably 120 ° C. or lower, more preferably 99 ° C. or lower, and further preferably 90 ° C. or lower from the viewpoint that deformation of the test piece can be suppressed.

  Molded products made of the thermoplastic resin composition of the present invention include automobile parts (interior / exterior parts, etc.), electrical / electronic parts (various housings, gears, gears, etc.), home appliance parts, building members, civil engineering members, agricultural materials. And can be used for various purposes such as daily necessities. Specifically, air flow meter, air pump, thermostat housing, engine mount, ignition hobbin, ignition case, clutch bobbin, sensor housing, idle speed control valve, vacuum switching valve, ECU housing, vacuum pump case, inhibitor switch, rotation sensor, Accelerometer, Distributor cap, Coil base, Actuator case for ABS, Top and bottom of radiator tank, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer, Distribution Turcap, vapor canister housing Air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, automotive underhood parts, torque control levers, safety belt parts, register blades , Washer lever, window regulator handle, window regulator handle knob, passing light lever, sun visor bracket, various motor housings, spare tire covers, console box, finish plate, cowl side rim, scuff plate, pillar, tool box, door trim, etc. Automotive interior parts, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, hoodles Represented by various automotive connectors such as bars, wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles and other automotive exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, etc. Car parts. Also, notebook computer housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile personal computers and handheld mobiles, recording media (CD, DVD, PD, FDD) Etc.) Electrical and electronic parts represented by drive housings and internal parts, copier housings and internal parts, facsimile housings and internal parts, parabolic antennas and the like. Furthermore, audio equipment parts such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video cameras, audio / laser discs (registered trademark) / compact discs, lighting parts, refrigerator parts, Examples include home and office electrical product parts such as air conditioner parts, typewriter parts, and word processor parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, motor cases, switches, capacitors, variable capacitors Case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor Electric and electronic parts such as brush holders, transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels , Heat insulation walls, adjusters, plastic bundles, ceiling fishing gear, stairs, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other fishery related parts, vegetation nets, vegetation mats, grass bags, Weed prevention net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dehydration bag, concrete formwork and other civil engineering related members, gears, screws, springs, bearings, levers, key stems, Cams, ratchets, rollers, water supply parts, toy parts, fans, tegs, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, clocks, and other mechanical parts, multi-films, tunnel films, bird seats, vegetation Nonwoven fabric for protection, pot for seedling, vegetation pile, seed string tape, germination sheet, house lining sheet, agricultural PVC film stopper, slow-release fertilizer, root prevention , Garden net, insect net, infant tree net, print laminate, fertilizer bag, sample bag, sandbag, animal damage prevention net, inducement string, wind net, etc., paper diaper, sanitary wrapping material, cotton swab, towel , Hygiene items such as toilet seat wipes, medical non-woven fabrics (stitching reinforcements, anti-adhesion membranes, prosthetic repair materials), wound dressings, wound tape bandages, sticker base fabrics, surgical sutures, fracture reinforcements, medical Medical supplies such as film, calendar, stationery, clothing, food, cosmetics packaging film, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, bottles, baskets, etc. Tableware, hot fill containers, microwave cooking containers, cosmetic containers, wraps, foam buffer, paper laminar, detergent / shampoo bottles, beverage bottles, cups Wrapping, candy packaging, shrink labels, lid materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, electrical / electronic parts, etc. Containers and packaging for films, natural fiber composites, polo shirts, T-shirts, innerwear, uniforms, sweaters, socks, ties, and other clothing, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki Goods, carrier tape, print lamination, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, nonwoven fabric, hot melt binder, magnetic material , Zinc sulfide, electrode materials, etc. Binder, optical element, conductive embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage filter, clear file, coating agent It is useful as an adhesive, bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter and so on.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, these do not limit this invention. Moreover, the raw material used and the code | symbol in a table | surface are shown below.

(A ′) Polylactic acid resin precursor (A′-1) Poly L lactic acid resin (D body 1.2%, Mw (PMMA conversion) 220,000, melting point 168 ° C., MFR = 3.0 g / 10 min (190 ° C, 21.2N))
(A'-2) Poly L-lactic acid resin (D body 1.2%, Mw (PMMA conversion) 160,000, melting point 168 ° C., MFR = 13.5 g / 10 min (190 ° C., 21.2 N))
(A′-3) Poly L lactic acid resin (“H400” manufactured by Mitsui Chemicals, 1.3% D, Mw (PMMA conversion) 200,000, melting point 167 ° C., MFR = 3.2 g / 10 min (190 ° C., 21.2N))
(A′-4) Poly L lactic acid resin (“H100” manufactured by Mitsui Chemicals, D-form 1.3%, Mw (converted to PMMA) 160,000, melting point 167 ° C., MFR = 13.7 g / 10 min (190 ° C., 21.2 N)).

(C) Chain extender (C-1) Epoxy group-containing styrene / acrylic acid ester copolymer ("JONCRYL ADR-4368" manufactured by BASF, Mw (PMMA conversion) 8,000, epoxy equivalent 285 g / mol)
(C-2) Epoxy group-containing styrene / acrylic acid ester copolymer ("ARUFON UG-4030" manufactured by Toagosei Co., Ltd., Mw (PMMA conversion) 11,000, epoxy equivalent 556 g / mol)
(C-3) Polycarbodiimide (Nisshinbo's "HMV-8CA", carbodiimide equivalent 278 g / mol)
(C-4) Epoxy group-containing olefinic copolymer (Sumitomo Chemical "bond first E", epoxy equivalent 1176 g / mol)
(C-5) Epoxy group-containing olefin-based copolymer (“MODIPA A4200” manufactured by NOF Corporation, epoxy equivalent 943 g / mol).

(B) Polyolefin resin (B-1) Polypropylene resin (homopolymer, “J108M” manufactured by Prime Polymer, MFR = 18.4 g / 10 min (190 ° C., 21.2 N), MFR = 45 g / 10 min (230 ° C. 21.2 N), melting point 169 ° C.)
(B-2) Polypropylene resin (Homopolymer, Prime Polymer “S119”, MFR = 25.1 g / 10 min (190 ° C., 21.2 N), MFR = 60 g / 10 min (230 ° C., 21.2 N), Melting point 169 ° C)
(B-3) Polypropylene resin (block polymer, “J708UG” manufactured by Prime Polymer, MFR = 20.2 g / 10 min (190 ° C., 21.2 N), MFR = 45 g / 10 min (230 ° C., 21.2 N), Melting point 169 ° C)
(B-4) Polypropylene resin (Random polymer, “MG03B” manufactured by Nippon Polypro, MFR = 12.2 g / 10 min (190 ° C., 21.2 N), MFR = 30 g / 10 min (230 ° C., 21.2 N), Melting point 159 ° C)
(B-5) Polypropylene resin (Random polymer, “MG05ES” manufactured by Nippon Polypro, MFR = 14.8 g / 10 min (190 ° C., 21.2 N), MFR = 45 g / 10 min (230 ° C., 21.2 N), Melting point 159 ° C)
(B-6) Polypropylene resin (Random polymer, “J229E” made by prime polymer, MFR = 22.4 g / 10 min (190 ° C., 21.2 N), MFR = 50 g / 10 min (230 ° C., 21.2 N), Melting point 159 ° C)
(B-7) Polypropylene resin (homopolymer, “J106G” manufactured by Prime Polymer, MFR = 6.4 g / 10 min (190 ° C., 21.2 N), MFR = 15 g / 10 min (230 ° C., 21.2 N), Mp 169 ° C).

(D) Conjugated diene polymer (D-1) Conjugated diene polymer (D-1-1) SEBS (manufactured by Asahi Kasei Chemicals "Tuftec H1031" with an MFR exceeding 30 g / 10 min at 230 ° C and 21.2N load condition ”Styrene content 30 wt%, MFR = 150 g / 10 min (230 ° C., 21.2 N))
(D-1-2) SEPS (Kuraray “Septon 2002”, styrene content 30% by weight, MFR = 70 g / 10 min (230 ° C., 21.2 N))
(D-1-3) SBBS (“Tough Tech P1500” manufactured by Asahi Kasei Chemicals Co., Ltd., styrene content 30% by weight, MFR = 35 g / 10 min (230 ° C., 21.2 N)).

(D-2) Conjugated diene polymer modified with a polar functional group (D-2-1) Imino group-modified SEBS ("Tough Tech MP10" manufactured by Asahi Kasei Chemicals Co., Ltd., styrene content 30% by weight, MFR = 4 g / 10 min (230 ° C, 21.2N))
(D-2-2) Amino group-modified SEBS (“Dynalon 8630P” manufactured by JSR, styrene content 15% by weight, MFR = 15 g / 10 min (230 ° C., 21.2 N))
(D-2-3) Acid anhydride-modified SEBS (“Tuftec M1913” manufactured by Asahi Kasei Chemicals, styrene content 30% by weight, MFR = 5 g / 10 min (230 ° C., 21.2 N)).

(D-3) Conjugated diene polymer (D-3-1) SEBS ("Tuftec H1041" manufactured by Asahi Kasei Chemicals Co., Ltd.) having an MFR of 30 g / 10 min or less at 230 ° C and 21.2N load condition, styrene content 30 wt% , MFR = 5 g / 10 min (230 ° C., 21.2 N)).

(E) Phosphorus compound (E-1) Phosphate compound (“ADEKA STAB AX-71” manufactured by ADEKA)
(E-2) Phosphite compound (“ADEKA STAB PEP-8” manufactured by ADEKA).

(F) Ethylene / α-olefin copolymer (F-1) Ethylene / 1-butene (“Tafmer A-35070S” manufactured by Mitsui Chemicals, density 870 kg / m ³ , MFR = 35 g / 10 min (190 ° C., 21. 2N))
(F-2) Ethylene / 1-hexene (“Excellen CX4002” manufactured by Sumitomo Chemical Co., Ltd., density 880 kg / m ³ , MFR = 8 g / 10 min (190 ° C., 21.2 N))
(F-3) Ethylene / 1-butene (“Tafmer A-4085S” manufactured by Mitsui Chemicals, density 885 kg / m ³ , MFR = 3.6 g / 10 min (190 ° C., 21.2 N)).

(G) Filler (G-1) Talc ("P-6" manufactured by Nippon Talc).

(H) (C) A carboxyl group-reactive compound different from the chain extender (H-1) polycarbodiimide (“Carbodilite LA-1” manufactured by Nisshinbo).

  The measurement methods and determination methods used in the examples and comparative examples of the present invention are shown below.

(1) Heat resistance (low load DTUL)
According to ISO75, the deflection temperature under load (load 0.45 MPa) of a molded product having a length of 80 mm, a width of 10 mm and a thickness of 4 mm was measured by a flatwise method.

(2) Impact resistance (Charpy impact strength)
According to ISO179-1, the Charpy impact strength at 23 ° C. of a molded product having a notch length of 80 mm × width of 10 mm × thickness of 4 mm was measured.

(3) Impact resistance (Fracture mode in high-speed surface impact test)
A high-speed surface impact test (speed: 1 m / s) of a molded product of 10 mm × 10 mm × 3 mm was performed according to ASTM D3763-2 using “SURVOPULSER” manufactured by Shimadzu, and the determination was made according to the following criteria.
○: Ductile fracture △: Slightly ductile fracture ×: Brittle fracture.

(4) Peeling resistance Three square plate molded products of 10 mm × 10 mm × 3 mm were prepared. In the vicinity of the part, 100 square grid cuts were made with a cutter knife at intervals of 1 mm, cellophane tape was adhered onto the grid, and was peeled off at an angle of 90 ° with respect to the square plate surface. Thereafter, the state of the surface of the molded product was observed, the squares peeled in a total of 300 squares were measured, and judged according to the following criteria.
0: No peeling 1: Peeling 5% or less 2: Peeling 5-15% or less 3: Peeling 15-30% or less 4: Peeling 35-50% or less 5: Peeling 50% or more.

  Further, the same evaluation was performed on a 10 mm × 10 mm × 3 mm square plate molded product obtained by injecting molding after retaining in a molding machine for 30 minutes.

[Examples 1, 2, 4 and Comparative Examples 1-7]
Kneading method: Side feed kneading method 1 (X-1)
In the composition shown in Table 1 and Table 2, (A ′) polylactic acid resin precursor or (A ′) polylactic acid resin precursor and (C) chain extender were blended, cylinder diameter 30 mm, L / D = Raw material is charged from the main feeder of a twin-screw extruder with a 45.5 sampling valve (TEX30XSSST manufactured by Nippon Steel Works), melt kneaded under conditions of a cylinder temperature of 230 ° C. and a rotation speed of 200 rpm, and the position of L / D = 35 (B) The polyolefin resin is introduced from the side feeder provided in Table 1 and Table 2 and the strand discharged from the discharge port is cooled by a water-cooled cooling bath and then pelletized by a pelletizer. A thermoplastic resin composition was obtained. At that time, a molten sample of (A) polylactic acid resin was collected from a sampling valve of an extruder provided in front of the side feeder (main feeder side), and (A-1-1) polylactic acid resin (Example) 1), (A-1-2) polylactic acid resin (Example 2), (A-2-1) polylactic acid resin (Example 4), (A-1-4) polylactic acid resin (comparison) Examples 1, 2), (A-2-2) Polylactic acid resin (Comparative Example 3), (A-1-5) Polylactic acid resin (Comparative Example 4), (A-1-6) Polylactic acid Resin (Comparative Example 5), (A-2-3) Polylactic acid resin (Comparative Example 6), (A-1-7) Melt of polylactic acid resin (Comparative Example 7) at 190 ° C. and 21.2 N load The flow rate (MFR _A ) was measured. (B) Table 1 and Table 2 show the results of melt flow rate (MFR _B ) and MFR _A / MFR _B at 190 ° C. and 21.2 N load for polyolefin resins.

  The obtained thermoplastic resin composition is injection molded at a cylinder temperature of 210 ° C. and a mold temperature of 80 ° C. using an injection molding machine (FKS80 manufactured by Komatsu) for evaluation of heat resistance, impact resistance and peel resistance. The molded article was obtained and evaluated as shown in the above (1) to (4). The results are shown in Tables 1 and 2.

[Example 3]
Kneading method: Two-stage kneading method (Y-1)
In the composition shown in Table 1, (A ′) a polylactic acid resin precursor and (C) a chain extender were blended, and a cylinder diameter 30 mm, L / D = 35 twin screw extruder (TEX30α manufactured by Nippon Steel) Raw materials were charged from the main feeder and melt kneaded under the conditions of a cylinder temperature of 230 ° C. and a rotation speed of 200 rpm. The obtained (A-1-3) polylactic acid-based resin and (B) polyolefin-based resin were twin-screw extruded with a sampling valve having a cylinder diameter of 30 mm and L / D = 45.5 so as to have the composition shown in Table 1. Raw material from the main feeder of the machine (Nippon Steel Works TEX30XSSST), melt kneading under the conditions of a cylinder temperature of 230 ° C. and a rotation speed of 200 rpm, the strand discharged from the discharge port is cooled by a water-cooled cooling bath, and then the pelletizer To obtain a thermoplastic resin composition. As in Example 1, Table 1 shows the evaluation results shown in MFR _A , MFR _B , MFR _A / MFR _B, and (1) to (4) above.

[Examples 5, 6, 8-14 and Comparative Examples 8-14]
Kneading method: Side feed kneading method 2 (X-2)
In the composition shown in Table 1 and Table 2, (A ′) polylactic acid resin precursor, (D) conjugated diene polymer, (E) phosphorus compound, or (A ′) polylactic acid resin precursor, (C) Chain extender, (D) Conjugated diene polymer, (E) Phosphorus compound, twin diameter extruder with sampling valve with cylinder diameter 30mm, L / D = 45.5 (manufactured by Nippon Steel Works) The raw materials are charged from the main feeder of TEX30XSSST), melt kneaded under the conditions of a cylinder temperature of 230 ° C. and a rotational speed of 200 rpm, and from the side feeder provided at the position of L / D = 35, the compositions shown in Table 1 and Table 2 As such, (B) a polyolefin resin, (G) an inorganic filler, (H) (C) a carboxyl group-reactive compound different from the chain extender is charged, and the strand discharged from the discharge port is cooled by water cooling. bus After cooling, it was pelleted by a pelletizer to obtain a thermoplastic resin composition. At that time, a mixed molten sample of (A) polylactic acid resin and (D) conjugated diene polymer was sampled from a sampling valve of an extruder provided in front of the side feeder (main feeder side), and hexadiene as a solvent. After dissolving in fluoroisopropanol and removing insoluble matter ((D) conjugated diene polymer), the solvent was volatilized from the solution, and (A-1-8) polylactic acid resin (Examples 5, 6, 9 to 11, 14), (A-2-4) Polylactic acid resin (Example 8), (A-1-9) Polylactic acid resin (Example 12), (A-1-10) Polylactic acid resin (Example 13), (A-1-11) Polylactic acid resin (Comparative Examples 8, 9, 11-14), (A-2-5) Polylactic acid resin (Comparative Example 10) at 190 ° C., 21 The melt flow rate (MFR _A ) at 2N load was measured. (B) Table 1 and Table 2 show the results of melt flow rate (MFR _B ) and MFR _A / MFR _B at 190 ° C. and 21.2 N load of the polyolefin-based resin and the evaluation results shown in the above (1) to (4). Shown in

[Example 7]
Kneading method: Two-stage kneading method (Y-1)
(A ') Polylactic acid resin precursor, (C) Chain extender, and (E) Phosphorus compound are blended in the composition shown in Table 1, and a twin-screw extruder with a cylinder diameter of 30 mm and L / D = 35 ( Raw materials were charged from the main feeder of TEX30α manufactured by Nippon Steel Works, and melt kneading was performed under conditions of a cylinder temperature of 230 ° C. and a rotation speed of 200 rpm. The obtained (A-1-12) polylactic acid resin, (B) polyolefin resin, and (D) conjugated diene polymer had a cylinder diameter of 30 mm and L / D = 45 so as to have the composition shown in Table 1. The raw material is charged from the main feeder of a twin screw extruder with a sampling valve (TEX30XSSST manufactured by Nippon Steel), melt kneaded under the conditions of a cylinder temperature of 230 ° C. and a rotation speed of 200 rpm, and the strand discharged from the discharge port After cooling with a water-cooled cooling bath, it was pelletized with a pelletizer to obtain a thermoplastic resin composition. As in Example 1, Table 1 shows the evaluation results shown in MFR _A , MFR _B , MFR _A / MFR _B, and (1) to (4) above.

From Examples 1 to 4 and Comparative Examples 1 to 7, MFR _A / MFR _B is 0.01 or more and less than 0.1, and (A) a polylactic acid resin and (B) a polyolefin resin are blended. It can be seen that the thermoplastic resin composition is excellent in heat resistance, impact resistance and peel resistance. Moreover, it turns out that it is further excellent in heat resistance, impact resistance, and peeling resistance by mix | blending a conjugated diene type polymer from Example 5. Moreover, from Examples 6 to 13, it can be seen that the peel resistance is remarkably improved by further adding a phosphorus compound.

[Examples 16, 19, and 23]
Kneading method: Side feed kneading method 1 (X-1)
With composition shown in Table 3, (A ′) polylactic acid resin precursor, (C) chain extender, (E) phosphorus compound, blended with a sampling valve with a cylinder diameter of 30 mm and L / D = 45.5 Raw materials are charged from the main feeder of a twin screw extruder (TEX30XSSST manufactured by Nippon Steel), melt kneading is performed at a cylinder temperature of 230 ° C. and a rotation speed of 200 rpm, and from a side feeder provided at a position of L / D = 35, (B) polyolefin resin, (D) conjugated diene polymer, (F) ethylene / α-olefin copolymer, (G) inorganic filler, (H) (C) ) A carboxyl group-reactive compound different from the chain extender is charged, and the strand discharged from the discharge port is cooled by a water-cooled cooling bath and then pelletized by a pelletizer to obtain a thermoplastic resin composition. . At that time, (A) a molten sample of polylactic acid resin was collected from a sampling valve of an extruder provided in front of the side feeder (main feeder side), and (A-1-13) 190 of polylactic acid resin was collected. The melt flow rate (MFR _A ) at 2 ° C. and 21.2 N load was measured. Table 3 shows the results of the melt flow rate (MFR _B ) and MFR _A / MFR _B at 190 ° C. and 21.2 N load of the polyolefin resin and the evaluation results shown in the above (1) to (4).

[Examples 15, 18, 21, 22, 25-38 and Comparative Examples 15, 17, 19, 21-24]
Kneading method: Side feed kneading method 2 (X-2)
(A ′) polylactic acid resin precursor, (D) conjugated diene polymer, (E) phosphorus compound, or (A ′) polylactic acid resin with the composition shown in Table 3, Table 4 and Table 5. Precursor, (C) Chain extender, (D) Conjugated diene polymer, (E) Phosphorus compound, twin diameter extruder with sampling valve with cylinder diameter 30mm, L / D = 45.5 (Japan) Raw materials were charged from the main feeder of TEX30XSSST (manufactured by Steelworks), melt kneading was performed under conditions of a cylinder temperature of 230 ° C. and a rotation speed of 200 rpm, and from the side feeder provided at the position of L / D = 35, Tables 3, 4 and Carboxyl group different from (B) polyolefin resin, (F) ethylene / α-olefin copolymer, (G) inorganic filler, (H) (C) chain extender so as to have the composition shown in Table 5. Input reactive compounds The strand discharged from the discharge port was cooled with a water-cooled cooling bath and then pelletized with a pelletizer to obtain a thermoplastic resin composition. At that time, a mixed molten sample of (A) polylactic acid resin and (D) conjugated diene polymer was sampled from a sampling valve of an extruder provided in front of the side feeder (main feeder side), and hexadiene as a solvent. After dissolving in fluoroisopropanol and removing insoluble matter ((D) conjugated diene polymer), the solvent was volatilized from the solution, and (A-1-8) polylactic acid resin (Examples 15, 18, 21, 22, 25, 29-38), (A-3-1) polylactic acid resin (Example 26), (A-4-1) polylactic acid resin (Examples 27 and 28), (A-1- 11) Polylactic acid resin (Comparative Examples 15, 17, 19, 21), (A-3-2) Polylactic acid resin (Comparative Example 22), (A-4-2) Polylactic acid resin (Comparative Example 23) 24) Melt flow at 190 ° C and 21.2N load Was measured rate (MFR _A). (B) The results of melt flow rate (MFR _B ) and MFR _A / MFR _B at 190 ° C. and 21.2 N load of the polyolefin resin and the evaluation results shown in the above (1) to (4) are shown in Tables 3, 4 and Table 5 shows.

[Examples 17, 20, and 24]
Kneading method: Two-stage kneading method (Y-1)
(A ') Polylactic acid resin precursor, (C) Chain extender, and (E) Phosphorus compound, with a composition shown in Table 3, a twin screw extruder with a cylinder diameter of 30 mm and L / D = 35 ( Raw materials were charged from the main feeder of TEX30α manufactured by Nippon Steel Works, and melt kneading was performed under conditions of a cylinder temperature of 230 ° C. and a rotation speed of 200 rpm. The obtained (A-1-12) polylactic acid resin and (B) polyolefin resin, (D) conjugated diene polymer, (F) ethylene / α-olefin copolymer, (G) inorganic filler, (H) (C) A twin-screw extruder equipped with a sampling valve having a cylinder diameter of 30 mm and L / D = 45.5 (Nippon Steel) so that the carboxyl group-reactive compound different from the chain extender has the composition shown in Table 3. The raw material is charged from the main feeder of TEX30XSSST manufactured by Tokushima, melt kneaded under the conditions of a cylinder temperature of 230 ° C. and a rotation speed of 200 rpm, the strand discharged from the discharge port is cooled by a water-cooled cooling bath, and then pelletized by a pelletizer, A thermoplastic resin composition was obtained. As in Example 1, Table 3 shows the evaluation results shown in MFR _A , MFR _B , MFR _A / MFR _B, and (1) to (4) above.

[Comparative Examples 16, 18, 20]
Kneading method: Batch kneading method (Z-1)
(A ') polylactic acid resin precursor, (B) polyolefin resin, (C) chain extender (not shown in the table, (A'-1) polylactic acid resin precursor) (C-1) chain extender 1.0 part by weight), (D) conjugated diene polymer, (E) phosphorus compound, (F) ethylene / α-olefin copolymer, (G) Inorganic filler, (H) (C) A carboxyl-reactive compound different from the chain extender is blended, and a twin-screw extruder with a sampling valve having a cylinder diameter of 30 mm and L / D = 45.5 (Nippon Steel) The raw material is charged from the main feeder of TEX30XSSST manufactured by Tokushima, melt kneaded under the conditions of a cylinder temperature of 230 ° C. and a rotation speed of 200 rpm, the strand discharged from the discharge port is cooled by a water-cooled cooling bath, and then pelletized by a pelletizer, heat A plastic resin composition was obtained. (A′-1) Polylactic acid resin precursor, that is, (A-1) Melt flow rate (MFR _A ) at 190 ° C. and 21.2 N load of polylactic acid resin, (B) 190 ° C. of polyolefin resin, 21 Table 5 shows the evaluation results of the melt flow rate (MFR _B ) and MFR _A / MFR _{B at} a load of 2 N and the evaluation results shown in the above (1) to (4).

From Examples 15 to 28 and Comparative Examples 15 to 24, MFR _A / MFR _B is 0.01 or more and less than 0.1 (A) polylactic acid resin and (B) polyolefin resin. The thermoplastic resin composition is remarkably excellent in heat resistance, impact resistance and peel resistance. (D) Conjugated diene polymer, (E) Phosphorus compound, (G) Inorganic filler, (H) (C It can be seen that the impact resistance is further improved by further blending (F) an ethylene / α-olefin copolymer with a carboxyl group-reactive compound different from the chain extender.

  Moreover, from Example 18 and 29-34, 230 degreeC, 21.2. Rather than mix | blending only the conjugated diene type polymer whose MFR in 230 degreeC and a 21.2N load condition is 30 g / 10min or less (Example 34). It can be seen that the conjugated diene polymer having an MFR in a 2N load condition of more than 30 g / 10 min is blended (Examples 18, 29, 31 to 33) is superior in heat resistance, impact resistance, and peel resistance. A conjugated diene polymer having an MFR of more than 30 g / 10 min at 230 ° C. and 21.2 N loading conditions, and a polar functionality having an MFR of 30 g / 10 min or less at 230 ° C. and 21.2 N loading conditions. By incorporating a conjugated diene polymer modified with a group (especially an amino group or an imino group) (Examples 18, 31, and 32), remarkable heat resistance and impact resistance are achieved. It can be seen that excellent sex, the peeling resistance.

  Further, from Examples 18, 31 and 37, SEBS (implementation) was conducted rather than compounding SEPS (Example 31) as a conjugated diene polymer having an MFR exceeding 30 g / 10 min at 230 ° C. and 21.2 N load condition. It can be seen that Example 18) or SBBS (Example 37) is more excellent in heat resistance, impact resistance, and peel resistance.

  Furthermore, from Examples 37 and 38, by adding an ethylene / 1-butene copolymer having a specific density and viscosity as the (F) ethylene / α-olefin copolymer, more heat resistance and impact resistance are obtained. It turns out that it is excellent.

Claims (16)

(A) A thermoplastic resin composition comprising 1 to 99% by weight of a polylactic acid resin and (B) 99 to 1% by weight of a polyolefin resin, wherein (A) the polylactic acid resin is (A ′ And (A) polylactic acid resin precursor, and (A ') polylactic acid resin precursor 100 parts by weight with (C) chain extender 0.01 to 3 parts by weight, and (A) poly the ratio of 190 ° C. of the lactic acid resin, the melt flow rate at 21.2N load conditions (MFR _a) and (B) 190 ° C. of the polyolefin resin, the melt flow rate at 21.2N load conditions _{(MFR B)} (MFR a / A thermoplastic resin composition comprising (A) a polylactic acid-based resin and (B) a polyolefin-based resin having an MFR _B ) of 0.01 or more and less than 0.1. The thermoplastic resin composition according to claim 1, wherein the chain extender (C) is a polymer containing an epoxy group and / or a polymer containing a carbodiimide group. The thermoplastic resin composition according to claim 2, wherein the epoxy equivalent of the polymer containing the epoxy group and the carbodiimide equivalent of the polymer containing the carbodiimide group are 50 to 800 g / mol. 2. The (C) chain extender is at least one selected from a styrene polymer containing an epoxy group, an acrylic polymer containing an epoxy group, and a copolymer thereof. -The thermoplastic resin composition in any one of 3. Further, (D) a conjugated diene polymer is formed by blending 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) polyolefin resin. The thermoplastic resin composition according to claim 1. 6. The (D) conjugated diene polymer comprises (D-1) a conjugated diene polymer having a melt flow rate of more than 30 g / 10 minutes at 230 ° C. and a 21.2N load condition. Thermoplastic resin composition. The thermoplastic resin composition according to claim 5 or 6, wherein the (D) conjugated diene polymer includes (D-2) a conjugated diene polymer modified with a polar functional group. (D) The conjugated diene polymer is a block copolymer containing a block mainly containing a conjugated diene and a block mainly containing an aromatic vinyl unit, or a hydrogenated block copolymer thereof. The thermoplastic resin composition according to any one of claims 5 to 7, which is characterized by the following. (D) The conjugated diene polymer is not modified with a polar functional group (D-1) a conjugated diene polymer having a melt flow rate of more than 30 g / 10 min at 230 ° C. and 21.2 N load condition, and 230 ° C. The thermoplastic resin according to any one of claims 5 to 8, comprising a conjugated diene polymer modified with (D-2) a polar functional group having an MFR under a 21.2N load condition of 30 g / 10 min or less. Resin composition. The polar functional group is any one or more of an acid anhydride group, a carboxyl group, an amino group, an imino group, an alkoxysilyl group, a silanol group, a silyl ether group, a hydroxyl group, and an epoxy group. Item 10. The thermoplastic resin composition according to Item 7 or 9. The thermoplastic resin composition according to claim 10, wherein the polar functional group is an amino group and / or an imino group. Further, 0.01 to 10 parts by weight of (E) phosphorus compound is blended with respect to 100 parts by weight of the total amount of (A) polylactic acid resin and (B) polyolefin resin. The thermoplastic resin composition in any one of -11. Furthermore, (B) an ethylene / α-olefin copolymer different from the polyolefin resin is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total amount of (A) polylactic acid resin and (B) polyolefin resin. The thermoplastic resin composition according to any one of claims 1 to 12, which is blended. (A ') Polylactic acid-based resin precursor and (A') Polylactic acid-based resin precursor 100 parts by weight melt-kneaded (C) 0.01-3 parts by weight of chain extender (A) Polylactic acid (A) Polylactic acid resin and (B) polyolefin resin in which MFR _A / MFR _B is 0.01 or more and less than 0.1 are obtained after melt-based resin is obtained. Item 14. A method for producing a thermoplastic resin composition according to any one of Items 1 to 13. A thermoplastic resin composition obtained by the production method according to claim 14. A molded article comprising the thermoplastic resin composition according to claim 1.