JP5505065B2 - Resin composition, process for producing the same, and molded article comprising the same - Google Patents

Description

  The present invention includes (A) a polylactic acid-based resin, (B) a polyolefin-based resin, and (C-1) a conjugated diene-based polymer having an MFR of more than 30 g / 10 min at 230 ° C. and 21.2 N load conditions (C The present invention relates to a resin composition comprising a conjugated diene polymer and excellent in moldability, heat resistance, impact resistance and peel resistance, 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. and can be melt-molded. Therefore, it is expected as a biopolymer that can replace resin produced from fossil raw materials such as petroleum.

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. However, simply blending a plurality of resins has a problem that the peel resistance decreases.

  Patent Document 1 discloses a method for producing a resin composition containing a biodegradable resin and having excellent impact resistance, and a molded product obtained from the resin composition. However, in Patent Document 1, although the impact resistance has a certain improvement effect, it is still insufficient, and there is no disclosure about the properties such as moldability and peel resistance, and the moldability, heat resistance and impact resistance are not disclosed at all. There is no suggestion of a solution for obtaining a resin composition that is excellent in both properties such as property and peel resistance.

  Patent Document 2 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 as a constituent component, and a molded product comprising the same. . However, in the invention of Patent Document 2, although the moldability and peel resistance have some improvement effect, they are still insufficient, and any of the properties such as moldability, heat resistance, impact resistance, peel resistance, etc. There is no suggestion of a solution for obtaining an excellent resin composition.

  Patent Document 3 discloses a resin composition containing a crystalline polypropylene polymer, a polylactic acid resin, an elastomer different from an ethylene polymer having an epoxy group, and an ethylene polymer having an epoxy group. However, in Patent Document 3, although the impact resistance has a certain improvement effect, it is still insufficient, and there is no disclosure about characteristics such as heat resistance and peel resistance, and formability, heat resistance, and impact resistance are not disclosed at all. There is no suggestion of a solution for obtaining a resin composition that is excellent in both properties such as property and peel resistance.

  Patent Document 4 discloses a resin composition comprising a polylactic acid resin, a polyolefin resin, and a compatibilizing agent. However, in Patent Document 4, although moldability, impact resistance, and heat resistance have some improvement effect, they are still insufficient, and any of the characteristics such as moldability, heat resistance, impact resistance, peel resistance, etc. There is no suggestion of a solution for obtaining an excellent resin composition.

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

JP 2009-138123 A (page 1-2, Examples) JP-A-2006-241445 (page 1-2, Examples) JP 2006-52248 A (page 1-2, Examples) JP 2008-38142 A (page 1-3, Examples)

  It is an object of the present invention to provide a resin composition having excellent properties such as moldability, heat resistance, impact resistance, and peel resistance, and a molded article comprising the same, which have been difficult in the above-described prior art. To do.

  As a result of investigations to solve the above problems, the present inventors have found that (A) polylactic acid resin, (B) polyolefin resin, and (C-1) MFR under 230 ° C. and 21.2 N load conditions is 30 g / 10 min. The present inventors have found that the above-mentioned problems can be solved by blending (C) a conjugated diene polymer containing a conjugated diene polymer in excess of the present invention.

That is, the present invention
(1) The total amount of (A) polylactic acid resin and (B) polyolefin resin is 100 parts by weight, and (A) 1 to 99 parts by weight of polylactic acid resin, and (B) 99 to 1 parts by weight of polyolefin resin. (C-1) a conjugated diene polymer having an MFR of more than 30 g / 10 min at 230 ° C. and a 21.2N load condition, and (C-2) a conjugated diene polymer modified with a polar functional group (C ) A resin composition comprising 1 to 50 parts by weight of a conjugated diene polymer ,
(C) A resin composition in which the component (C-1) is 20 to 80% by weight and the component (C-2) is 80 to 20% by weight based on the whole conjugated diene polymer ,
(2) The block copolymer in which the (C) conjugated diene polymer includes a block having a conjugated diene as a main component and a block having an aromatic vinyl unit as a main component, or a hydrogenated block copolymer thereof. The resin composition according to (1),
(3) The (C) conjugated diene polymer is not modified with a functional group (C-1) a conjugated diene polymer having an MFR of more than 30 g / 10 min at 230 ° C. and a 21.2 N load condition, and 230 The resin composition according to (1) or (2), comprising (C-2) a conjugated diene polymer modified with a polar functional group having an MFR of 30 g / 10 min or less at 2 ° C. and 21.2 N load condition,
(4) The polar functional group is any one or more of an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group (1) -The resin composition in any one of (3),
(5) The resin composition according to (4), wherein the polar functional group is an amino group and / or an imino group,
(6) Further, (D) 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. (5) The resin composition according to any one of
(7) (A) 190 ℃ polylactic acid-based resin, 190 ° C. The melt flow rate (MFR _A) and (B) a polyolefin resin in 21.2N load conditions, the melt flow rate at 21.2N load conditions (MFR _B ) Ratio (MFR _A / MFR _B ) is 0.01 or more and 3 or less, and (A) a polylactic acid resin and (B) a polyolefin resin are blended (1) to ( 6) The resin composition according to any one of
(8) The resin composition according to any one of (1) to (7), further comprising (F) an ethylene / α-olefin copolymer that is different from (B) a polyolefin-based resin,
(9) (A) A polylactic acid resin and (C) a conjugated diene polymer are melt-kneaded, and then (B) a polyolefin-based resin and other additives are melt-kneaded. A process for producing the resin composition according to claim 1,
(10) (1) to (8) obtained by melt kneading (A) polylactic acid resin and (C) conjugated diene polymer, and then (B) melt kneading polyolefin resin and other additives. A resin composition according to any one of
(11) A molded article comprising the resin composition according to any one of (1) to (8) and (10).

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

  In the present invention, the (A) polylactic acid-based resin is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. 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 having a high optical purity of the lactic acid component from the viewpoint of heat resistance. That is, among the total lactic acid components of the polylactic acid-based resin, it is preferable that the L-form is contained at 80% or more, or the D-form is contained at 80% or more, the L-form is contained at 90% or more, or the D-form is 90% More preferably, the L-form is contained at 95% or more, or the D-form is contained at 95% or more, the L-form is contained at 98% or more, or the D-form is contained at 98% or more. Is most preferred. Moreover, the upper limit of the content of L-form or D-form is usually 100% or less.

  In the present invention, as the polylactic acid-based resin, 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 a polylactic acid-based resin, a known polymerization method can be used, and a direct polymerization method from lactic acid, a ring-opening polymerization method via lactide, or the like can be used.

  In the present invention, the molecular weight and molecular weight distribution of the polylactic acid-based resin are not particularly limited as long as it can be substantially molded, but it is easy to control the phase structure and the impact resistance is improved. In this respect, the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more, further preferably 100,000 or more, and particularly preferably 200,000 or more. 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 herein 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 polylactic acid resin is not particularly limited, but is preferably 120 ° C. or higher, and more preferably 150 ° C. or higher.

In the present invention, the melt flow rate (MFR _A ) at 190 ° C. and 21.2N load condition of the (A) polylactic acid resin is excellent in moldability, heat resistance, impact resistance, peel resistance, and the like. It is preferably 0.1 to 20 g / 10 minutes, more preferably 0.3 to 18 g / 10 minutes, and further preferably 0.5 to 15 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.

  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, a polyethylene resin, a polypropylene resin, and a 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 heat resistance, polypropylene is preferable. A resin is more preferable, and a polyethylene resin is more preferable in terms of toughness.

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

  In the present invention, when the polyolefin-based 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, a resin composition having excellent moldability and heat resistance. 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 refers to deuterated o-dichlorobenzene as a solvent and is observed as syndiotacticity, heterotacticity, and isotacticity in 13C-NMR measurement at 110 ° C. This is a value that can be calculated by expressing the percentage of the integrated intensity of each peak as a percentage, with the total integrated intensity of the peaks of the straight chain branched methyl groups of 20.2 ppm, 20.8 ppm, and 21.5 ppm as 100%.

  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, when the (B) polyolefin-based resin is a polypropylene resin, the melt flow rate (MFR _B ) is 5 to 50 g / m in terms of excellent moldability, heat resistance, impact resistance, and peel resistance. It is preferably 10 minutes, more preferably 8 to 40 g / 10 minutes, and further preferably 10 to 30 g / 10 minutes. The melt flow rate (MFR) here is a value measured at 190 ° C. and 21.2 N load according to JIS K7210 using “Melt Indexer” manufactured by Toyo Seiki.

  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 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, durability and chemical resistance. More preferably, 1 to 40 parts by weight is further preferred, and (B) polyolefin-based resin is 99 to 1 part by weight, from the viewpoint of moldability, impact resistance, heat resistance, durability and chemical resistance, 99 to 20 parts by weight is preferred, 99 to 40 parts by weight is more preferred, and 99 to 60 parts by weight is even more preferred.

  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 heat resistance, moldability, durability, and chemical 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. Furthermore, from the viewpoints of moldability, heat resistance, impact resistance, transparency and appearance, 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. 70 nm or less is most preferable. 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, a conjugated diene polymer is blended as the component (C), but (C-1) a conjugated diene polymer having an MFR exceeding 230 g / 10 min at 230 ° C. and a 21.2N load condition is blended. It is necessary. (C-1) Compatibility of (A) polylactic acid-based resin and (B) polyolefin-based resin by blending a conjugated diene-based polymer with an MFR exceeding 30 g / 10 min at 230 ° C. and 21.2 N load conditions And a resin composition excellent in moldability, peel resistance, impact resistance and heat resistance can be obtained.

  In the present invention, the (C) 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 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 with aromatic vinyl units or hydrogenated copolymers thereof. Specific examples include styrene / butadiene random copolymers, styrene / butadiene block copolymers, and styrene / butadiene / styrene block copolymers. Polymer (SBS), styrene / isoprene random copolymer, styrene / isoprene block copolymer, styrene / isoprene / styrene block copolymer (SIS), graft copolymer of styrene and polybutadiene, butadiene / acrylonitrile copolymer Polymer, styrene / butadiene / butylene / styrene block Copolymer (SBBS), styrene / ethylene / butylene / styrene block copolymer (SEBS), styrene / ethylene / propylene block copolymer (SEP), styrene / ethylene / propylene / styrene block copolymer (SEPS), 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, SEPS, SEBS or SEPS is more preferable, and SEBS is most preferable.

  In the present invention, when the 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, and peeling resistance In terms of excellent properties, 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, (C-1) it is necessary to blend a conjugated diene polymer having an MFR of more than 30 g / 10 min at 230 ° C. and 21.2 N load condition, but the moldability, heat resistance and impact resistance are required. In terms of excellent peel resistance, the MFR is preferably 50 g / 10 min or more, more preferably 100 g / 10 min or more, further preferably 125 g / 10 min or more, and 150 g / 10 Most preferably, it is greater than or equal to minutes. A preferable upper limit of MFR is 300 g / 10 minutes.

  In the present invention, as the (C) conjugated diene polymer, (C-1) a conjugated diene polymer having an MFR exceeding 30 g / 10 min at 230 ° C. and a 21.2N load condition is an essential component. -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 use (C-2) a conjugated diene polymer modified with a polar functional group as the (C) 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. The MFR of the conjugated diene polymer modified with a polar functional group may be any value, but the MFR under 230 ° C. 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.

  (C-1) Conjugated diene polymer modified with a polar functional group as described above as a conjugated diene polymer having an MFR exceeding 30 g / 10 min at 230 ° C. and 21.2 N load, which is an essential component of the present invention It is also possible to use a polymer.

  As described above, in the present invention, (C-1) MFR under the condition of 230 ° C. and 21.2N load contains a conjugated diene polymer exceeding 30 g / 10 minutes as an essential component. Conjugated diene polymer having a molecular weight of 30 g / 10 min or less and (C-2) conjugated diene polymer modified with a polar functional group can be used in any combination.

  In the present invention, a preferred combination of (C) conjugated diene polymer is (C-1) not modified with a polar functional group. (C-1) Conjugation with MFR exceeding 30 g / 10 min at 230 ° C. and 21.2 N load conditions A combination of a diene polymer and a conjugated diene polymer modified with a (C-2) polar functional group having an MFR of 30 g / 10 min or less at 230 ° C. and a 21.2 N load condition.

  In the present invention, the blending amount of (C) conjugated diene polymer is excellent in moldability, heat resistance, impact resistance and peel resistance, and (A) polylactic acid resin and (B) polyolefin resin. It is 1-50 weight part with respect to the total amount of 100 weight part, and 3-30 weight part is especially preferable. The proportion of the conjugated diene polymer in which the MFR in the (C-1) 230 ° C., 21.2 N load condition of the essential component (C-1) exceeds 30 g / 10 min in the conjugated diene polymer was 100% by weight. It may be an arbitrary ratio. Preferably, the component (C-1) in the (C) conjugated diene polymer is 10% by weight or more, more preferably 30% by weight or more.

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

  In the present invention, as a preferred embodiment, (C-1) a conjugated diene polymer that is not modified with a polar functional group at 230 ° C. and a 21.2N load condition exceeds 30 g / 10 minutes, and 230 ° C. When a conjugated diene polymer modified with a (C-2) polar functional group having an MFR under 21.2N load condition of 30 g / 10 min or less is used in combination, each compounding amount is (C) conjugated diene heavy (C-1) component is preferably 20 to 80% by weight, (C-2) component is preferably 80 to 20% by weight, and more preferably (C-1) component is 30 to 70% by weight, based on the entire coalescence. (C-2) A component is 70 to 30 weight%.

  In the present invention, it is preferable to add (D) a phosphorus compound from the viewpoint of excellent thermal stability. (A) The polylactic acid-based resin may be thermally decomposed during melt-kneading and melt-molding, and by adding (D) a phosphorus-based compound, thermal decomposition can be suppressed and thermal stability can be improved. . Examples of phosphorus compounds include phosphite compounds and phosphate compounds. Specific examples of such phosphite compounds include tetrakis [2-t-butyl-4-thio (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -5-methylphenyl] -1, 6-hexamethylene-bis (N-hydroxyethyl-N-methylsemicarbazide) -diphosphite, tetrakis [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-hydroxyethylcarbonylhydrazide-diphosphite, tetrakis [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-) 5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid di-sali Roylhydrazide-diphosphite, tetrakis [2-tert-butyl-4-thio (2′-methyl-4′-hydroxy-5′-tert-butylphenyl) -5-methylphenyl] -di (hydroxyethylcarbonyl) hydrazide— Diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -N, N'-bis (hydroxyethyl) oxamide -Diphosphite and the like are mentioned, and those in which at least one PO bond is bonded to an aromatic group are more preferable. Specific examples include tris (2,4-di-t-butylphenyl) phosphite, Tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene phosphonite, bis (2,4-di-t-butylphenyl) Pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) Octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite— 5-t-butyl-phenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4'-isopropylidenebis (phenyl-dialkyl phosphite) and the like Tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di) t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4, 4′-biphenylene phosphonite 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 Co., Ltd. 618, 619G, 624 and the like.

  Specific examples of the phosphate compound include monostearyl acid phosphate, distearyl acid phosphate, methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, isodecyl acid phosphate, etc., among which monostearyl acid phosphate Distearyl acid phosphate is 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. Among them, “ADEKA STAB” AX-71 (dioctadecyl phosphate), PEP-8 (distearyl pentaerythritol diphosphite), PEP-36 (cyclic neopentatetrayl bis (2,6-t-butyl) manufactured by ADEKA are preferable. -4-methylphenyl) phosphite), most preferably "ADK STAB" AX-71.

  In the present invention, the blending amount of the phosphorus compound (D) 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 (D) the phosphorus compound is not particularly limited, and (A) a method of melt kneading at or above the melting point of the polylactic acid resin or after dissolving and mixing in a solvent, the solvent is removed. Although a method etc. can be mentioned, The method of melt-kneading above the melting | fusing point of (A) polylactic acid-type resin is preferable at the point that it can manufacture efficiently. 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 this invention, the temperature which mix | blends (D) phosphorus type compound has the preferable temperature of 180-250 degreeC, and the temperature of 190-230 degreeC is more preferable at the point that it is excellent in a mechanical characteristic.

  In the present invention, the pressure at which (D) the phosphorus compound is blended may be any of reduced pressure, normal pressure and increased pressure, and is preferably reduced pressure in that the generated gas can be removed during melt-kneading.

  In the present invention, (D) when mixing in a solvent as a method for blending the phosphorus compound, a solvent in which the polymer and the monomer are dissolved is used. As the solvent, for example, chloroform, methylene chloride, 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, (D) a phosphorus compound is added, 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. The resin composition which has a preferable phase structure in which a fall is suppressed can be obtained.

In the present invention, (A) 190 ° C. of the polylactic acid-based resin, 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 the ratio of _{B) (MFR a / MFR B} ) is, moldability, heat resistance, in terms of excellent impact resistance and peeling resistance, preferably from 0.01 to 3, in 0.01 More preferably, it is more preferably 0.01 to 0.5, and most preferably 0.01 to 0.1. The melt flow rate (MFR) here is a value measured at 190 ° C. and 21.2 N load according to JIS K7210 using “Melt Indexer” manufactured by Toyo Seiki.

In the present invention, in order to set the MFR _A / MFR _B to the most preferable range of 0.01 to 0.1, (A) a polylactic acid resin and (E) a chain extender are reacted, and (A) _A method of increasing the melt flow rate (MFR _A ) of polylactic acid resin at 190 ° C. and 21.2 N load condition is preferably used.

In the present invention, (A) polylactic acid-based resin includes those obtained by reacting (A) polylactic acid-based resin with (E) chain extender, and (E) chain extender is used. (A) The melt flow rate (MFR _A ) of the polylactic acid-based resin is the melt flow rate of the product obtained by reacting the (A) polylactic acid-based resin with the (E) chain extender.

  In the present invention, the (E) 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 in the skeleton molecular chain. Although there is 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 (E) 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 (E) the chain extender 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 (E) the chain extender 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 (E) chain extender 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, when (E) a chain extender is used, the blending ratio of (A) polylactic acid resin to (E) chain extender is (E) 100 parts by weight of polylactic acid resin (E) chain extender. 0.01 to 3 parts by weight is preferred, (E) 0.05 to 2.5 parts by weight of chain extender is more preferred, and (E) 0.1 to 2.0 parts by weight of chain extender is most preferred.

  In the present invention, there is no particular limitation on the method of reacting (A) the polylactic acid resin and (E) the chain extender, and (A) the polylactic acid resin and (E) the chain extender are dissolved in a soluble solvent. Examples include a method of reacting under heating and stirring, a method of kneading and reacting (A) a polylactic acid-based resin and (E) a chain extender in a heated and melted state, etc., from the viewpoint of promoting the reaction in a short time, Preferably, a method in which (A) a polylactic acid-based resin and (E) a chain extender are kneaded and reacted in a heated and melted state can be used.

  In the present invention, the method of kneading and reacting (A) the polylactic acid-based resin and (E) the chain extender in a heated and melted state is not particularly limited, but is preferably a heat-melting and kneading apparatus such as an extruder or a kneader. The method of making it react by using is used, More preferably, it is the method of making it react 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, 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 resin and (E) a chain extension A method in which (A) a polylactic acid resin and (B) a polyolefin resin are melt-kneaded after melt-kneading the agent is preferred. As a specific production method, for example, (A) a polylactic acid resin and (E) a chain extender are previously melt-kneaded in an extruder, and then (A) a polylactic acid resin and (B) a polyolefin resin are extruded. (A) Polylactic acid resin and (E) chain extender are supplied from the main feeder of the extruder, and (B) polyolefin resin is extruded. Examples thereof include a method (side feed kneading method) in which (A) a polylactic acid resin and (B) a polyolefin resin are melt-kneaded from a side feeder installed in the middle of the machine.

In the present invention, when the thermoplastic resin composition is produced by the side feed kneading method, the MFR _A is kneaded with the (B) polyolefin resin supplied from the side feeder installed in the middle of the extruder. (A) The melt flow rate of the polylactic acid resin at 190 ° C. and 21.2N load condition before the measurement is performed. For example, (B) in front of the side feeder for supplying the polyolefin resin (main Using an extruder equipped with a sampling valve on the feeder side), (A) a method for measuring the melt flow rate of polylactic acid resin sampled from the sampling valve at 190 ° C. and 21.2 N load conditions, and (A) poly Side feeder that supplies (B) polyolefin resin from main feeder that supplies lactic acid resin Using another extruder with equal L / D (L: extruder screw length, D: extruder screw diameter), (A) a polylactic acid resin was produced in advance and produced (A ) A method of measuring the melt flow rate of polylactic acid resin at 190 ° C. and 21.2N load condition.

  In the present invention, the melt kneading temperature when (A) the polylactic acid-based resin and (E) the chain extender are heated, melt-kneaded and reacted is equal to or higher than the melting point of (A) the polylactic acid-based resin and (E) the chain extender. If it is, there will be no restriction | limiting in particular, From a viewpoint of reactivity and a moldability, Preferably it is 150 to 270 degreeC, More preferably, it is 160 to 260 degreeC, Most preferably, it is 170 to 250 degreeC.

  In the present invention, the reaction time when (A) the polylactic acid resin and (E) the chain extender are heated and melt-kneaded and reacted is not particularly limited, but is preferable from the viewpoint of reactivity and moldability. Is 5 seconds to 1800 seconds, more preferably 10 seconds to 1200 seconds, and most preferably 20 seconds to 600 seconds.

  Further, in the present invention, other than the conjugated diene polymer may be contained, for example, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer, acid anhydride group, carboxyl Group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, olefin resin containing at least one functional group selected from hydroxyl group and epoxy group, acid anhydride group, carboxyl group, amino group Examples thereof include acrylic resins and ionomer resins containing at least one functional group selected from a group, an imino group, an alkoxysilyl group, a silanol group, a silyl ether group, a hydroxyl group and an epoxy group.

  In this invention, it is preferable to mix | blend (F) ethylene / alpha-olefin copolymer different from (B) polyolefin resin from a viewpoint of an impact-resistant improvement.

  In the present invention, the (F) ethylene / α-olefin copolymer is a copolymer of ethylene and at least one kind of α-olefin 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.

  (B) When blending (F) ethylene / α-olefin copolymer different from polyolefin resin, the total amount of (A) polylactic acid resin and (B) polyolefin resin is 100 parts by weight. -50 weight part is preferable, More preferably, it is 1-30 weight part.

  In the present invention, fillers, plasticizers, carboxyl group-reactive compounds, stabilizers (antioxidants, ultraviolet absorbers, etc.), lubricants, release agents, flame retardants, dyes and Colorants including 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 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, wollastonite, sepiolite, asbestos, slag fiber, zonolite, elastadite, Fibrous inorganic fillers such as gypsum fiber, silica fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, glass flake, non-swellable mica, graphite, metal foil, ceramic beads, talc, clay, Mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, Plate-like and granular inorganic fillers such as aluminum oxalate, silicon oxide, gypsum, novaculite, dosonite and clay, 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 powder, protein, starch And organic fillers in the form of fibers, powders or chips, such as rice husks, wood chips, okara, waste paper pulverized materials, and clothing pulverized materials. 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, 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 1 to 300 parts by weight, more preferably 5 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. preferable.

  In the present invention, it is preferable to blend a plasticizer from the viewpoint that a 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 this invention, it is preferable to mix | blend the carboxyl group reactive compound different from (E) chain extender at the point which can improve the durability and toughness of the resin composition obtained further. The carboxyl group-reactive compound is not particularly limited as long as it is a compound reactive with the carboxyl end group of (A) polylactic acid resin, but (A) thermal decomposition or hydrolysis of polylactic acid resin. It is more preferable if it is reactive with the carboxyl group of acidic low molecular weight compounds such as lactic acid and formic acid produced by the above, and is also a compound reactive with the hydroxyl group end group of acidic low molecular weight compounds generated by thermal decomposition. More preferably. Examples of such carboxyl group-reactive compounds include glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, glycidyl imide compounds, alicyclic epoxy compounds, epoxy group-containing compounds, 2,2′-m-phenylenebis (2- Oxazoline), oxazoline compounds such as 2,2′-p-phenylenebis (2-oxazoline), oxazine compounds, N, N′-di-2,6-diisopropylphenylcarbodiimide, 2,6,2 ′, 6′- It is preferable to use at least one compound selected from carbodiimide compounds such as tetraisopropyldiphenylcarbodiimide and polycarbodiimide, and epoxy group-containing compounds and / or carbodiimide compounds are particularly preferable. As the carboxyl group-reactive compound, one or more compounds can be arbitrarily selected and used.

  In the present invention, the compounding amount of the carboxyl group-reactive compound is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the (A) polylactic acid resin and (B) polyolefin resin. 05 to 5 parts by weight is more preferable.

  In the present invention, it is preferable to further add a reaction catalyst of a carboxyl group-reactive compound. The reaction catalyst here is a compound having an effect of promoting the reaction between the carboxyl group-reactive compound and the terminal of the (A) polylactic acid-based resin or the carboxyl group of the acidic low molecular weight compound. A compound having an effect of promoting the reaction is preferable, and the reaction catalyst of the carboxyl group-reactive compound preferably has an effect of promoting the reaction with the hydroxyl group of the acidic low molecular weight compound generated by thermal decomposition. 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 resin composition of the present invention is not particularly limited as long as the requirements specified in the present invention are satisfied. For example, (A) a polylactic acid resin, (B) a polyolefin resin, and (C) a conjugated diene heavy polymer. And a method in which other additives, if necessary, are reacted in a soluble solvent under heating and stirring, such as (A) polylactic acid resin, (B) polyolefin resin, and (C) conjugated diene polymer. In addition, there may be mentioned a method of kneading and reacting in a state where other additives are heated and melted as necessary, from the viewpoint of promoting the reaction in a short time, preferably, for example, (A) a polylactic acid resin, A method of kneading and reacting (B) a polyolefin resin, (C) a conjugated diene polymer, and, if necessary, other additives as heated and melted can be used.

  In the present invention, (A) a polylactic acid-based resin, (B) a polyolefin-based resin, and (C) a conjugated diene-based polymer, and other additives as necessary are kneaded and reacted in a heated and melted state. Although there is no particular limitation, a reaction method is preferably used by using a heat-melt kneading apparatus such as an extruder or a kneader, and a reaction method is more preferably used 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, when producing a thermoplastic resin composition by a melt kneading method using a single screw or twin screw extruder, (C) a conjugated diene polymer, (D) a phosphorus compound, ( When E) chain extender, (F) ethylene / α-olefin copolymer and other additives are blended, they can be blended at any location, preferably (A) polylactic acid resin, (E (A) Polylactic acid-based resin and (B) Polyolefin-based resin after (A) polylactic acid-based resin pellets are obtained by melt-kneading the chain extender and optionally (D) phosphorus-based compound with an extruder in advance. Resin, optionally (C) conjugated diene polymer, (F) ethylene / α-olefin copolymer and other additives are fed from the main feeder of the extruder and melt kneaded (two-stage kneading method), extrusion Machine main feeder (A) polylactic acid resin, (E) chain extender and optionally (C) conjugated diene polymer, (D) phosphorus compound, (B) polyolefin resin, optionally (F) A method in which an ethylene / α-olefin copolymer and other additives are supplied from a side feeder installed in the middle of an extruder and (A) a polylactic acid-based resin and (B) a polyolefin-based resin are melt-kneaded (side-feed kneading method) ) And the like to produce a thermoplastic resin composition.

In the present invention, when the thermoplastic resin composition is produced by the side feed kneading method, the MFR _A is kneaded with the (B) polyolefin resin supplied from the side feeder installed in the middle of the extruder. (A) The melt flow rate of the polylactic acid resin at 190 ° C. and 21.2N load condition before the measurement is performed. For example, (B) in front of the side feeder for supplying the polyolefin resin (main Using an extruder equipped with a sampling valve on the feeder side), (A) a method for measuring the melt flow rate of polylactic acid resin sampled from the sampling valve at 190 ° C. and 21.2 N load conditions, and (A) poly Side feeder that supplies (B) polyolefin resin from main feeder that supplies lactic acid resin (A) polylactic acid resin previously reacted with a chain extender (E) using another extruder having equal L / D (L: extruder screw length, D: extruder screw diameter) And (A) a method of measuring the melt flow rate of the produced (A) polylactic acid resin at 190 ° C. and 21.2 N load condition. In addition, when (A) polylactic acid-based resin, (E) chain extender and optionally (C) conjugated diene-based polymer are supplied from the main feeder of the extruder by side feed kneading method, when measuring MFR _A (C) It is necessary to remove the conjugated diene polymer. In this case, as a method of removing (C) the conjugated diene polymer, for example, (A) a solvent in which the polylactic acid resin is soluble and (C) 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 the case of producing a thermoplastic resin composition by the side feed kneading method, 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. / D is 100%, preferably 30% to 95% from the main feeder, more preferably 40% to 92%, most preferably 50% to 90% from the main feeder. In the present invention, the melt-kneading temperature when producing the resin composition is preferably 170 to 270 ° C, more preferably 175 to 265 ° C, and particularly preferably 180 to 260 ° C.

  The 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 articles made of the resin composition of the present invention are used in various applications such as automobile parts (interior / exterior parts, etc.), electrical / electronic parts (various housings, gears, gears, etc.), building members, civil engineering members, agricultural materials, and daily necessities. Can be used. 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 packaging film, tray, blister, knife, fork, spoon, tube, plastic can, pouch, container, tank, basket, etc. Fill containers, microwave cooking containers, cosmetic containers, wraps, foam buffers, paper laminates, shampoo bottles, beverage bottles, cups, candy packaging, chestnuts Containers such as link 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, wrapping films for electrical and electronic parts, etc. Packaging, natural fiber composites, polo shirts, T-shirts, innerwear, uniforms, sweaters, socks, ties, and other clothing, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tape, Print lamination, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, non-woven fabric hot melt binder, magnetic material, zinc sulfide, electrode Powder binders for materials, optical elements, 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, adhesive, bag, chair It is useful as a table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter and so on.

  From the viewpoint of impact resistance, the resin composition of the present invention preferably has an Izod impact strength of 45 J / m or more, more preferably 55 J / m or more, and further preferably 70 J / m or more. It is preferably 100 J / m or more. Here, the Izod impact strength is an Izod impact strength of a strip-shaped molded article having a 3 mm thickness notch, measured according to ASTM D256.

  From the viewpoint of heat resistance, the resin composition of the present invention preferably has a deflection temperature under a load of 0.45 MPa of 70 ° C. or higher, more preferably 80 ° C. or higher, and 85 ° C. or higher. More preferably, it is particularly preferably 90 ° C. or higher, and most preferably 100 ° C. or higher. Here, the deflection temperature under load is a deflection temperature under load of a molded product of 12.7 mm × 127 mm × 3 mm, measured according to ASTM D648.

  In terms of impact resistance and heat resistance, the resin composition of the present invention preferably has an Izod impact strength of 55 J / m or more, a deflection temperature under a load of 0.45 MPa of 85 ° C. or more, and an Izod impact strength of 60 J. / M or more, the deflection temperature under load at 0.45 MPa is more preferably 90 ° C. or more, the Izod impact strength is 70 J / m or more, and the deflection temperature under load at 0.45 MPa is more preferably 100 ° C. or more. .

  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 (A-1) Poly L lactic acid resin (D-form 1.2%, MFR 14 g / 10 min (190 ° C., 21.2 N), Mw (converted to PMMA) 160,000, melting point 168 ° C.)
(A-2) Poly L lactic acid resin (D body 1.2%, MFR 3.5 g / 10 min (190 ° C., 21.2 N), Mw (PMMA conversion) 210,000, melting point 168 ° C.).

(B) Polyolefin resin (B-1) Polypropylene resin (homopolymer, prime polymer S119, MFR 24 g / 10 min (190 ° C., 21.2 N), melting point 169 ° C.)
(B-2) Polypropylene resin (homopolymer, prime polymer J108M, MFR 18.4 g / 10 min (190 ° C., 21.2 N), melting point 169 ° C.)
(B-3) Polypropylene resin (homopolymer, prime polymer J106G, MFR 6.4 g / 10 min (190 ° C., 21.2 N), melting point 169 ° C.)
(B-4) Polypropylene resin (block polymer, prime polymer J708UG, MFR 18.4 g / 10 min (190 ° C., 21.2 N), melting point 169 ° C.)
(B-5) Polypropylene resin (random polymer, Nippon Polypro MG03B, MFR 12.1 g / 10 min (190 ° C., 21.2 N), melting point 159 ° C.)
(B-6) Polypropylene resin (random polymer, Nippon Polypro MG05ES, MFR 18.4 g / 10 min (190 ° C., 21.2 N), melting point 159 ° C.).

(C-1) Conjugated diene polymer (M-1-1) SEBS ("Tough Tech" H1031, manufactured by Asahi Kasei Chemicals Co., Ltd., 30% by weight of styrene) with MFR exceeding 30 g / 10 min at 230 ° C and 21.2N load condition , MFR 150 g / 10 min (230 ° C., 21.2 N))
(C-1-2) SEBS (Kuraray “Septon” 8076, styrene content 30% by weight, MFR 65 g / 10 min (230 ° C., 21.2 N))
(C-1-3) SEPS (Kuraray “Septon” 2002, styrene content 30% by weight, MFR 70 g / 10 min (230 ° C., 21.2 N)).

(C-2) Conjugated diene polymer modified with a polar functional group (C-2-1) Imino group-modified SEBS (Asahi Kasei Chemicals "Toughtech" MP10, styrene content 30 wt%, MFR 4 g / 10 min (230 ° C, 21.2N))
(C-2-2) Imino group-modified SEBS (“Tough Tech” N503, manufactured by Asahi Kasei Chemicals Co., Ltd., styrene content: 30% by weight, MFR: 20 g / 10 min (230 ° C., 21.2 N))
(C-2-3) Amino group-modified SEBS (“Dynalon” 8630P manufactured by JSR, styrene content 15% by weight, MFR 15 g / 10 min (230 ° C., 21.2 N)).

(C-3) Conjugated diene polymer (M-3-1) SEBS ("Tough Tech" H1041, manufactured by Asahi Kasei Chemicals Co., Ltd., 30% by weight of styrene) having an MFR of 30 g / 10 min or less at 230 ° C and 21.2N load condition , MFR 5 g / 10 min (230 ° C., 21.2 N))
(C-3-2) SEPS (Kuraray “Septon” 4033, styrene content 30% by weight, MFR 5 g / 10 min (230 ° C., 21.2 N).

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

(E) Chain extender (E-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)
(E-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).

(F) Ethylene-α-olefin copolymer (F-1) Ethylene / butene (Mitsui Chemicals “Toughmer” A-35070S, density 870 kg / m 3, MFR 35 g / 10 min (190 ° C., 21.2 N))
(F-2) Ethylene / butene (Mitsui Chemicals “Toughmer” A-0550S, density 864 kg / m 3, MFR 0.5 g / 10 min (190 ° C., 21.2 N))
(F-3) Ethylene / butene (“Excellen” CX5505 manufactured by Sumitomo Chemical Co., Ltd., density 870 kg / m 3, MFR 16 g / 10 min (190 ° C., 21.2 N))
(F-4) Ethylene / hexene (“Excellen” CX4002, manufactured by Sumitomo Chemical Co., Ltd., density 880 kg / m 3, MFR 8 g / 10 min (190 ° C., 21.2 N)).

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

(H) Plasticizer (H-1) Polyethylene glycol (PEG6000S manufactured by Sanyo Chemical Industries).

(I) Carboxyl group-reactive compound (I-1) Polycarbodiimide (“Carbodilite” LA-1 manufactured by Nisshinbo).

(J) Other thermoplastic resin (J-1) Polyethylene wax (“Hi-X” 1300J, Mitsui Petrochemical Co., Ltd., MFR 115 g / 10 min (230 ° C., 21.2 N), 13 g / 10 min (190 ° C., 21.2 N))
(J-2) High flow polystyrene (G120K manufactured by Nippon Polystyrene, MFR 56.3 g / 10 min (230 ° C., 21.2 N), 30 g / 10 min (200 ° C., 5 kgf)).

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

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

(2) Fluidity (MFR)
190 ° C. ((A) polylactic acid resin, (B) polyolefin resin, (E) ethylene / α-olefin copolymer) and 230 ° C. according to JIS K7210, using “Melt Indexer” manufactured by Toyo Seiki ((C) Conjugated diene polymer) Measured at 21.2 N load.

(3) Formability (molding cycle time)
Using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), injection molding is performed at a cylinder temperature of 210 ° C. and a mold temperature of 80 ° C., and a tensile test piece that can be subjected to a tensile test is formed from the mold. At the time of taking out, the shortest time for obtaining a solidified molded product without deformation was measured as the molding cycle time. It can be said that the shorter the molding cycle time, the better the moldability.

(4) Impact resistance (Izod impact strength)
In accordance with ASTM D256, the Izod impact strength of a 3 mm thick notched strip-shaped product was measured.

(5) Impact resistance (high-speed surface impact strength)
A high-speed surface impact test (speed: 5 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 judged according to the following criteria.
○: Ductile fracture △: Slightly ductile fracture ×: Brittle fracture.

(6) Heat resistance (DTUL)
According to ASTM D648, the deflection temperature under load (load 0.45 MPa) of a molded article of 12.7 mm × 127 mm × 3 mm was measured.

(7) Peeling resistance 10mm x 10mm x 3mm square plate molded product A grid-like cut is made at 1mm intervals with a cutter knife in the vicinity of the gate, and cellophane tape is adhered on the grid, and against the square plate surface After peeling off instantaneously at an angle of 90 °, the state of the surface of the molded product was observed, the squares peeled in 100 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 4 to 10, Comparative Examples 1 to 9 , 19 to 21 ]
The raw materials are blended as shown in Table 1 and Table 2, using a 30 mm diameter, L / D = 45 twin screw extruder (TEX-30α manufactured by Nippon Steel), cylinder temperature 210 ° C. (or 230 ° C.), rotation Melt kneading was performed under the conditions of several 200 rpm to obtain a resin composition.

The obtained resin composition was injection-molded at a cylinder temperature of 210 ° C. and a mold temperature of 80 ° C. using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) to obtain a molded product for peel resistance evaluation. .
Tables 1 and 2 show the results of evaluation of peel resistance using the obtained molded product.

From the results of Table 1 and Table 2, in Comparative Examples 19 to 21 in which a conjugated diene polymer having an MFR exceeding 30 g / 10 minutes was blended, the peel resistance was higher than those of Comparative Examples 5 and 6 having an MFR of 30 g / 10 minutes or less. It turns out that it improves a little .

In Example 4, a conjugated diene polymer having an MFR of more than 30 g / 10 minutes and a conjugated diene polymer modified with a polar functional group having an MFR of 30 g / 10 minutes or less were used in combination, and Comparative Examples 5 and 6 It can be seen that the peel resistance is improved from Comparative Examples 7 and 19 to 21 in which a conjugated diene polymer modified with a polar functional group having an MFR of 30 g / 10 min or less is blended alone.

  In Examples 5 to 7, it can be seen that by increasing the kneading temperature from 210 ° C. to 230 ° C., the peel resistance is further improved as compared with Example 4 and is equivalent to the polypropylene resin of Comparative Example 2.

In Examples 8,9, (A) 190 ℃ of polylactic acid resin, the melt flow rate at 21.2N load conditions _{(MFR A) (B) 190} ℃ polyolefin resin having a melt flow at 21.2N load conditions By controlling the ratio of the rate (MFR _B ) (MFR _A / MFR _B ), it can be seen that the peel resistance is improved compared to Example 4 and Example 10 and is equivalent to the polypropylene resin of Comparative Example 2.

In any of Examples 4 to 10, Comparative Examples 3 to 5 in which polylactic acid and polypropylene are simply blended, Comparative Example 8 in which polyethylene is blended in place of the conjugated diene polymer, instead of the conjugated diene polymer It turns out that peeling resistance improves from the comparative example 9 which mix | blended polystyrene.

[Examples 12 to 40, Comparative Examples 10 to 18 and 22 ]
The raw materials were blended as shown in Tables 3 to 6, and a cylinder temperature of 210 ° C. (or 230 ° C.) was rotated using a 30 mm diameter, L / D = 45 twin screw extruder (TEX-30α manufactured by Nippon Steel). Melt kneading was performed under the condition of several 200 rpm to obtain a resin composition.

For Examples 21 to 24 and 29 to 32, (A) polylactic acid resin, (C) conjugated diene polymer, and (D) phosphorus compound were previously melt-kneaded at 230 ° C. (first kneading). After obtaining the resin composition, (B) a polyolefin-based resin and other additives were melt-kneaded (210 kneaded) at 210 ° C. For Example 33, (A) polylactic acid-based resin, (C) conjugate After a diene polymer, (D) phosphorus compound, and (E) chain extender are melt kneaded at 230 ° C. (first kneading) to obtain a resin composition, (B) polyolefin resin and other additions The agent was melt-kneaded at 210 ° C. (second kneading) to obtain a resin composition (two-stage kneading method). In addition, about the melt flow rate (MFR _A ) in 190 degreeC and 21.2N load conditions of (A) polylactic acid-type resin, the resin composition obtained by 1st kneading | mixing is (A) in hexafluoro isopropanol. The melt flow rate (MFR _A ) at 190 ° C. and 21.2 N load condition of (A) polylactic acid resin obtained by dissolving only the polylactic acid resin and volatilizing the solvent from the solution was measured.

For Examples 34 and 35, (A) polylactic acid resin, (C) conjugated diene polymer, and (D) phosphorus compound were supplied from the main feeder of the twin-screw extruder, and the position of L / D = 35 (B) A polyolefin-based resin and other additives are supplied from the side feeder provided in, and melt-kneaded at 230 ° C. For Examples 36 and 37, (A) polylactic acid-based resin, (C) conjugated diene-based A polymer, (D) a phosphorus compound, and (E) a chain extender are supplied from a main feeder of a twin screw extruder, and (B) a polyolefin resin and other additives are added from a side feeder provided at a position of L / D = 35. An agent was supplied, and melt kneading was performed at 230 ° C. to obtain a resin composition (side feed kneading method). For (A) the melt flow rate (MFR _A ) of polylactic acid resin at 190 ° C. and 21.2N load, (B) a sampling valve is placed in front of the side feeder (main feeder side) for supplying the polyolefin resin. (A) Polylactic acid type obtained by dissolving only (A) polylactic acid resin in hexafluoroisopropanol and evaporating the solvent from the resin composition collected from the sampling valve of the provided extruder 190 ° C. of the resin was measured melt flow rate (MFR _a) of 21.2N load conditions.

The obtained resin composition was injection molded at a cylinder temperature of 210 ° C. and a mold temperature of 80 ° C. using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) to obtain molded products for various evaluations.
Tables 3 to 6 show the results of various evaluations using the obtained molded product.

From the results of Tables 3 to 6, in Example 1 2 to 14, MFR is formulated alone conjugated diene polymer of greater than 30 g / 10 min, or conjugated diene heavy that MFR exceeds 30 g / 10 min The combined conjugated diene polymer modified with a polar functional group having an MFR of 30 g / 10 min or less is used alone by combining the conjugated diene polymer modified with a polar functional group having an MFR of 30 g / 10 min or less. It turns out that heat resistance, impact resistance, and peeling resistance improve from the comparative examples 11-13 mix | blended by (3).

In Example 15, (A) 190 ° C. of the polylactic acid-based resin, 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 ( by controlling the ratio of the _{MFR B) (MFR a / MFR} B), it can be seen that improved peeling resistance than example 12.

  In Example 16, it can be seen that by increasing the kneading temperature from 210 ° C. to 230 ° C., the heat resistance, impact resistance, and peel resistance are improved compared to Example 12.

  In Examples 17 and 18, the base polypropylene-based resin was changed from a homopolymer alone to a block polymer alone, whereby heat resistance, impact resistance and peel resistance were improved compared to Comparative Examples 14 and 16, and Example 12 It can be seen that the heat resistance and impact resistance are further improved. Moreover, in Example 17, kneading | mixing temperature is 230 degreeC and it turns out that heat resistance and impact resistance improve from Example 18 whose kneading | mixing temperature is 210 degreeC.

  In Example 19, the base polypropylene resin was changed from a homopolymer alone to a random polymer alone, whereby heat resistance, impact resistance and peel resistance were improved compared to Comparative Example 15, and impact resistance was more than Example 12. It can also be seen that the surface impact is improved.

  In Example 20, it can be seen that by adding a phosphate-based phosphorus compound, the heat resistance, impact resistance, and peel resistance after 30-minute residence in a molding machine are improved.

  In Example 21, a polylactic acid-based resin and a conjugated diene-based polymer were previously melt-kneaded to obtain a resin composition, and then heat-kneaded with a polyolefin-based resin and other additives. It can be seen that the resistance, impact resistance and peel resistance are improved.

  In Example 22, a phosphate phosphorus compound was blended, and after a polylactic acid resin and a conjugated diene polymer were previously melt-kneaded to obtain a resin composition, a polyolefin resin and other additives were used. And kneading and kneading improve heat resistance, impact resistance, and peel resistance from Example 20, and heat resistance, impact resistance, and peel resistance after 30 minutes of residence in a molding machine from Example 21. I understand that.

  In Example 23, it can be seen that the same high heat resistance, impact resistance and peel resistance as in Example 22 can be maintained without blending a plasticizer.

  In Example 24, it can be seen that by adding a phosphite-based phosphorus compound, high heat resistance, impact resistance and peel resistance equivalent to those of Example 22 are maintained.

  In Example 25, it can be seen that by adding the ethylene-α-olefin copolymer, the impact resistance and the surface impact are improved without significantly lowering the peel resistance compared to Example 12.

  In Examples 26 and 27, by adding an ethylene-α-olefin copolymer and changing the base polypropylene resin from a homopolymer to a block polymer or a random polymer, the impact resistance is higher than those of Examples 18, 19 and 25. It can be seen that the property and the surface impact are improved.

  In Example 28, it can be seen that high impact resistance and surface impact equivalent to those in Example 27 are maintained without blending a plasticizer.

  In Example 29, ethylene / α-olefin was blended, and a polylactic acid resin and a conjugated diene polymer were previously melt-kneaded to obtain a resin composition, and then melt-kneaded with a polyolefin resin. It can be seen that the peel resistance is improved while maintaining the high impact resistance and surface impact equivalent to those of Example 27.

  In Example 30, it can be seen that by adding a phosphorus compound, the heat resistance, impact resistance, and peeling resistance before and after 30-minute residence in the molding machine are improved from Example 29.

  In Example 31, it can be seen that even when the base polymer is changed to a random polymer having a different MFR, the same high heat resistance, impact resistance, surface impact and peel resistance as those in Example 30 are maintained.

In Example 32,33, (A) 190 ℃ of polylactic acid resin, the melt flow rate at 21.2N load conditions _{(MFR A) (B) 190} ℃ polyolefin resin having a melt flow at 21.2N load conditions It can be seen that by controlling the rate (MFR _B ) ratio (MFR _A / MFR _B ), heat resistance and impact resistance are improved while maintaining high surface impact and peel resistance equivalent to those of Example 31. .

  In Example 34, by changing the kneading method from the two-stage kneading method to the side feed method, heat resistance and impact resistance are improved while maintaining high surface impact and peeling resistance equivalent to those in Example 31. I understand.

In Example 35,36,37, (A) 190 ℃ of polylactic acid resin, the melt flow rate at 21.2N load conditions _{(MFR A) (B) 190} ℃ polyolefin resin, in 21.2N load conditions By controlling the melt flow rate (MFR _B ) ratio (MFR _A / MFR _B ), heat resistance and impact resistance are improved while maintaining high surface impact and peel resistance equivalent to those of Example 34. I understand. In Examples 38-40, even if it changes an ethylene / alpha-olefin copolymer, it turns out that the high heat resistance equivalent to Example 27, impact resistance, surface impact, and peeling resistance are maintained.

In any of Examples 12 to 40, it can be seen that the impact resistance and the peel resistance are superior from Comparative Example 10 in which polylactic acid and polypropylene are blended, and Comparative Example 17 in which polylactic acid, polypropylene and a phosphorus compound are blended. In Comparative Example 18 was blended polylactic acid and polypropylene and ethylene / alpha-olefin copolymer, although the impact resistance is improved peel resistance inferior to any of the Examples 12-40.

Claims (11)

(A) 1 to 99 parts by weight of polylactic acid resin, (B) 99 to 1 part by weight of polyolefin resin, (C) -1) A conjugated diene polymer including a conjugated diene polymer having an MFR of more than 30 g / 10 min at 230 ° C. and a 21.2N load condition, and (C-2) a conjugated diene polymer modified with a polar functional group. A resin composition comprising 1 to 50 parts by weight of a polymer ,
(C) The resin composition whose (C-1) component is 20 to 80 weight% and (C-2) component is 80 to 20 weight% with respect to the whole conjugated diene polymer . The (C) conjugated diene polymer is a block copolymer containing a block containing a conjugated diene as a main component and a block containing an aromatic vinyl unit as a main component, or a hydrogenated block copolymer thereof. Item 2. The resin composition according to Item 1. The (C) conjugated diene polymer is not modified with a functional group (C-1) a conjugated diene polymer having an MFR of more than 30 g / 10 min at 230 ° C. and 21.2 N load condition, and 230 ° C., 21 The resin composition of Claim 1 or 2 containing the conjugated diene type polymer modified by the (C-2) polar functional group whose MFR in 2N load conditions is 30 g / 10min or less. 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 resin composition according to any one of the above. The resin composition according to claim 4, wherein the polar functional group is an amino group and / or an imino group. Furthermore, (D) Phosphorus compound is formed by blending 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. 2. The resin composition according to item 1. (A) Ratio of melt flow rate (MFR _A ) at 190 ° C. and 21.2N load condition of polylactic acid resin to (B) melt flow rate (MFR _B ) at 190 ° C. and 21.2N load condition of polyolefin resin _(MFR a / _{MFR B)} is 0.01 or more, 3 or less is (a) the polylactic acid-based resin and (B) any one of claims 1 to 6, characterized in that by blending the polyolefin resin 2. The resin composition according to item 1. Furthermore, the resin composition of any one of Claims 1-7 formed by mix | blending (F) ethylene / alpha-olefin copolymer different from (B) polyolefin resin. The resin according to any one of claims 1 to 8, wherein (A) a polylactic acid resin and (C) a conjugated diene polymer are melt-kneaded, and then (B) a polyolefin-based resin and other additives are melt-kneaded. A method for producing the composition. 9. (A) A polylactic acid resin and (C) a conjugated diene polymer are melt-kneaded, and then (B) a polyolefin-based resin and other additives are melt-kneaded. Resin composition. The molded article which consists of a resin composition of any one of Claims 1-8 and 10.