JP5267307B2 - Method for producing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a resin composition excellent in moldability, heat resistance, impact resistance and peeling resistance. <P>SOLUTION: The method for producing a resin composition includes melt kneading (A) 1-99 pts.wt. polylactic acid resin, (B) 99-1 pts.wt. polyolefin resin, provided that the total amount of the polylactic acid resin (A) and the polyolefin resin (B) is 100 pts.wt., and (C) 1-50 pts.wt. reactive compatibilizer containing at least one of functional groups selected from the group consisting 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 at a temperature in excess of 250&deg;C. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  In the present invention, the total amount of (A) polylactic acid resin and (B) polyolefin resin is 100 parts by weight, and (A) polylactic acid resin 1 to 99 parts by weight, (B) polyolefin resin 99 to 1 part by weight. And (C) a reactivity containing at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The present invention relates to a method for producing a resin composition comprising 1 to 50 parts by weight of a compatibilizing agent, and is characterized by melt-kneading at a temperature exceeding 250 ° C.

  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 thermoplastic resin composition comprising a lactic acid-based resin, a polypropylene-based resin, and an aromatic vinyl / conjugated diene block copolymer modified with a polar functional group, and a molded article comprising the same. . However, in the invention of Patent Document 1, melt kneading is performed at 180 ° C. when producing the resin composition, and the moldability and peel resistance have some improvement effect, but are still insufficient and the moldability However, there is no suggestion of a solution means for obtaining a resin composition having excellent properties such as heat resistance, impact resistance, and peel resistance.

  Patent Document 2 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. In Patent Document 2, melt kneading is performed at a cylinder temperature of 200 ° C. when producing a resin composition, and although impact resistance has some improvement effect, it is still insufficient, heat resistance, peel resistance, etc. There is no disclosure about the characteristics of the above, and no solution means for obtaining a resin composition excellent in all of the characteristics such as moldability, heat resistance, impact resistance, and peel resistance is suggested.

  Patent Document 3 discloses a resin composition comprising a polylactic acid resin, a polyolefin resin, and a compatibilizing agent. In Patent Document 3, melt kneading is performed at a cylinder temperature of 200 ° C. when producing a resin composition, and moldability, impact resistance and heat resistance have some improvement effects, but are still insufficient. There is no suggestion of a solution for obtaining a resin composition having excellent properties such as heat resistance, heat resistance, impact resistance, and peel resistance.

  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 2006-241445 A (1-2, 19 pages, Examples) JP 2006-52248 A (page 1-2, Examples) JP 2008-38142 A (page 1-3, Examples)

  This invention makes it a subject to provide the resin composition which is excellent in all the characteristics, such as a moldability, heat resistance, an impact resistance, and peeling resistance, which was difficult in the prior art mentioned above.

  As a result of studying the above problems, the present inventors have determined that 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. (B) 99 to 1 part by weight of a polyolefin resin and (C) an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group It has been found that the above-mentioned problems can be solved by melt-kneading 1 to 50 parts by weight of a reactive compatibilizer containing at least one functional group at a temperature exceeding 250 ° C., and the present invention has been achieved.

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. And (C) a reactive phase containing at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group A method for producing a resin composition in which 1 to 50 parts by weight of a solubilizer is melt-kneaded at a temperature of more than 250 ° C. and 280 ° C. or less,
(2) at least one selected from (A) polylactic acid resin and (C) acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The reactive compatibilizing agent containing the functional group is melt-kneaded at a temperature exceeding 250 ° C. and not higher than 280 ° C., and then (B) melt-kneading with a polyolefin-based resin. Method,
(3) The method for producing a resin composition according to the above (1) or (2), wherein the (C) reactive compatibilizing agent is any one or more selected from the following:
(C-1) Polyolefin system containing at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group Resin (C-2) Acrylic containing at least one functional group selected from acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group Resin or styrenic resin (C-3) at least one function selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group Conjugated diene polymer containing a group (4) Melting and kneading temperature is 255 ° C or higher Method for producing a resin composition according to any one of 280 ° C. or less above (1) to (3),
It is.

  The resin composition obtained by the production method of the present invention is excellent in moldability, heat resistance, impact resistance and peel 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.

  The present invention includes the following (A) polylactic acid resin, (B) polyolefin resin, (C) acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group. It is important to melt-knead at a temperature exceeding 250 ° C. when producing a resin composition comprising a reactive compatibilizing agent containing at least one functional group selected from hydroxyl group and epoxy group It is. First, each component will be described.

  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 (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 dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and the like, unsaturated carboxylic acid or derivative thereof and carboxylic acid vinyl ester The modified polyolefin resin modified with such a compound is not included.

  Specific examples include polyethylene resins, polypropylene resins, poly 1-butene resins, poly 1-pentene resins, poly 4-methyl-1-pentene resins and other homopolymers, ethylene / α-olefin copolymers, or these Non-conjugated diene monomers such as 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5- (1′-propenyl) -2-norbornene And a copolymer obtained by copolymerizing one or more of the above.

  In the present invention, the 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 of ˜20 include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 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, and 12-ethyl-1-tetradecene and combinations thereof. Among these α-olefins, a copolymer using an α-olefin having 3 to 12 carbon atoms is preferable from the viewpoint of improving mechanical strength. This ethylene / α-olefin copolymer preferably has an α-olefin content of 1 to 30 mol%, more preferably 2 to 25 mol%, and still more preferably 3 to 20 mol%.

  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 resin is a polypropylene resin, the melt flow rate (MFR) is 1 to 100 g / 10 in that it is excellent in moldability, heat resistance, impact resistance, peel resistance and the like. Minutes, preferably 10 to 100 g / 10 minutes, more preferably 30 to 100 g / 10 minutes.

  In the present invention, the blending ratio of (A) polylactic acid resin and (B) polyolefin resin is (A) when the total amount of (A) polylactic acid resin and (B) polyolefin resin is 100 parts by weight. ) The polylactic acid resin is 1 to 99 parts by weight, preferably 1 to 80 parts by weight, more preferably 1 to 60 parts by weight from the viewpoints of moldability, heat resistance, impact resistance and peel resistance. ~ 40 parts by weight is more preferable, and (B) polyolefin resin is 99 to 1 parts by weight, and 99 to 20 parts by weight is preferable from the viewpoint of moldability, heat resistance, impact resistance, and peel resistance. -40 parts by weight is more preferable, and 99-60 parts by weight is more preferable.

In the present invention, the ratio η _A / η _B of (A) the melt viscosity (η _A ) of the polylactic acid resin and (B) the polyolefin resin melt viscosity (η _B ) at a shear rate of 243 sec ⁻¹ at 210 ° C. 3 ≦ η _A / η _B ≦ 6, more preferably 4 ≦ η _A / η _B ≦ 5, from the viewpoint of excellent properties, heat resistance, impact resistance, and peel resistance. In the present invention, it contains (C) at least one functional group selected from 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 reactive compatibilizing agent is to promote the compatibilization with (A) polylactic acid resin and (B) polyolefin resin, and has the effect of finely dispersing (A) component and (B) component. It is what you have.

In the present invention, the reactive compatibilizer as component (C) is (C) an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group, and epoxy. It is a reactive compatibilizing agent containing at least one functional group selected from the group, and is at least one selected from the following in terms of excellent moldability, heat resistance, impact resistance and peel resistance It is preferable.
(C-1) Polyolefin system containing at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group resin.
(C-2) Conjugated dienes containing at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group Polymer.
(C-3) An acrylic group containing at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group Resin or styrene resin.

  In the present invention, it contains (C) at least one functional group selected from 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 functional group of the reactive compatibilizer is preferably at least one functional group selected from an amino group, an imino group, and an epoxy group in terms of excellent moldability, heat resistance, impact resistance, and peel resistance. .

  (C-1) at least one functional group selected from (C-1) acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group used in the present invention As the polyolefin-based resin to be contained, an olefin homopolymer may be used as long as it contains a predetermined functional group, or a copolymer having a main component of olefin and a copolymerizable compound with olefin may be used. In terms of impact resistance, toughness, peel resistance and paintability, the olefin content is 50% by weight or more, preferably 60% by weight or more, and the compound copolymerizable with the olefin is less than 50% by weight, preferably 40% by weight. An olefin copolymer having less than% is preferred. In the present invention, the olefin includes ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, Examples of the olefin include 1-tetradecene, 1-hexadecene, and 1-octadecene, and these may be used alone or in combination of two or more. In the present invention, examples of the compound copolymerizable with olefin include unsaturated carboxylic acid or its derivative and carboxylic acid vinyl ester. Specifically, acrylic acid, methacrylic acid, methyl acrylate, Methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-methacrylic acid t- Butyl, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, stear acrylate , Stearyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid ester or methacrylic acid ester of polyethylene glycol or polypropylene glycol, trimethoxysilylpropyl acrylate, trimethyl methacrylate Unsaturated carboxylic acids containing (meth) acrylic acid esters such as methoxysilylpropyl, methyldimethoxysilylpropyl acrylate, methyldimethoxysilylpropyl methacrylate, methyl α-hydroxymethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate Acid or its derivatives, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, capryl Vinyl acetate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate and vinyl cyclohexanecarboxylate Functional aliphatic vinyl carboxylates, vinyl benzoates and vinyl cinnamates and other aromatic carboxylates, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotonate and vinyl sorbate Carboxylic acid vinyl ester etc. can be mentioned, and these may be used alone or in combination of two or more, and in terms of impact resistance, toughness, peel resistance, paintability, appearance and surface hardness, Any one of (meth) acrylic acid ester and vinyl acetate There we are preferable.

  (C-1) at least one functional group selected from (C-1) acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group used in the present invention As the polyolefin resin to be contained, the vinyl acetate content or the (meth) acrylic acid ester content is 15% by weight to 40% by weight because it is excellent in moldability, heat resistance, impact resistance and peel resistance. %, Preferably 25% to 40% by weight, and more preferably 30% to 40% by weight. Here, the vinyl acetate content is a value measured according to JIS K 7192, and the (meth) acrylic acid ester content contains a (meth) acrylic acid ester whose contents are known in advance (C- 1) FT of polyolefin resin containing at least one functional group selected from acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group -Measurement curve of each content by measuring IR spectrum, (C-1) acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol containing (meth) acrylic acid ester A polymer containing at least one functional group selected from a group, a silyl ether group, a hydroxyl group and an epoxy group. It is the value calculated from the calibration curve by measuring the FT-IR spectrum of the reolefinic resin.

  In the present invention, (C-1) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The polyolefin-based resin contained has a melt flow rate in the range of 1 to 300 g / 10 min at 190 ° C. and 21.2 N load in terms of excellent moldability, heat resistance, impact resistance and peel resistance. It is preferable that it is 2-50 g / 10 minutes, and it is further more preferable that it is 5-30 g / 10 minutes. Here, the melt flow rate is a value measured according to JIS K 7210.

  (C-1) At least one selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group that can be used in the present invention Examples of polyolefin-based resins containing functional groups include “Bond First” manufactured by Sumitomo Chemical, “Lex Pearl” manufactured by Nippon Polyethylene, “Toughmer” manufactured by Mitsui Chemicals, “Modiper” manufactured by Nippon Oil and Fats, and “Modyper” manufactured by Sanyo Chemical Industries Umex ”, Arkema“ Orevac ”, Arkema“ Rotada ”, Arkema“ Bondyne ”, Arkema“ Evadine ”, Mitsui DuPont Polychemical“ Nucleel ”, Dow Chemical“ Primacol ”, etc. Can do.

  In the present invention, (C-2) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The conjugated diene-based polymer to be contained is a conjugated diene homopolymer, a copolymer of a conjugated diene and a compound copolymerizable with a conjugated diene, or the like as long as it contains a predetermined functional group. Any of the above hydrogenated copolymers may be used, but in terms of excellent moldability, heat resistance, impact resistance, peel resistance, paintability and surface hardness, a compound capable of copolymerizing with a conjugated diene and a conjugated diene Or a hydrogenated copolymer thereof is preferred, and the conjugated diene is the main component in that it is excellent in moldability, heat resistance, impact resistance, peel resistance, paintability and surface hardness. A block copolymer containing a block composed mainly of a block copolymer and a compound copolymerizable with a conjugated diene, or a hydrogenated block copolymer thereof is more preferable. Formability, heat resistance, impact resistance, and peeling resistance A block copolymer in which a block mainly composed of a conjugated diene exists on the inside and a block mainly composed of a compound copolymerizable with the conjugated diene exists on the outside, or those The hydrogenated block copolymer 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, heat resistance and paintability. More preferred are copolymers of system units and aromatic vinyl units or hydrogenated copolymers thereof. Specific examples include styrene / butadiene random copolymers, styrene / butadiene block copolymers, styrene / butadiene / Styrene block copolymer (SBS), styrene / isoprene random copolymer, styrene / isoprene block copolymer, styrene / isoprene / styrene block copolymer (SIS), polybutadiene grafted with styrene, butadiene / Acrylonitrile copolymer, styrene / butadiene / butylene / carbon Ren 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)) and the like. 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 10 to 40% by weight in terms of excellent peelability. Is more preferable, and it is further more preferable that it is 15 to 35 weight% at the point that it is excellent in a moldability and heat resistance.

  In the present invention, the melt flow rate (MFR) of the conjugated diene polymer under the conditions of 230 ° C. and 21.2N load may be any value, but the moldability, heat resistance, impact resistance and peel resistance are not limited. Is preferably 1 g / 10 min or more, more preferably 5 g / 10 min or more, still more preferably 18 g / 10 min or more, particularly in terms of excellent peelability. It is particularly preferably 50 g / 10 min or more, and most preferably 100 g / 10 min or more.

  In the present invention, (C-3) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The acrylic resin or styrene resin to be contained is more preferably an epoxy group-containing acrylic resin or styrene resin.

  In the present invention, (C-3) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The weight average molecular weight of the acrylic resin or styrene resin to be contained is preferably a polymer having 1000 to 300,000. Here, the weight average molecular weight is a polymethyl methacrylate (PMMA) conversion weight average molecular weight measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  In the present invention, (C-3) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The acrylic resin or styrene resin to be contained only needs to contain a (meth) acrylic ester vinyl unit or a styrene vinyl unit as a main component, more preferably 60% by weight or more, and still more preferably 80% by weight or more. Further, a copolymer obtained by copolymerizing other vinyl monomer component units excluding the olefin monomer, preferably 40% by weight or less, more preferably 20% by weight or less may be used. In the present invention, the component (C-3) is at least one selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group. In the case of a styrenic resin containing a kind of functional group, it is sufficient that the styrenic vinyl unit is contained even a little from the point of being excellent in moldability, heat resistance, impact resistance and peel resistance. % By weight is preferable, and 5 to 10% by weight is more preferable.

  In the present invention, specific examples of the raw material monomer for forming the (meth) acrylic ester vinyl unit are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, and acrylic acid n. -Butyl, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, acrylic Isobornyl acid, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylic acid Droxypropyl, hydroxypropyl methacrylate, polyethylene glycol or polypropylene glycol acrylic ester or methacrylic ester, trimethoxysilylpropyl acrylate, trimethoxysilylpropyl methacrylate, methyldimethoxysilylpropyl acrylate, methyldimethoxysilylpropyl methacrylate , Α-hydroxymethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl acrylate, and the like. In terms of durability, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, N-butyl crylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, methacrylic acid Preferred are cyclohexyl acid, isobornyl acrylate, isobornyl methacrylate, acrylonitrile, methacrylonitrile, and further methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, acrylic 2-ethylhexyl acid, 2-ethylhexyl methacrylate, acrylonitrile and methacrylonitrile are preferable, and methyl methacrylate is more preferable in terms of heat resistance. These may be used alone or in combination of two or more.

  In the present invention, specific examples of the raw material monomer for forming the styrene-based vinyl unit include styrene, α-methylstyrene, p-methylstyrene, α-methyl-p-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, 1-vinylnaphthalene, chlorostyrene, bromostyrene, divinylbenzene, vinyltoluene and the like can be mentioned. Among them, styrene and α-methylstyrene are preferably used. These may be used alone or in combination of two or more.

  In the present invention, (C-3) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group As the acrylic resin or styrene resin to be contained, a conjugated diene polymer having a styrene unit is excluded.

  In the present invention, (C-3) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The melt flow rate (MFR) of the acrylic resin or styrene resin to be contained is preferably 1 to 30 g / 10 minutes in terms of excellent moldability, heat resistance, impact resistance, and peel resistance. It is more preferably 2 to 15 g / 10 minutes, and further preferably 3 to 13 g / 10 minutes.

  In the present invention, (C-3) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group When the acrylic resin or styrene resin to be contained is an epoxy group-containing acrylic resin or styrene resin, the epoxy value is 0.1 to 10 meq in terms of moldability, heat resistance, impact resistance and peel resistance. / G, preferably 1 to 7 meq / g, more preferably 2 to 4.5 meq / g, and 2.5 to 4 meq / g. It is particularly preferred. Using an epoxy with an epoxy value of 0.1 meq / g or more will have a sufficient effect of improving heat resistance, and using an epoxy with an epoxy value of 10 meq / g or less will reduce moldability due to gelation or the like. This is preferable because there is not. Here, the epoxy value is a value measured by a hydrochloric acid-dioxane method. In addition, the epoxy value of the polymer containing a glycidyl group-containing vinyl-based unit can be adjusted by adjusting the content of the glycidyl group-containing vinyl-based unit.

  In the present invention, (C-3) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The glass transition temperature of the acrylic resin or styrene resin to be contained is not particularly limited, but is preferably in the range of 30 to 100 ° C., and in the range of 40 to 70 ° C. in terms of excellent handling properties. More preferably, it is the range of 50-65 degreeC. The glass transition temperature here is a value measured by DSC according to the method described in JIS K7121, and is the midpoint glass transition temperature when the temperature is raised at 20 ° C./min. (C-3) Contains at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The glass transition temperature of the acrylic resin or styrene resin can be controlled by adjusting the composition of the copolymer component. The glass transition temperature can usually be increased by copolymerizing aromatic vinyl units such as styrene, and can be decreased by copolymerizing (meth) acrylic ester vinyl units such as butyl acrylate. it can.

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

  In the present invention, (C-3) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The acrylic resin or styrene resin to be contained may use a sulfur compound as a chain transfer agent (molecular weight modifier) in order to obtain a low molecular weight product. In that case, the polymer usually contains sulfur. Here, although sulfur content is not specifically limited, From the viewpoint of suppressing unpleasant odor, it is preferable that the sulfur content is small. Specifically, the sulfur atom is preferably 1000 ppm or less, more preferably 100 ppm or less, further preferably 10 ppm or less, and most preferably 1 ppm or less.

  In the present invention, (C-3) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The method for producing the acrylic resin or styrene resin to be contained is not particularly limited as long as the conditions specified in the present invention are satisfied. Known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization Can be used. When using these methods, a polymerization initiator, a chain transfer agent, a solvent, and the like may be used. These are finally obtained (C-3) acid anhydride groups, carboxyl groups, amino groups, It may remain as an impurity in an acrylic resin or styrene resin containing at least one functional group selected from an imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group. The amount of these impurities is not particularly limited, but it is preferable that the amount of impurities is small from the viewpoint of suppressing a decrease in heat resistance and weather resistance. Specifically, the amount of impurities is preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 3% by weight or less, particularly 1% by weight or less, with respect to the finally obtained polymer. Most preferred.

  (C-3) acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group satisfying the molecular weight, glass transition temperature, nonvolatile component amount, sulfur content, impurity amount, etc. As a method for producing an acrylic resin or styrene resin containing at least one functional group selected from a silyl ether group, a hydroxyl group and an epoxy group, a high temperature of 150 ° C. or higher and pressure conditions (preferably The method of continuous bulk polymerization in a short time (preferably 5 to 30 minutes) in 1 MPa or more does not use a polymerization initiator, a chain transfer agent, or a solvent that causes a high polymerization rate, impurities or sulfur content. More preferable in terms.

  (C-3) at least one selected from acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group that can be used in the present invention Examples of the product of acrylic resin or styrene resin containing a functional group include “ARUFON” manufactured by Toagosei Co., Ltd. and “JONCRYL” manufactured by Johnson Polymer.

  In the present invention, it contains (C) at least one functional group selected from 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 compounding amount of the reactive compatibilizer is 1 to 50 parts by weight, preferably 3 to 40 parts by weight, more preferably 100 parts by weight of the total amount of (A) and (B). Is less than 1 part by weight, the effect as a compatibilizing agent is small, and if it exceeds 50 parts by weight, the mechanical properties deteriorate, which is not preferable.

In the present invention, as the phase structure of the resin composition, a phase structure in which either (A) a polylactic acid resin or (B) a polyolefin resin is a dispersed phase and the other is a continuous phase (matrix phase). However, from the viewpoint of moldability, heat resistance, impact resistance and peel resistance, it is preferable that (A) the polylactic acid-based resin forms a dispersed phase and (B) the polyolefin-based resin forms a continuous phase. . Further, from the viewpoint of moldability, heat resistance, impact resistance and peel resistance, the average particle size of the dispersed phase is preferably 1 μm or less, more preferably 700 nm or less, further preferably 500 nm or less, particularly preferably 100 nm or less, Most preferred is 70 nm or less. Further, as a phase structure of the resin composition, (A) a polylactic acid resin forms a dispersed phase, and (C) an acid anhydride group, a carboxyl group, an amino group, an imino group, an alkoxysilyl group, It is preferable that a reactive compatibilizer containing at least one functional group selected from a silanol group, a silyl ether group, a hydroxyl group, and an epoxy group forms a phase structure that becomes a dispersed phase, moldability, heat resistance, From the viewpoint of impact resistance and peel resistance, the area of the component (C) dispersed phase in the component (A) dispersed phase is preferably 10% or more, more preferably 20% or more, 25% More preferably, it is more preferably 30% or more.
The phase structure in the present invention can be confirmed by observation using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). In the present invention, the magnification is 10,000 times using TEM. It is preferable to confirm with. 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. (A) at least selected from (C) acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group in the polylactic acid resin dispersed phase The area of the reactive compatibilizer dispersed phase containing one type of functional group was measured by digitizing a photograph observed with an electron microscope and subjecting it to image processing according to a conventional method.

  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 , Organic fillers in the form of fibers, powders or chips, such as rice husks, wood chips, okara, waste paper grinds, clothing grinds. 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 at the point which can improve further durability and toughness of the resin composition obtained by mix | blending a carboxyl group reactive compound. 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 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 (A) polylactic acid resin and (B) polyolefin resin, 0.05 -5 parts by weight is more preferred.

  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.

  In the present invention, (C-3) at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The melt flow rate (MFR) of the acrylic resin or styrene resin to be contained is preferably 1 to 30 g / 10 minutes in terms of excellent moldability, heat resistance, impact resistance, and peel resistance. It is more preferably 2 to 15 g / 10 minutes, and further preferably 3 to 13 g / 10 minutes.

  In the present invention, the melt flow rate (MFR) of the carboxyl group-reactive compound is more than 30 g / 10 minutes, and 30 to 30 in terms of excellent moldability, heat resistance, impact resistance, and peel resistance. It is preferably 300 g / 10 minutes, more preferably 35 to 200 g / 10 minutes, and even more preferably 40 to 100 g / 10 minutes.

  In the present invention, (A) polylactic acid resin, (B) polyolefin resin, (C) acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and It is important to melt-knead the reactive compatibilizing agent containing at least one functional group selected from epoxy groups and, if necessary, other additives at a temperature exceeding 250 ° C. Here, the temperature of melt kneading is the temperature of a cylinder such as an extruder.

  In the present invention, it contains (C) at least one functional group selected from 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. By melt-kneading the reactive compatibilizer at a temperature exceeding 250 ° C., the reaction with the terminal of (A) polylactic acid resin is promoted, and (A) the polylactic acid resin and (B) polyolefin resin Since the interfacial adhesion is improved, a resin composition excellent in moldability, heat resistance, impact resistance and peel resistance can be obtained, and in particular, it cannot be obtained by melt-kneading at a temperature of 250 ° C. or lower. In particular, a resin composition having excellent peel resistance can be obtained.

  Examples of the melt kneading of the resin composition of the present invention include a melt kneading method using a single screw or twin screw extruder, and (A) a polylactic acid resin, (B) a polyolefin resin, and (C) an acid. Reactive compatibilizers containing at least one functional group selected from an anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group in a lump A method of blending and melt-kneading at a temperature exceeding 250 ° C., (A) polylactic acid resin and (C) acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, A reactive compatibilizing agent containing at least one functional group selected from a hydroxyl group and an epoxy group was blended and melt-kneaded at a temperature exceeding 250 ° C. Furthermore, (B) a method of melt-kneading with a polyolefin resin, from the main feeder, (A) a polylactic acid resin and (C) an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl A method of supplying a reactive resin containing at least one functional group selected from an ether group, a hydroxyl group and an epoxy group, and supplying (B) a polyolefin-based resin from a side feeder at the tip of an extruder, etc. (A) a polylactic acid resin, (B) a polyolefin resin, and (C) an acid anhydride group, carboxyl in terms of excellent balance of moldability, heat resistance, impact resistance and peel resistance. Group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group A method in which a reactive compatibilizer containing at least one selected functional group is batch-blended and melt-kneaded at a temperature exceeding 250 ° C. is preferred, (A) a polylactic acid resin and (C) an acid anhydride group, A reactive compatibilizing agent containing at least one functional group selected from 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 is blended, and the temperature exceeds 250 ° C. (B) A method of further melt-kneading with the polyolefin-based resin after melt-kneading in (1) is more preferable. In addition, you may mix | blend another additive as needed, and either the method of supplying from a main feeder or the method of supplying from a side feeder may be sufficient as another additive.

  In the present invention, the melt kneading temperature at the time of producing the resin composition is more than 250 ° C, preferably 250 ° C to 280 ° C, more preferably 255 ° C to 275 ° C, and particularly preferably 260 ° C to 270 ° 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 70 ° C. or higher, from the viewpoint of heat resistance, moldability, and appearance. 120 degrees C or less is preferable from the point that a deformation | transformation can be suppressed, 99 degrees C or less is more preferable, and 90 degrees C or less is further more preferable.

  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, door trim and other automotive interior parts, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers , Hood louver, wheel cover, wheel cap, grill apron cover frame, lamp reflector, lamp bezel Automotive exterior parts such as door handles, mention may be made of wire harness connector, SMJ connector, PCB connector, the auto parts typified by various connector for automobiles such as door grommet connector. 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.

  From the viewpoint 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 70 J. / M or more, the deflection temperature under load at 0.45 MPa is more preferably 100 ° C. or more, the Izod impact strength is at least 100 J / m, 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 body 1.2%, Mw (converted to PMMA) 160,000, melting point 168 ° C.)

(B) Polyolefin-based resin (B-1) Polypropylene resin (homopolymer, prime polymer J108M, MFR 45 g / 10 min (230 ° C., 21.2 N), melting point 169 ° C.)
(B-2) Polypropylene resin (block polymer, prime polymer J708UG, MFR 45 g / 10 min (230 ° C., 21.2 N), melting point 169 ° C.)

(C) Compatibilizer (C-1) At least one function selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group Group-containing polyolefin-based resin (C-1-1) ethylene / glycidyl methacrylate copolymer resin (“Sumitomo Chemical“ bond first ”E, melting point 88 ° C., glycidyl methacrylate 12% by weight, MFR 3 g / 10 min (190 ° C. 21.2N))
(C-1-2) ethylene / methyl acrylate / glycidyl methacrylate copolymer resin (Sumitomo Chemical "bond first" 7M, methyl acrylate content 30% by weight, glycidyl methacrylate content 6% by weight, MFR 9 g / 10 Min (190 ° C, 21.2N))
(C-2) Conjugated dienes containing at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group -Based polymer (C-2-1) maleic anhydride-modified SEBS ("Tough Tech" M1962, manufactured by Asahi Kasei Chemicals Co., Ltd., styrene content 30 wt%, MFR 150 g / 10 min (230 ° C, 21.2 N))
(C-2-2) Imine group-modified SEBS (“Tough Tech” MP10, manufactured by Asahi Kasei Chemicals Co., Ltd., styrene content 30% by weight, MFR 4 g / 10 min (230 ° C., 21.2 N))
(C-2-3) Imine 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-2-4) Amino group-modified SEBS (“Dynalon” 8630P manufactured by JSR, styrene content 15% by weight, MFR 15 g / 10 min (230 ° C., 21.2 N))

(D) Filler (D-1) Talc (Nihon Talc P-6)

(E) Plasticizer (E-1) Polyethylene glycol (PEG 6000S manufactured by Sanyo Chemical Industries)

(F) Carboxyl group reactive compound (F-1) Polycarbodiimide (Nisshinbo “Carbodilite” LA-1)

(G) Other polymer (G-1) SEBS (“Tough Tech” H1031, manufactured by Asahi Kasei Chemicals Co., Ltd., styrene content 30% by weight, MFR 150 g / 10 min (230 ° C., 21.2 N))

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

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

(2) Fluidity (MFR)
According to JIS K7210, it measured at 190 degreeC or 230 degreeC and a 21.2N load.

(3) Formability Regarding the formability, when a tensile test piece that can be subjected to a tensile test was taken out from the mold, the shortest time during which a solidified molded product without deformation was obtained 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) 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.

(6) Peeling resistance A grid-like cut is made in the vicinity of the square gate with a cutter knife at intervals of 1 mm, cellophane tape is adhered onto the grid, and instantaneously at an angle of 90 ° to the square plate surface. After peeling off, the state of the surface of the molded product was observed 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

[Examples 1-8, Comparative Examples 1-8]
The raw materials shown in Table 1 are batch-blended, and melt-kneaded at a predetermined melt-kneading temperature and a rotation speed of 200 rpm using a 30 mm diameter twin-screw extruder (TEX-30α manufactured by Nippon Steel) to obtain a resin composition. Obtained.

  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.

  Table 1 shows the results of various evaluations using the obtained molded product.

  From the results in Table 1, it can be seen that the (A) component, the (B) component, and the (C) component are blended and melt-kneaded at 260 ° C. so that the moldability and the peel resistance are excellent.

[Examples 9 to 17, Comparative Examples 9 to 16]
Using the raw materials shown in Table 2, first, the (A) component and the (C) component are blended, and using a 30 mm diameter twin screw extruder (Nippon Steel Works TEX-30α), a predetermined melt kneading temperature and rotation speed Melt kneading was performed at 200 rpm to obtain a resin composition. Thereafter, the resin composition obtained by melt-kneading the component (A) and the component (C) and the component (B) are blended, and a 30-mm diameter twin screw extruder (TEX-30α manufactured by Nippon Steel Works) is used. Was melt kneaded under the conditions of the melt kneading temperature and the rotational speed of 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 molded products for various evaluations.

  Table 2 shows the results of various evaluations using the obtained molded product.

  From the results of Table 2, it can be seen that the components (A) and (C) are blended, melt-kneaded at 260 ° C., and then melt-kneaded with the component (B), thereby being excellent in moldability and peel resistance. .

[Examples 18 to 23, Comparative Examples 17 and 18]
The raw materials shown in Table 3 are batch-blended and melt kneaded at a predetermined melt kneading temperature and a rotation speed of 200 rpm using a 30 mm diameter twin screw extruder (TEX-30α manufactured by Nippon Steel Works) to obtain a resin composition. Obtained.

  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.

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

  From the results in Table 3, by blending (A) component, (B) component (C) component and other additives, and melt-kneading at 260 ° C., moldability, heat resistance, impact resistance and peel resistance It turns out that it is excellent.

[Examples 24 to 30, Comparative Examples 19 to 21]
Using the raw materials shown in Table 4, first, the (A) component and the (C) component were blended, and using a 30 mm diameter twin screw extruder (TEX-30α manufactured by Nippon Steel), a predetermined melt kneading temperature and rotation speed Melt kneading was performed at 200 rpm to obtain a resin composition. Thereafter, the resin composition obtained by melt-kneading the component (A) and the component (C) and the component (B) are blended, and a 30-mm diameter twin screw extruder (TEX-30α manufactured by Nippon Steel Works) is used. Was melt kneaded under the conditions of the melt kneading temperature and the rotational speed of 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 molded products for various evaluations.

  Table 4 shows the results of various evaluations using the obtained molded product.

  From the results of Table 4, after blending the component (A) and the component (C) and melt-kneading at 260 ° C., further melt-kneading with the component (B) and other additives, moldability, heat resistance, It can be seen that it has excellent impact resistance and peel resistance, and in particular, excellent impact resistance.

Claims (4)

(A) 1 to 99 parts by weight of a polylactic acid resin, (B) 99 to 1 part by weight of a polyolefin resin, and (C), where the total amount of the polylactic acid resin and (B) polyolefin resin is 100 parts by weight. ) Reactive compatibilizer 1 containing at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group A method for producing a resin composition, in which -50 parts by weight are melt-kneaded at a temperature exceeding 250 ° C and not more than 280 ° C. (A) at least one functional group selected from polylactic acid resin and (C) acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group The method for producing a resin composition according to claim 1, wherein a reactive compatibilizing agent containing is melt-kneaded at a temperature of more than 250 ° C and not more than 280 ° C, and further (B) melt-kneaded with the polyolefin resin. The method for producing a resin composition according to claim 1 or 2, wherein the (C) reactive compatibilizing agent is at least one selected from the following.
(C-1) Polyolefin system containing at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group Resin (C-2) Acrylic containing at least one functional group selected from acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group Resin or styrenic resin (C-3) at least one function selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group Conjugated diene polymer containing a group The method for producing a resin composition according to any one of claims 1 to 3, wherein the melt kneading temperature is from 255C to 280C.