JP2012067148A - Polylactic acid-containing polypropylene resin composition for extrusion molding, method for producing the same, and extrusion molded product comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polylactic acid-containing polypropylene resin composition for extrusion molding which has an excellent flexural modulus, excellent heat resistance and impact resistance and an excellent melt tension and can easily form an extrusion molded product such as a blow molded product, a method for producing the same, and an extrusion molded product comprising the same.SOLUTION: The polylactic acid-containing polypropylene resin composition for extrusion molding contains 30-89.5 wt.% of the following component (A), 0.1-5 wt.% of a component (B), 10-50 wt.% of a component (C), and 0.4-15 wt.% of a component (D), and has an MFR (230°C) of ≤5 g/10 min, a flexural modulus of ≥1,500 MPa, a melt tension at 190°C of ≥10 g, and a heat distortion temperature of ≥80°C. The component (A): a polypropylene resin having an MFR (230°C) of ≤10 g/10 min and a flexural modulus of 1,800-2,600 MPa, the component (B): a maleic acid-modified polyolefinic resin or the like, the component (C): a polylactic acid-based resin having an MFR (190°C) of 1-7 g/10 min, the component (D): an epoxy-modified polyolefinic resin.

Description

  The present invention relates to a polylactic acid-containing polypropylene resin composition for extrusion molding, a process for producing the same, and an extrusion-molded body comprising the same. More specifically, the present invention has excellent bending elastic modulus, heat resistance and impact resistance, and excellent melt tension. The present invention relates to a polylactic acid-containing polypropylene resin composition for extrusion molding, which can easily form an extrusion molded body (particularly a blow (hollow) molded body), a method for producing the same, and an extrusion molded body comprising the same.

In recent years, with increasing awareness of environmental problems, used resin products are required to decompose and disappear over time in the natural environment and ultimately have no adverse effect on the natural environment. Conventional resins are stable in the natural environment for a long time and have a low bulk specific gravity.Therefore, there are problems that promote the shortening of the life of the landfill site and damage the natural landscape and the living environment of wild animals and plants. It was pointed out. Therefore, biodegradable resins have attracted attention. Biodegradable resins are known to gradually disintegrate and decompose by hydrolysis and biodegradation in soil and water, and finally become harmless degradation products by the action of microorganisms. In addition, waste treatment can be easily performed by composting.
Furthermore, in recent years, it has been required from the viewpoint of environmental protection to use a material derived from a plant material, not a material derived from a conventional petrochemical product, as a material for a resin. It can be derived from plant raw materials, and biodegradable resins are also attracting attention from this point of view.

Biodegradable resins that have begun to be put into practical use include aliphatic polyesters, modified PVA, cellulose ester compounds, starch modified products, and blends thereof. Each of these biodegradable resins has unique characteristics, and application development according to these characteristics can be considered.
Among them, aliphatic polyesters are beginning to be widely used because they have a wide range of properties and molding processability similar to general-purpose resins.
Among aliphatic polyesters, lactic acid resins are excellent in transparency, rigidity, heat resistance, and the like, and thus are attracting attention in the packaging film field and injection molding field as alternative materials for polystyrene and polyethylene terephthalate.
On the other hand, a resin used in the extrusion molding field such as blow molding must be excellent in melt tension. However, in general, biodegradable resins such as the lactic acid-based resins have a high temperature dependency of viscosity, and thus the problem of unstable melt tension that greatly affects the extrusion (working) property becomes obvious.

  Polylactic acid, which is typical as a lactic acid-based resin, has a disadvantage that it is inferior in heat resistance and impact resistance as compared with general-purpose resins such as polypropylene. Therefore, various attempts have been made to improve the properties of polylactic acid. For example, Patent Document 1 discloses a fiber-reinforced molded body composed of 100 parts by weight of aliphatic polyester and 5 to 500 parts by weight of reinforcing biodegradable fibers having an average fiber length of 1 to 50 mm. Based on such improved technology, lactic acid-based resins are being developed for various uses, but their physical properties are not sufficient as compared with general-purpose resins, and their use has been limited.

Furthermore, as a method for improving the physical properties of a resin such as polylactic acid, a conventionally known technique is a polymer blend or a polymer alloy. Various resins are forcibly mixed and kneaded to improve impact resistance, flexibility, rigidity, and heat resistance (see, for example, Patent Documents 2 to 4).
Patent Document 2 discloses a naturally decomposable resin composition comprising 85 to 99% by weight of an aliphatic polyester mainly composed of lactic acid and 1 to 15% by weight of syndiotactic polypropylene. Patent Document 3 discloses a thermoplastic resin component (A) derived from fossil resources, a thermoplastic resin component (B) derived from biomass, and both a thermoplastic resin component (A) and a thermoplastic resin component (B). A thermoplastic resin molded article containing a thermoplastic resin component (C) that is compatible or dispersible with respect to the thermoplastic resin molded article is disclosed. However, impact resistance is insufficient for automobiles. Furthermore, Patent Document 4 discloses a polylactic acid resin composition having improved impact resistance by mixing a modified olefin compound with polylactic acid.
Although the physical properties of the resin have been improved in this way, in general, different types of polymers are hardly compatible with each other, and the performance has not been sufficiently improved.

Therefore, a method for improving the compatibility between different kinds of polymers by adding a compatibilizing agent has been proposed.
For example, Patent Document 5 discloses a film obtained by heating and melting a composition obtained by blending an aliphatic polyester resin and a polyolefin resin with a graft polymer having a comb structure as a compatibilizing agent. Patent Document 6 discloses a thermoplastic resin composition containing a lactic acid resin, a polypropylene resin, and a specific compatibilizer as constituent components. Further, Patent Document 7 discloses an extrudable resin in which a low density polyethylene is blended with a styrene / ethylene / butylene / styrene block copolymer as a compatibilizer in a blend system of a lactic acid resin and a polypropylene resin. A composition is disclosed.
However, it is a polypropylene resin composition containing a lactic acid-based resin such as polylactic acid, and can form an extruded product that can be used for automobile parts having excellent impact resistance and heat-resistant rigidity due to polymer alloy. A composition has not yet been obtained.

JP-A-9-169897 JP-A-10-251498 JP 2006-70210 A JP 9-316310 A JP-A-6-263892 JP 2006-131716 A JP 2009-179750 A

  Under such circumstances, the problems of the conventional polylactic acid-containing polypropylene resin composition and the molded product are eliminated, and an excellent flexural modulus suitable for obtaining an extruded product, particularly an extruded product for automobile parts, Polylactic acid-containing polypropylene resin composition for extrusion molding that can easily form extrusion moldings such as blow moldings by having heat resistance and impact resistance and additionally having excellent melt tension necessary for extrusion molding There is a demand for an article, a method for producing the same, and an extruded product comprising the same.

  In view of the above-mentioned problems of the prior art, the object of the present invention is to provide an excellent bending elastic modulus, heat resistance and impact resistance, and in addition to having an excellent melt tension necessary for extrusion molding, It is an object to provide a polylactic acid-containing polypropylene resin composition for extrusion, which can easily form an extrusion-molded body such as the above, a method for producing the same, and an extrusion-molded body comprising the same.

  As a result of intensive studies to solve the above problems, the present inventors have specified specific components (A) to (D) or specific components (A) to (E) in which component (E) is further blended. When a resin composition containing a large amount was prepared, it was found that an extrusion-molded body having excellent bending elastic modulus, heat resistance, impact resistance and melt tension can be easily formed. Moreover, the manufacturing method of the said polylactic acid containing polypropylene resin composition by the kneading | mixing method which consists of two specific processes was also discovered. These findings have been further studied and the present invention has been completed.

That is, according to the first invention of the present invention, the following component (A) 30 to 89.5 wt%, component (B) 0.1 to 5 wt%, and component (C) 10 to 50 wt% And a resin composition containing 0.4 to 15% by weight of component (D), the melt flow rate (230 ° C., 21.18 N) is 5 g / 10 min or less, measured according to ISO 178 Polylactic acid-containing polypropylene resin composition for extrusion molding having a flexural modulus of 1500 MPa or more, a melt tension at 190 ° C. of 10 g or more, and a heat distortion temperature measured according to ISO 75-2 of 80 ° C. or more. Is provided.
Component (A): Polypropylene resin having a melt flow rate (230 ° C., 21.18 N) of 10 g / 10 min or less and a flexural modulus measured according to ISO 178 of 1800 to 2600 MPa Component (B): anhydrous Maleic acid-modified polyolefin resin and / or hydroxy-modified polyolefin resin Component (C): Polylactic acid resin having a melt flow rate (190 ° C., 21.18 N) of 1 to 7 g / 10 min Component (D): Epoxy-modified Polyolefin resin

Moreover, according to the second invention of the present invention, in the first invention, the extrusion further comprises 1-30 wt% of the elastomer as the component (E) with respect to the total amount of the resin composition. A polylactic acid-containing polypropylene resin composition for molding is provided.
Furthermore, according to the third invention of the present invention, in the first or second invention, the polypropylene resin of component (A) is a propylene homopolymer (A1), and propylene is homopolymerized in at least two stages, Of the polymer parts produced at each stage, when the intrinsic viscosity of the polymer part with the highest molecular weight is [η] _H and the intrinsic viscosity of the polymer part with the lowest molecular weight is [η] _L , [η] _H And [η] _L satisfy the relational expression (1), and a polylactic acid-containing polypropylene resin composition for extrusion molding is provided.
3.0 ≦ [η] _H − [η] _L ≦ 6.5 (1)

According to a fourth invention of the present invention, in any one of the first to third inventions, the component (B) is a maleic anhydride-modified polyolefin resin, and the acid amount is 0.05 to 5 in terms of maleic anhydride. There is provided a polylactic acid-containing polypropylene resin composition for extrusion molding characterized by being 10% by weight.
According to the fifth aspect of the present invention, in any one of the first to fourth aspects, the component (C) is polylactic acid and contains L-lactic acid or D-lactic acid as a main component. A polylactic acid-containing polypropylene resin composition for extrusion molding is provided.
Furthermore, according to the sixth invention of the present invention, in any one of the first to fifth inventions, the component (D) is an ethylene-glycidyl methacrylate copolymer, which contains polylactic acid for extrusion molding A polypropylene resin composition is provided.

On the other hand, according to the seventh invention of the present invention, the polylactic acid-containing resin composition for extrusion molding according to any one of the first to sixth inventions, comprising the following steps (I) and (II): A manufacturing method is provided.
Step (I): Step of melting and kneading 10 to 50% by weight of the following component (C) and 0.4 to 15% by weight of component (D) Step (II): Melting and kneading obtained in the step (I) The step of melt-kneading the following component (A) 30 to 89.5 wt% and component (B) 0.1 to 5 wt% into the resin composition Component (A): Melt flow rate (230 ° C., 21 .18N) is a polypropylene resin having a flexural modulus measured in accordance with ISO 178 of 1800 to 2600 MPa of 10 g / 10 min or less. Component (B): Maleic anhydride-modified polyolefin resin and / or hydroxy-modified polyolefin system Resin Component (C): Polylactic acid resin having a melt flow rate (190 ° C., 21.18 N) of 1 to 7 g / 10 minutes Component (D): Epoxy-modified polyolefin resin According to the eighth invention, in the seventh invention, in the step (II), 1-30 wt% of the elastomer as the component (E) is further melt-kneaded with respect to the total amount of the resin composition. The manufacturing method of the polylactic acid containing resin composition for extrusion molding characterized by the above-mentioned is provided.

In addition, according to the ninth aspect of the present invention, there is provided a molded body obtained by extruding the polylactic acid-containing polypropylene resin composition for extrusion molding according to any one of the first to sixth aspects.
Furthermore, according to the 10th invention of this invention, the molded object formed by blow-molding the polylactic acid containing polypropylene resin composition for extrusion molding which concerns on any one of the 1st-6th invention is provided.

  According to the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention and the extrusion molded body comprising the same, it has excellent bending elastic modulus, heat resistance and impact resistance, and in addition, has excellent melt tension necessary for extrusion molding. By having it, an extrusion-molded body such as a blow-molded body can be easily formed, so that there is an effect that it can be suitably used for applications such as automobile parts. Moreover, according to the manufacturing method of this invention, there exists an effect that the said polylactic acid containing polypropylene resin composition for extrusion molding can be manufactured easily.

  Hereinafter, the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention, the production method thereof, and the extrusion-molded body comprising the same will be described in detail for each item.

I. Polylactic acid-containing polypropylene resin composition for extrusion molding The polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention comprises 30 to 89.5% by weight of the following components (A) and 0.1 to 5 components (B). The component (E) contains 10 to 50% by weight, component (C) 10 to 50% by weight, and component (D) 0.4 to 15% by weight. 1) to 30% by weight, characterized by having the following specific physical properties and melting characteristics necessary for extrusion molding.

That is, the resin composition has a melt flow rate (hereinafter referred to as MFR) (230 ° C., 21.18 N) of 5 g / 10 min or less, preferably 0.01 g to 4.5 g / 10 min, more preferably 0.1 g to 4 g / 10 min, the flexural modulus measured according to ISO 178 is 1500 MPa or more, preferably 1600 MPa or more, more preferably 1700 MPa or more, and the melt tension at 190 ° C. is 10 g or more, preferably Each physical property is 10.5 to 30 g, more preferably 11 to 28 g, and the heat distortion temperature measured according to ISO 75-2 is 80 ° C. or higher, preferably 81 ° C. or higher, more preferably 82 ° C. or higher. And has melting characteristics.
Here, when the MFR (230 ° C., 21.18 N) exceeds 5 g / 10 minutes, or the melt tension at 190 ° C. is less than 10 g, extrusion molding (processing) such as blow moldability of the resin composition of the present invention. ) Properties are reduced, and it becomes difficult to form (process) the extruded product. Further, if the flexural modulus is less than 1500 MPa or the heat distortion temperature is less than 80 ° C., the heat resistance rigidity of the resin composition and the extrusion-molded product is insufficient.

1. Each component (1) component (A) of the resin composition: polypropylene resin The polypropylene resin of the component (A) according to the present invention (hereinafter also simply referred to as component A) is MFR (230 ° C., 21.18 N), It is 10 g / 10 min or less, preferably 0.05-5 g / 10 min or less, more preferably 0.1-2 g / 10 min or less. When the MFR exceeds 10 g / 10 min, the melt tension is lowered and it is not suitable for forming an extrusion-molded body such as a blow-molded body.

  Component A according to the present invention has a flexural modulus measured in accordance with ISO178 of 1800 to 2600 MPa, preferably 1850 to 2550 MPa, more preferably 1900 to 2500 MPa. When the flexural modulus is less than 1800 MPa, the flexural modulus of the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention is lowered. On the other hand, when it exceeds 2600 MPa, impact resistance is lowered.

The component A according to the present invention is either a propylene homopolymer (A1) or a propylene / ethylene block copolymer (A2) having a propylene homopolymer and a propylene / ethylene copolymer.
The preferred propylene homopolymer (A1) used in the present invention is a propylene copolymer in which a comonomer such as ethylene and 1-butene is copolymerized in addition to a propylene homopolymer, as long as the object of the present invention is not significantly impaired. Is also included. In this case, the amount of comonomer is preferably less than about 1% by weight.

The propylene homopolymer (A1) preferably used in the present invention is obtained by homopolymerizing propylene in at least two stages, and among the polymer parts produced in each stage, a polymer part having the highest molecular weight (also referred to as a high molecular weight polymer). the intrinsic viscosity) [eta] _H, intrinsic viscosity of the lowest polymer portion of the molecular weight (also referred to as a low molecular weight polymer) [eta] when the _L, [eta] _H and [eta] _L and has the following formula It is preferable to satisfy (1), more preferably the following formula (1) ′ is satisfied.
3.0 ≦ [η] _H − [η] _L ≦ 6.5 (1)
3.5 ≦ [η] _H − [η] _L ≦ 5.5 (1) ′

  If it is less than the minimum of said Formula (1), the melt tension of the polylactic acid containing polypropylene resin composition for extrusion molding will fall, and there exists a tendency for extrusion molding (working) properties, such as blow molding (working) property, to fall. On the other hand, if the upper limit is exceeded, the molecular weight disparity becomes excessive and the non-uniformity becomes large, so that the extrusion (working) property tends to deteriorate, for example, the flow tends to be non-uniform.

When the polymerization is performed in two stages, the ratio of the production amount in each stage is preferably 35 to 65% by weight, more preferably 40 to 60% by weight, while the low molecular weight polymer is polymerized. Preferably it is 35 to 65% by weight, more preferably 40 to 60% by weight. Here, the total of the high molecular weight polymer and the low molecular weight polymer is 100% by weight. Within this range, good melt fluidity can be obtained, and the kneading state at the time of granulation becomes good, which is preferable.
Further, when the propylene homopolymer (A1) is polymerized in three or more stages, it is preferable that the polymer part in each stage is in an amount close to an equal amount, and the amount ratio between the high molecular weight polymer and the low molecular weight polymer Is 0.5 to 1.5, more preferably 0.75 to 1.25. Within this range, good melt fluidity is obtained, and the kneading state during granulation is also good.

Here, the polymerization ratio of the polymer at each stage is obtained from the mass balance, and the intrinsic viscosity is calculated from the intrinsic viscosity measured at 135 ° C. in the tetralin solution of the polymer at the end of each stage polymerization by the following formula (2) Ask for.
W ^T _n × [η] ^T _n = W ^T _n−1 × [η] ^T _n−1 + (W ^T _n −W ^T _n−1 ) × [η] _n (2)

In formula (2), W ^T _n-1 is the total amount of the polymer up to the n-1 stage, W ^T _n is the total amount of the polymer up to the n stage, [η] ^T _n-1 is the intrinsic viscosity of the polymer at the end of the n-1 stage polymerization, [η] ^T _n is the intrinsic viscosity of the polymer at the end of the n stage polymerization, and [η] _n is the n stage. It is the intrinsic viscosity of the polymer of the eye, and n is an integer of 2 or more and does not exceed the number of all polymerization stages.

A typical example of the method for producing the propylene homopolymer (A1) according to the present invention is as follows, but is not limited to this method.
It can be obtained by polymerizing propylene in multiple stages in the presence of the following catalyst.
For example, an organoaluminum compound (I) such as triethylaluminum or diethylaluminum monochloride, or a reaction product (VI) of an organoaluminum compound (I) and an electron donor (a) such as diisoaluminum ether is converted to titanium tetrachloride ( The solid product (II) obtained by reacting with c) is further reacted with an electron donor (a) and an electron acceptor (b), for example, titanium tetrachloride. In combination with an aluminum compound (IV), such as triethylaluminum, diethylaluminum monochloride, etc., and an aromatic carboxylic acid ester (V), such as methyl p-toluate, the aromatic carboxylic acid ester (V) and the solid product ( III) The molar ratio V / III = 0.1 to 10.0.

Multistage polymerization can be carried out by using a single polymerization tank by changing the temperature, pressure, and concentration of chain transfer agent such as hydrogen stepwise, which are polymerization conditions, The polymerization may be performed using a plurality of polymerization tanks having different polymerization conditions such as the concentration of a chain transfer agent such as hydrogen, or a combination of both.
As the polymerization mode, known modes such as bulk polymerization, solution polymerization, and gas phase polymerization can be adopted. The polymerization mode of each polymerization stage may be the same or different.
The propylene homopolymer (A1) according to the present invention is characterized in that the difference in intrinsic viscosity between the highest molecular weight polymer and the lowest molecular weight polymer is relatively large. In determining the polymerization conditions, the highest molecular weight polymer is obtained in the absence of a chain transfer agent such as hydrogen and the lowest molecular weight polymer is obtained in the presence of sufficient chain transfer agent. It is preferable to carry out below.

In the propylene homopolymer (A1) according to the present invention, the relationship between the isotactic pentad fraction (P) and the MFR preferably satisfies the following formula (3). Propylene homopolymers that do not satisfy this relationship tend to have a flexural modulus that is difficult to satisfy the requirements of the present invention.
1 ≧ P ≧ 0.015 × log (MFR) +0.955 (3)

Here, the isotactic pentad fraction (P) is a propylene-based polymer molecular chain measured by the method described in Macromolecules, 925-926 (1973), that is, using ¹³ C-NMR. Is the isotactic fraction in pentad units. In other words, the fraction means a fraction of propylene monomer in which five propylene monomer units are isotactically bonded continuously. The spectral peak assignment method in the measurement using ¹³ C-NMR is based on Macromolecules, 687-689 (1975). Specifically, the measurement by ¹³ C-NMR can be performed by using a 270 MHz apparatus of FT-NMR and improving the signal detection limit of 27000 times to 0.001 in terms of isotactic pentad fraction.

  Component A according to the present invention may be a propylene / ethylene block copolymer (A2) having a propylene homopolymer portion and a propylene / ethylene copolymer portion. The propylene homopolymer portion in the propylene / ethylene block copolymer (A2) preferably has the same structure as the propylene homopolymer (A1).

The propylene / ethylene block copolymer (A2) can be obtained by a method including a propylene homopolymer polymerization step and a propylene / ethylene random copolymer polymerization step.
In the propylene homopolymer polymerization step, it is preferable to produce a propylene homopolymer having the same properties as the propylene homopolymer (A1). The order of the propylene homopolymer polymerization step and the propylene / ethylene random copolymer polymerization step is not particularly limited. The property of the propylene homopolymer portion is determined by measuring the property of the propylene homopolymer obtained by separately performing only the propylene homopolymer polymerization step.

  The proportion of the propylene / ethylene copolymer portion determined as the 23 ° C. xylene-soluble content is preferably 7% by weight or less when the total amount of the propylene / ethylene block copolymer (A2) is 100% by weight. When the proportion of the propylene / ethylene copolymer portion exceeds 7% by weight, it tends to be difficult to satisfy the requirements for the flexural modulus. In addition, you may use these components A in mixture of 2 or more types.

  In the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention, the content of component A is 30% by weight or more, preferably 37.5% by weight or more, more preferably 45% by weight, based on the total amount of the resin composition. That's it. If the content is less than 30% by weight, the heat resistance, rigidity and impact resistance of the resin composition and the extruded product of the present invention are lowered. The content of component A is 89.5% by weight or less, preferably 84.3% by weight or less, more preferably 79.1% by weight or less. If it exceeds 89.5% by weight, the resin composition of the present invention cannot be said to be an environmentally friendly resin composition.

(2) Component (B): Maleic anhydride-modified polyolefin resin and / or hydroxy-modified polyolefin resin Maleic anhydride-modified polyolefin resin and / or hydroxy-modified polyolefin resin (hereinafter referred to as component (B) according to the present invention) The component B) is not particularly limited as long as it is a modified polyolefin resin not containing an epoxy group, and a conventionally known one can be used.
Here, the maleic anhydride-modified polyolefin resin is, for example, polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-α-olefin-nonconjugated diene compound copolymer (EPDM, etc.), ethylene-aromatic monovinyl. A polyolefin such as a compound-conjugated diene compound copolymer elastomer is graft-copolymerized with maleic anhydride and chemically modified. This graft copolymerization is carried out, for example, by reacting the polyolefin with maleic anhydride in a suitable solvent using a radical generator such as benzoyl peroxide. Maleic anhydride can also be introduced into the polymer chain by random or block copolymerization with a polyolefin monomer.

  Examples of the graft reaction conditions include di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2, Dialkyl peroxides such as 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyisopropylcarbonate, 2, Peroxyesters such as 5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3, diacyl peroxides such as benzoyl peroxide Diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di (hydro An organic peroxide such as hydroperoxides such as oxy) hexane is used in a molten state or solution at a temperature of about 80 to 300 ° C. using about 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyolefin. The method of making it react in a state is mentioned.

Similarly, the hydroxy-modified polyolefin resin is a modified polyolefin resin containing a hydroxyl group. The hydroxy-modified polyolefin resin may have a hydroxyl group at an appropriate site, for example, at the end of the main chain or at the side chain.
Examples of the olefin resin constituting the hydroxy-modified polyolefin resin include homo- or copolymers of α-olefins such as ethylene, propylene, butene, 4-methylpentene-1, hexene, octene, nonene, decene, dodecene, Examples include a copolymer of the α-olefin and a copolymerizable monomer.
Preferred hydroxy-modified polyolefin resins include hydroxy-modified polyethylene resins (for example, low density, medium density or high density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, ethylene- (meth) acrylate copolymer). , Ethylene-vinyl acetate copolymers, etc.), hydroxy-modified polypropylene resins (eg, polypropylene homopolymers such as isotactic polypropylene), random copolymers of propylene and α-olefins (eg, ethylene, butene, hexane, etc.) And propylene-α-olefin block copolymer), hydroxy-modified poly (4-methylpentene-1), and the like.

Examples of the monomer for introducing the reactive group include a monomer having a hydroxyl group (for example, allyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc.). It can be illustrated.
Moreover, the modification amount by the monomer which has a hydroxyl group is 0.1 to 20 weight% with respect to polyolefin resin, Preferably it is about 0.5 to 10 weight%. The average molecular weight of the hydroxy-modified polyolefin resin is not particularly limited.

  The hydroxy-modified polyolefin resin preferably has a hydroxyl value defined by JIS K0070 of 1 to 100 mgKOH / g. If the hydroxyl value is less than 1 mgKOH / g, impact resistance tends to deteriorate, whereas if it exceeds 100 mgKOH / g, extrusion (working) properties such as blow moldability tend to deteriorate. Such a hydroxy-modified polyolefin resin can be appropriately selected from commercially available products, and examples thereof include Umex manufactured by Sanyo Chemical Industries.

  Preferred components B include those modified by graft polymerization of maleic anhydride to an olefin polymer mainly composed of ethylene and / or propylene, and olefins and maleic anhydride mainly composed of ethylene and / or propylene. Examples thereof include those modified by copolymerization with an acid. Specific examples include a combination of polyethylene / maleic anhydride grafted ethylene / butene-1 copolymer or a combination of polypropylene / maleic anhydride grafted polypropylene.

When Component B according to the present invention is a maleic anhydride-modified polyolefin resin, the acid amount (sometimes referred to as an acid-modified amount or a graft ratio) is not particularly limited, but is preferably an average in terms of maleic anhydride. 0.05 to 10% by weight, preferably 0.07 to 5% by weight.
As an example of such a maleic anhydride-modified polyolefin resin, “OREVAC CA100” manufactured by Arkema Co., Ltd. can be mentioned.
If the amount of acid in component B is within this range, the impregnation and adhesion of the resin to the melt-kneaded resin composition composed of component (C) and component (D) will be sufficient, and impact resistance will be improved. It is easy to obtain a resin composition that is dramatically improved, and an excessive amount of acid does not impair the extrusion (working) property, and the entire component B becomes brittle and the impact resistance is not lost. Moreover, you may use these components B in mixture of 2 or more types.

In the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention, the content of component B is 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0, based on the total amount of the resin composition. .3% by weight or more. The content of component B is 5% by weight or less, preferably 4.5% by weight or less, more preferably 4% by weight or less.
When the content of component B is less than 0.1% by weight, the impregnation property and adhesion of the resin to the melt-kneaded resin composition composed of the component (C) and the component (D) become insufficient. The resin composition of the present invention having greatly improved impact properties cannot be obtained. On the other hand, when the content of Component B exceeds 5% by weight, the extrusion (processing) property is impaired, and the entire resin composition becomes brittle and the impact resistance is lost.

(3) Component (C): Polylactic acid-based resin The component (C) polylactic acid-based resin (hereinafter also simply referred to as Component C) according to the present invention has an MFR (190 ° C., 21.18 N) of 1 to 7 g. / 10 minutes, preferably 1.5 to 6 g / 10 minutes, more preferably 2 to 5 g / 10 minutes. When the MFR is less than 1 g / 10 min, the extrusion molding (processing) property (fluidity, etc.) of the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention and the appearance of the extrusion molded product are deteriorated. On the other hand, when MFR exceeds 7 g / 10 minutes, the melt tension required for extrusion molding such as blow molding of the resin composition is lowered.
Component C is preferably a polymer composition containing as a main component a polymer containing lactic acid units at least 50 mol% or more, preferably 75 mol% or more. Such a polylactic acid-based resin can be synthesized by polycondensation of lactic acid or ring-opening polymerization of lactide, which is a cyclic dimer of lactic acid, and can be synthesized with lactic acid as long as the properties of the polymer are not significantly impaired. A composition obtained by copolymerizing another copolymerizable monomer or a composition in which other resins and additives are mixed may be used.

Monomers that can be copolymerized with lactic acid include hydroxycarboxylic acids (eg, glycolic acid, caproic acid, etc.), aliphatic polyhydric alcohols (eg, butanediol, ethylene glycol, etc.) and aliphatic polycarboxylic acids (eg, succinic acid). Acid, adipic acid, etc.).
When the polylactic acid resin is a copolymer, the copolymer may be arranged in any manner such as a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. Further, at least a part of the copolymer is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol / propylene glycol copolymer, 1,3-butanediol, 1,4- Bifunctional or higher functional polyvalent such as butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol, glycerin, trimethylolpropane, etc. Alcohol; polyvalent isocyanates such as xylylene diisocyanate and 2,4-tolylene diisocyanate; polysaccharides such as cellulose, acetyl cellulose and ethyl cellulose may be copolymerized. Furthermore, at least a part may take any structure such as a linear shape, a ring shape, a branched shape, a star shape, and a three-dimensional network structure.

Component C is a method of directly dehydrating polycondensation of the raw material, or a ring-opening polymerization of a cyclic dimer of the lactic acid or hydroxycarboxylic acid, for example, a cyclic ester intermediate such as lactide, glycolide, or ε-caprolactone. It is obtained by the method.
When the raw material is produced by direct dehydration polycondensation, the raw material lactic acid, or lactic acid and hydroxycarboxylic acid, or aliphatic dicarboxylic acid and aliphatic diol are organic solvents, preferably phenyl ether Polymerization is carried out by a method in which azeotropic dehydration condensation is carried out in the presence of a solvent, and water is removed from the solvent distilled off by azeotropic distillation to bring the solvent into a substantially anhydrous state and returned to the reaction system.
The weight average molecular weight of Component C is preferably 50,000 to 1,000,000, more preferably 100,000 to 500,000. When the molecular weight is in the above range, heat resistance, impact resistance, and extrusion (working) property tend to be improved.

  Among such components C, polylactic acid is preferable. As polylactic acid, when the constituents of the L-form or D-form are increased, the heat resistance and the like are improved. In the present application, “mainly comprising” means that the amount of L-form or D-form is 90 mol% or more, preferably the amount of L-form or D-form is 90 mol% or more, more preferably 95 mol%. It is desirable that the amount be at least mol%, more preferably at least 98 mol%. As an example of such polylactic acid, “Terramac TP-4000” manufactured by Unitika Ltd. can be mentioned. Moreover, you may use these components C in mixture of 2 or more types.

The content of Component C in the present invention is 10% by weight or more, preferably 15% by weight or more, more preferably 20% by weight or more based on the total amount of the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention. On the other hand, the content of Component C is 50% by weight or less, preferably 45% by weight or less, more preferably 40% by weight or less.
If the content of component C is less than 10% by weight, it cannot be said that the resin composition is environmentally friendly. On the other hand, when the content of Component C exceeds 50% by weight, all physical properties of the resin composition are lowered.

(4) Component (D): Epoxy-modified polyolefin resin The component (D) epoxy-modified polyolefin resin (hereinafter, also simply referred to as component D) according to the present invention is a polyolefin-based polymer having an epoxy group introduced into the molecule. Resin.
This component D is composed of structural units based on ethylene or an α-olefin having 3 to 20 carbon atoms and an epoxy group-containing monomer, but based on other monomers as long as the properties of the component D are not significantly impaired. The unit may be contained in a very small amount, for example, 5% by weight or less.

Such a component D can be produced by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms and an epoxy group-containing monomer. Ethylene or an α-olefin having 3 to 20 carbon atoms and an epoxy group-containing monomer may be used alone or in combination of two or more.
Of ethylene and C3-C20 α-olefins, ethylene and propylene are preferred. That is, as component D, epoxy-modified polyethylene and epoxy-modified polypropylene are preferable, and epoxy-modified polyethylene is more preferable.
The MFR (190 ° C., 21.18 N) of the epoxy-modified polyethylene or epoxy-modified polypropylene is preferably 0.01 to 20 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes. If MFR is in this range, it is possible to easily obtain a polylactic acid-containing polypropylene resin composition for extrusion molding having excellent impact resistance, melt tension and the like.

  Examples of the epoxy group-containing monomer include glycidyl esters of α, β-unsaturated acids. The glycidyl ester of α, β-unsaturated acid is a compound represented by the following formula (4), specifically glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc., and glycidyl methacrylate is particularly preferable. . The content of the structural unit based on the glycidyl ester of α, β-unsaturated acid is suitably 1 to 50% by weight, preferably 3 to 40% by weight per 100% by weight of component D.

（式中、Ｒは、水素原子または炭素数１〜６のアルキル基を表す。）

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

In the copolymer obtained by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms and an epoxy group-containing monomer, a single amount of vinyl acetate, methyl acrylate or the like corresponding to the acid in the component B is further included. Although there is a polymer obtained by copolymerizing the body, in the present invention, it is classified as component D as long as an epoxy group-containing monomer is contained. Component D can also be produced by grafting polyolefin with an epoxy group-containing compound.
As described above, the ethylene-glycidyl methacrylate copolymer (E-GMA copolymer) using ethylene as the α-olefin and glycidyl methacrylate as the epoxy group-containing monomer is the resistance of the resin composition of the present invention. This is preferable from the viewpoint of further improving impact properties.
Examples of commercially available products include “Bond First (registered trademark)” manufactured by Sumitomo Chemical Co., Ltd. The content of GMA units in the copolymer is about 3 to 15% by weight. Moreover, you may use these components D in mixture of 2 or more types.

  In the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention, the content of component D is 0.4% by weight or more, preferably 0.5% or more, more preferably 0, based on the total amount of the resin composition. .6% by weight or more. The content of component D is 15% by weight or less, preferably 13% by weight or less, more preferably 10% by weight or less. When the content is less than 0.4% by weight, the melt tension required for extrusion molding such as blow molding of the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention is lowered. On the other hand, when the content of Component D exceeds 15% by weight, the heat resistance decreases.

(5) Component (E): Elastomer The elastomer of component (E) used in the present invention (hereinafter also simply referred to as component E) is not particularly limited, and various elastomers, specifically known ethylene It is possible to use a base elastomer or a styrene elastomer.
These components E may be used as a mixture of two or more.

Examples of the ethylene elastomer include an ethylene / α-olefin copolymer and an ethylene / α-olefin / diene terpolymer.
Specific examples include ethylene / propylene copolymer (ethylene propylene rubber; EPR), ethylene / butene copolymer (EBR), ethylene / hexene copolymer (EHR), ethylene / octene copolymer (EOR), ethylene -A propylene diene copolymer (EPDM) etc. are mentioned.
The method for producing these ethylene elastomers is not particularly limited, and is appropriately selected from known methods and conditions.
Moreover, a commercial item (for example, “Tuffmer A4050S” manufactured by Mitsui Chemicals, Inc., which is an ethylene / butene copolymer (EBR)) can also be used.

Moreover, as a styrene-type elastomer, a styrene-butadiene copolymer, a styrene-isoprene copolymer, or hydrogenated products thereof can be used. Preferably, the content of the A segment having a polystyrene structure is 1 to 80% by weight, preferably 5 to 50% by weight, more preferably 7 to 35% by weight, together with the B segment showing an ethylene / butene or ethylene / propylene structure A block copolymer having a structure represented by the following formula can be used.
A-B or A-B-A

When the content of the A segment exceeds 80% by weight, the impact resistance is inferior. In addition, content of a polystyrene structural unit is a value measured by conventional methods, such as an infrared spectrum analysis method and a < ¹³ > C-NMR method.
Specific examples include styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), hydrogenated styrene / butadiene rubber (HSBR), and styrene-ethylene / butylene copolymer (SEB). , Styrene-ethylene-propylene copolymer (SEP), Styrene-ethylene-butylene-styrene copolymer (SEBS), Styrene-ethylene-propylene-styrene copolymer (SEPS), Styrene-ethylene-ethylene-propylene-styrene Examples thereof include a copolymer (SEEPS), a styrene-butadiene / butylene-styrene copolymer (SBBS), and a styrene-ethylene / butylene-ethylene copolymer (SEBC).
Other hydrogenated polymer systems such as ethylene-ethylene / butylene-ethylene copolymer (CEBC) can also be used.
Here, for example, the elastomer copolymer having a block structure may be a mixture of a triblock structure and a diblock structure as shown in the structural formula. These block copolymers can be produced by a general anion living polymerization method or the like. For this, styrene, butadiene and styrene are successively polymerized to produce a triblock body, followed by hydrogenation (SEBS production method) and after the first production of a styrene-butadiene diblock copolymer. There is a method of hydrogenation after making a triblock body using a coupling agent. Moreover, the hydrogenated product (SEPS) of a styrene-isoprene-styrene triblock body can also be manufactured by using isoprene instead of butadiene.
Moreover, a commercial item can also be used, for example, "Clayton G1651H" by Kraton polymer company can be mentioned as an example of a styrene-ethylene butylene-styrene copolymer (SEBS).

  Among these components E, ethylene / butene copolymer (EBR), ethylene / octene copolymer (EOR), hydrogenated styrene / butadiene rubber (HSBR), styrene / ethylene / butylene / styrene copolymer (SEBS). ) And styrene-ethylene / propylene-styrene copolymer (SEPS).

  In the polylactic acid-containing resin composition for extrusion molding of the present invention, the content of the component E used is preferably 1% by weight or more, more preferably 2% by weight or more, and still more preferably based on the total amount of the resin composition. 3% by weight or more. The content of component E is preferably 30% by weight or less, more preferably 25% by weight or less, and still more preferably 20% by weight or less. When the component E is less than 1% by weight, the impact resistance of the resin composition and the extruded product tends to be lowered. Moreover, when it exceeds 30 weight%, there exists a tendency for heat resistance and rigidity to fall.

(6) Component (F): Optional component In the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention, in addition to the components A to D (optionally components A to E), if necessary, As long as the effects of the present invention are not significantly impaired, an optional component of component (F) (hereinafter also simply referred to as component F) may be blended.
Component F includes fillers, pigments for coloring, antioxidants such as phenols, sulfurs and phosphoruss, antistatic agents, light stabilizers such as hindered amines, ultraviolet absorbers, organic aluminum and talc. Examples thereof include a nucleating agent, a dispersing agent, a neutralizing agent, a foaming agent, a metal deactivator, a lubricant, a flame retardant, a thermoplastic resin other than components A to D, and an elastomer other than component E.
Component F may be added at the same time as components A to E or at any stage of step (I) and step (II) described later.

Here, the filler as the component F is effective in improving the heat resistance, rigidity, dimensional stability and the like of the polylactic acid-containing polypropylene resin composition for extrusion molding and the extruded product of the present invention.
As the filler, various known inorganic and organic fillers such as silica, diatomaceous earth, magnesium hydroxide, calcium carbonate, talc, clay, mica, wollastonite, carbon black, wood powder, basic magnesium sulfate fiber ( Magnesium oxysulfate fibers), potassium titanate fibers, carbon fibers, glass fibers, natural fibers such as cotton, synthetic fibers such as polyester, etc. Among them, talc and polyester synthetic fibers are particularly effective. To preferred.

2. Production Method The polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention can be produced by mixing, melting and kneading each of the above-described blending components at the blending ratio described above. Each component is compounded using a conventionally known melt-kneader such as a single screw extruder, twin screw extruder, Banbury mixer, roll kneader, etc. An extruder is most preferably used.
As the twin screw extruder, for example, TEX30α manufactured by Nippon Steel Works can be used for melt kneading.

The polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention can be preferably obtained by a production method including the following step (I) and step (II).
In step (I), the component (C): MFR (190 ° C., 21.18N) is 1 to 7 g / 10 min. And the component (D): epoxy-modified polyolefin resin is melt-kneaded. And step (II) includes the melt-kneaded resin composition obtained in step (I), component (A): polypropylene resin, component (B): maleic anhydride-modified polyolefin resin, and This is a step of melt-kneading the hydroxy-modified polyolefin resin.
In the step (II), it is preferable to melt and knead the elastomer as the component (E) in an amount of 1 to 30% by weight based on the total amount of the resin composition. Component F may be added at any stage of step (I) or step (II) as described above.
Step (I) and step (II) may be performed intermittently or continuously. Even if each of step (I) and step (II) is performed using a plurality of extruders, step (II) can be performed after performing step (I) using a single extruder. . For example, component C and component D are kneaded in the first stage of one extruder, and component A, component B, and optionally component E and / or component F are fed and added by side feed, and in the latter stage of the extruder. Polylactic acid-containing polypropylene resin composition for extrusion molding is obtained, or, for example, component A and component B, and optionally component E and / or component F are kneaded in the former stage of the extruder, and separated in advance (accompanying extrusion) The molten resin kneaded material of component C and component D melt-kneaded (that is, step (I)) is added by side feed, and a polylactic acid-containing polypropylene resin composition for extrusion molding can be obtained at a later stage. .

  Also, for example, in the biaxial kneader side feed method, component A, component B, and in some cases, component E and / or component F are supplied by the side feed method using a side feeder installed on the screw tip side. To do. That is, the component C and the component D in the step (I) are supplied from the root of the kneader and melt-kneaded in the first half of the biaxial kneading part, and the component A, the component B in the step (II), and further, Component E and / or Component F can be supplied using a side feeder and melt kneaded in the latter half of the biaxial kneading section to obtain the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention.

In the melt kneading in step (I) and step (II), the melt kneading temperature (resin temperature) is preferably 240 ° C. or less, more preferably 200 ° C. or less, and further preferably 190 ° C. or less. When the melt kneading temperature is outside the above range, the melt tension necessary for extrusion molding such as blow molding of the polylactic acid-containing polypropylene for extrusion molding of the present invention tends to decrease due to the viscosity of polylactic acid being easily increased. . The lower limit of the melt kneading temperature is not particularly limited as long as the components can be sufficiently melt kneaded, but is preferably 170 ° C.
If the temperature is lower than the temperature at which the melt kneading is possible, the production (melt kneading) of the polylactic acid-containing resin composition for extrusion molding of the present invention may be difficult, or the obtained performance may be insufficient.

II. Extrusion product of polylactic acid-containing polypropylene resin composition for extrusion molding The polypropylene resin composition for extrusion molding of the present invention can be suitably used for various extrusion moldings because it has performance such as high melt tension. That is, it has high applicability to extrusion molding such as blow (hollow) molding, sheet molding, profile extrusion molding, and film molding. For example, according to blow molding, various types of blow molded bodies to be described later can be manufactured, and sheet molding can be used for manufacturing industrial parts and products such as large foam sheets and interior members (deckboards, tonneau covers). And is preferably used.

  The polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention contains a plant-derived component, and in addition to being excellent in balance of physical properties, is excellent in extrusion moldability, particularly blow moldability. It is possible to easily form various blow molded bodies by being molded. These blow molded products include automotive interior and exterior parts such as instrument panels, trims, bumpers, and garnishes, home appliance parts such as TV cases, various industrial parts such as roofs, bonnets, and pallets for construction machinery and agricultural machinery. Products are listed, which are preferably used in a wide range of markets. In addition, since the polypropylene-based resin composition is a thermoplastic resin, it can be repeatedly used and can be said to be a material suitable for material recycling. It is possible to make a useful material for thermal recycling, and it has great industrial value in promoting the recycling campaign to protect the global environment.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited thereto without departing from the gist thereof.
In addition, the measurement of the various physical properties in an Example followed the following point. The materials used are shown below.

1. Measurement method (1) MFR
In accordance with JIS K7210, measurement was performed at a temperature of 230 ° C. under a load of 21.18 N (2.16 kg). The component (C) polylactic acid resin and the component (D) epoxy-modified polyolefin resin were measured at a temperature of 190 ° C. under a load of 21.18 N (2.16 kg).
(2) Flexural modulus Measured according to ISO 178 (JIS K7171 “Plastics—How to Obtain Bending Properties”) at a measurement atmosphere temperature of 23 ° C. and a bending speed of 2 mm / min.
(3) Melt tension (MT) (unit: g):
Using a capillograph manufactured by Toyo Seiki Seisakusho Co., Ltd., the resin was put into a cylinder with a diameter of 10 mm heated to a temperature of 190 ° C., and the molten resin was extruded through an orifice with a diameter of 2.095 mm and a length of 8 mm at a pushing speed of 10 mm / min. The film was taken up at a speed of 4 m / min, and the melt tension was measured.
(4) Thermal deformation temperature (HDT)
The thermal deformation temperature was measured in conformity with ISO75-2 (JIS K7191-2 “Plastics—Method of Determining Load Deflection Temperature—Part 2: Plastic and Ebonite”) (bending stress = 0.45 MPa).
(5) Charpy impact test (notched)
Charpy impact strength was measured according to JIS K7111. The measurement ambient temperature was 23 ° C.

2. Material (1) Component (A): Polypropylene resin (i) A-1: MFR manufactured by Nippon Polypro Co., Ltd. is 0.5 g / 10 min, Mw / Mn is 6, and isotactic pentad fraction is 0.967. Propylene homopolymer (3-stage polymerization product, polymerization ratio is 1st stage / second stage / third stage = 35/33/32 (% by weight), [η] of each stage is the first stage / second stage / 3 Stage = 2.0 / 3.7 / 5.8). The flexural modulus is 2300 MPa.
(Ii) A-2: Propylene homopolymer part having a Mw / Mn of 8 manufactured by Nippon Polypro Co., Ltd., the proportion of the propylene / ethylene copolymer part is 4% by weight, and the MFR is 0.5 g / 10 min. -Ethylene block copolymer. The flexural modulus is 2000 MPa.
(Iii) A-3: Propylene homopolymer portion having Mw / Mn of 8.6 manufactured by Nippon Polypro Co., Ltd., the proportion of propylene / ethylene copolymer portion is 18% by weight, and MFR is 0.5 g / 10 min. Propylene / ethylene block copolymer. The flexural modulus is 1200 MPa.
(Iv) A-4: Propylene homopolymer portion having Mw / Mn of 4.5 manufactured by Nippon Polypro Co., Ltd., the proportion of propylene / ethylene copolymer portion is 8% by weight, and MFR is 2.5 g / 10 min. Propylene / ethylene block copolymer. The flexural modulus is 1700 MPa.

(2) Component (B): Maleic anhydride-modified polyolefin resin (i) B-1: “OREVAC CA100” manufactured by Arkema (maleic anhydride graft ratio = 0.8 wt%).

(3) Component (C): Polylactic acid resin (i) C-1: “Terramac TP-4000” (polylactic acid (PLA) manufactured by Unitika Ltd. MFR (190 ° C., 21.18 N) = 3 g / 10 minutes ).

(4) Component (D): Epoxy-modified polyolefin resin (i) D-1: “Bond First E” (ethylene-glycidyl methacrylate copolymer (E-GMA copolymer) manufactured by Sumitomo Chemical Co., Ltd.) GMA content = 12% by weight MFR (190 ° C., 21.18 N) = 3 g / 10 min).

(5) Component (E): Elastomer (i) E-1: “Clayton G1651H” (styrene-ethylene-butylene-styrene copolymer (SEBS) manufactured by Kraton Polymer Co., styrene content = 33% by weight).
(Ii) E-2: “Tuffmer A4050S” manufactured by Mitsui Chemicals, Inc. (ethylene butene copolymer (EBR). Butene content = 32% by weight. MFR (230 ° C., 21.18N) = 7 g / 10 min).

3. Examples and Comparative Examples [Example 1]
In step (I), a phenolic antioxidant (BASF) is used as a stabilizer with respect to 100 parts by weight of a mixture of 90% by weight of C-1 as component C and 10% by weight of D-1 as component D. IRGANOX 1010 manufactured by Nihon Kogyo Co., Ltd. 0.1 parts by weight and 0.05 parts by weight of a phosphorus-based antioxidant (IRGAFOS 168 manufactured by BASF) were blended, and using a co-rotating twin screw extruder (manufactured by Nippon Steel Works: TEX30α). It was melt-kneaded at a screw speed of 300 rpm, an extrusion rate of 10 kg / H, and a kneading temperature of 180 ° C. to obtain a melt-kneaded resin composition.

In step (II), 33 wt% of the melt-kneaded resin composition obtained in step (I) (29.7 wt% of component C as resin component and 3.3 wt% of component D) and A-1 as component A For 100 parts by weight of a mixture containing 61% by weight of B, 1% by weight of B-1 as component B and 5% by weight of E-1 as component E, phenolic antioxidant (made by BASF) IRGANOX 1010) 0.1 parts by weight and phosphorus antioxidant (IRGAFOS168 manufactured by BASF) 0.05 parts by weight are blended, and screw rotation is performed using a co-rotating twin screw extruder (manufactured by Nippon Steel Works: TEX30α). It was melt-kneaded at several 300 rpm, an extrusion rate of 10 kg / H, and a kneading temperature of 180 ° C. to obtain a melt-kneaded resin composition.
The obtained pellets were injection molded under conditions of a mold temperature of 40 ° C. and a cylinder temperature of 200 ° C. to obtain various test pieces of a polylactic acid-containing polypropylene resin composition. Various physical properties were evaluated by the above methods using the obtained test pieces. The evaluation results are shown in Table 1.

[Example 2]
In Example 1, in the step (II), 22% by weight of the melt-kneaded resin composition obtained in the step (I) (19.8% by weight of component C and 2.2% by weight of component D as resin components) A melt-kneaded resin composition was obtained in the same manner as in Example 1 except that 72% by weight of A-1 was added as Component A, and evaluation was performed according to Example 1. The evaluation results are shown in Table 1.

[Example 3]
In Example 1, a melt-kneaded resin composition was obtained in the same manner as in Example 1 except that component A was changed to A-2, and evaluation was performed according to Example 1. The evaluation results are shown in Table 1.

[Example 4]
In Example 1, except that component E was changed to E-2, a melt-kneaded resin composition was obtained in the same manner as in Example 1, and evaluated according to Example 1. The evaluation results are shown in Table 1.

[Example 5]
In Example 1, a melt-kneaded resin composition was obtained in the same manner as in Example 1 except that 66% by weight of A-1 was blended as Component A and Component E was not blended. went. The evaluation results are shown in Table 1.

[Comparative Example 1]
In Example 1, a melt-kneaded resin composition was obtained in the same manner as in Example 1 except that the component A was changed to A-3, which is a comparative control compound component, and evaluated according to Example 1. The evaluation results are shown in Table 1.

[Comparative Example 2]
In Example 1, a melt-kneaded resin composition was obtained in the same manner as in Example 1 except that the component A was changed to A-4, which was a comparative control compound component, and evaluated according to Example 1. The evaluation results are shown in Table 1.

[Comparative Example 3]
In Example 1, component D is not blended in step (I), and the same stabilizer as in Example 1 is formulated with respect to 100 parts by weight of component C-1 and melt-kneaded. In Example (II), except that 30% by weight of the melt-kneaded resin composition obtained in step (I) (30% by weight of component C as the resin component) and 64% by weight of A-1 as component A were used. As in Example 1, a melt-kneaded resin composition was obtained and evaluated according to Example 1. The evaluation results are shown in Table 1.

[Comparative Example 4]
In Example 1, a melt-kneaded resin composition was obtained in the same manner as in Example 1 except that 62% by weight of A-1 was blended as Component A and Component B was not blended. went. The evaluation results are shown in Table 1.

[Evaluation]
As is clear from Table 1, the polylactic acid-containing polypropylene resin composition for extrusion molding shown in Examples 1 to 5 satisfying the respective requirements in the essential constituent elements of the present invention has good fluidity (MFR) and flexural elasticity. Rate, melt tension, heat distortion temperature and impact strength. For this reason, it is suitable for materials for extrusion molding such as for blow molding.
On the other hand, the polylactic acid-containing polypropylene resin composition for extrusion molding shown in Comparative Examples 1 to 4 is inferior due to poor performance balance.
For example, in Comparative Example 1 in which Component A: A-3, which is a comparative compound component, was blended, the melt tension was good, but the flexural modulus, thermal deformation temperature, and impact strength were significantly different from Example 1. . This indicates that it is essential that component A meets the requirements of the present invention.
Further, in Comparative Example 2 in which Component A: A-4, which is a comparative control compound component, was blended, the flexural modulus and heat distortion temperature were good, but the fluidity, melt tension and impact strength were significantly different from Example 1. Occurred. In this example, since melt tension is extremely small, extrusion moldability such as blow moldability is considered to be poor. This indicates that it is essential that component A meets the requirements of the present invention.

Further, in Comparative Example 3 in which Component D was not blended, the fluidity, bending elastic modulus, heat distortion temperature and impact strength were good, but the melt tension was significantly different from Example 1. Since the melt tension is also small in this example, extrusion moldability such as blow moldability is considered to be poor. This indicates that it is essential that component D meets the requirements of the present invention.
Further, in Comparative Example 4 in which Component B was not blended, the flexural modulus and heat distortion temperature were good, but the flowability, melt tension and impact strength were significantly different from Example 1. Since the melt tension is also small in this example, extrusion moldability such as blow moldability is considered to be poor. This indicates that it is essential that component B meets the requirements of the present invention.

The polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention has excellent bending elastic modulus, heat resistance and impact resistance, and also has melting characteristics necessary for extrusion molding such as blow molding. Extrudates such as blow-molded bodies can be easily formed, and various industrial parts fields, especially various extrudates that are thin, highly functional, and large, such as instrument panels, trims, bumpers, and garnishes. It can be suitably used for various applications such as interior / exterior parts for automobiles, home appliance parts such as TV cases, roofs, bonnets, pallets for construction machinery and agricultural machinery.
Moreover, according to the manufacturing method of this invention, the said polylactic acid containing polypropylene resin composition for extrusion molding can be manufactured easily.
Therefore, the polylactic acid-containing polypropylene resin composition for extrusion molding of the present invention, the production method thereof, and the extrusion-molded body comprising the same are very useful industrially.

Claims (10)

The following component (A) 30-89.5 wt%, component (B) 0.1-5 wt%, component (C) 10-50 wt%, and component (D) 0.4-15 wt% A resin composition comprising:
Melt flow rate (230 ° C., 21.18 N) is 5 g / 10 min or less, flexural modulus measured according to ISO 178 is 1500 MPa or more, 190 ° C. melt tension is 10 g or more, measured according to ISO 75-2 A polylactic acid-containing polypropylene resin composition for extrusion molding, wherein the heat distortion temperature is 80 ° C. or higher.
Component (A): Polypropylene resin having a melt flow rate (230 ° C., 21.18 N) of 10 g / 10 min or less and a flexural modulus measured according to ISO 178 of 1800 to 2600 MPa Component (B): anhydrous Maleic acid-modified polyolefin resin and / or hydroxy-modified polyolefin resin Component (C): Polylactic acid resin having a melt flow rate (190 ° C., 21.18 N) of 1 to 7 g / 10 min Component (D): Epoxy-modified Polyolefin resin   Furthermore, the polylactic acid containing polypropylene resin composition for extrusion molding of Claim 1 which contains the elastomer which is a component (E) 1-30 weight% with respect to the resin composition whole quantity. The polypropylene resin of component (A) is a propylene homopolymer (A1), and propylene is homopolymerized in at least two stages. Among the polymer parts produced in each stage, the intrinsic viscosity of the polymer part having the highest molecular weight. the [eta] _H, when the intrinsic viscosity of the lowest polymer portion of the molecular weight and [η] _L, claims and satisfies the [eta] _H and [eta] _L and the relationship (1) Item 3. The polylactic acid-containing polypropylene resin composition for extrusion molding according to Item 1 or 2.
3.0 ≦ [η] _H − [η] _L ≦ 6.5 (1)   The component (B) is a maleic anhydride-modified polyolefin resin and has an acid amount of 0.05 to 10% by weight in terms of maleic anhydride. Polylactic acid-containing polypropylene resin composition for extrusion molding.   The polylactic acid-containing polypropylene resin for extrusion molding according to any one of claims 1 to 4, wherein the component (C) is polylactic acid and contains L-lactic acid or D-lactic acid as a main component. Composition.   The polylactic acid-containing polypropylene resin composition for extrusion molding according to any one of claims 1 to 5, wherein the component (D) is an ethylene-glycidyl methacrylate copolymer. The process for producing a polylactic acid-containing resin composition for extrusion molding according to any one of claims 1 to 6, comprising the following steps (I) and (II).
Step (I): Step of melting and kneading 10 to 50% by weight of the following component (C) and 0.4 to 15% by weight of component (D) Step (II): Melting and kneading obtained in the step (I) The step of melt-kneading the following component (A) 30 to 89.5 wt% and component (B) 0.1 to 5 wt% into the resin composition Component (A): Melt flow rate (230 ° C., 21 .18N) is a polypropylene resin having a flexural modulus measured in accordance with ISO 178 of 1800 to 2600 MPa of 10 g / 10 min or less. Component (B): Maleic anhydride-modified polyolefin resin and / or hydroxy-modified polyolefin system Resin Component (C): Polylactic acid resin having a melt flow rate (190 ° C., 21.18 N) of 1 to 7 g / 10 minutes Component (D): Epoxy-modified polyolefin resin   8. The polylactic acid-containing resin for extrusion molding according to claim 7, wherein in the step (II), 1-30 wt% of the elastomer as the component (E) is further melt-kneaded with respect to the total amount of the resin composition. A method for producing the composition.   The molded object formed by extrusion molding the polylactic acid containing polypropylene resin composition for extrusion molding of any one of Claims 1-6.   The molded object formed by blow-molding the polylactic acid containing polypropylene resin composition for extrusion molding of any one of Claims 1-6.