JP2011111541A - Polylactic acid-containing master batch, method for producing the same, polylactic acid-containing propylene-based resin composition and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polylactic acid-containing master batch having excellent moldability (fluidity), forming a molded product having excellent physical property balances such as flexural modulus and impact strength, and having excellent environmental response, and improving commercial productivity (reducing production cost of the molded product), to provide a method for producing the master batch, to provide a polylactic acid-containing propylene-based resin composition, and to provide the molded product thereof. <P>SOLUTION: There are provided the polylactic acid-containing master batch etc., containing following components (A) to (D), and produced through a kneading step composed of following step (I), and step (II) subsequent thereto. The component (A): a polypropylene-based resin; component (B): an acid-modified polyolefin-based resin and/or a hydroxy-modified polyolefin-based resin; component (C): a polylactic acid-based resin; and component (D): an epoxy-modified polyolefin-based resin. The step (I): a step of melt kneading the component (C) with the component (D); and step (II): a step of melt kneading a product of the step (I) with the component (A) and component (B). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polylactic acid-containing masterbatch, a production method thereof, a polylactic acid-containing propylene-based resin composition and a molded body thereof, and more specifically, excellent moldability (fluidity), excellent bending elastic modulus, impact strength, and the like. A polylactic acid-containing masterbatch capable of forming a molded product having a balanced physical property, excellent in environmental friendliness, and improving commercial productivity (reducing the manufacturing cost of the molded product), its production method, and polylactic acid-containing propylene The present invention relates to a resin composition and a molded product thereof.

  In recent years, due to increasing environmental problems, used plastic products are required to decompose and disappear over time in the natural environment and ultimately have no adverse effect on the natural environment. Conventional plastics are stable in the natural environment over a long period of time and have a low bulk specific gravity, which leads to problems such as promoting the shortening of the life of landfills and damaging the natural landscape and the living environment of wild animals and plants. It was pointed out. Therefore, biodegradable resin materials 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.

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 resin materials 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 processability similar to general-purpose resins. Among aliphatic polyesters, lactic acid-based resins are excellent in transparency, rigidity, heat resistance, and the like, and thus have attracted attention in the packaging film field and injection molding field as alternative materials for polystyrene and polyethylene terephthalate.

Furthermore, in recent years, it has been required from the viewpoint of environmental protection to use plastics derived from plant raw materials instead of conventional petrochemical products as plastic raw materials.
Many biodegradable plastics including lactic acid resins can be derived from plant raw materials, and these resins are also attracting attention from the meaning.

  However, polylactic acid has a defect 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 article comprising 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.

  Further, as a conventionally known method for improving the physical properties of resins such as polylactic acid, there is a technique called polymer blend or polymer alloy. Attempts have been made to improve impact resistance, flexibility, rigidity, and heat resistance by forcibly mixing and kneading multiple types of resins. For example, 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 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, the compatibility of different polymers may be improved by adding a compatibilizing agent. For example, Patent Document 4 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-type structure as a compatibilizing agent. Patent Document 5 discloses a thermoplastic resin molded body made of a polyolefin resin and a polylactic acid resin and a thermoplastic resin having compatibility with both.
Further, Patent Document 6 includes a polyolefin, an aliphatic polyester-based biodegradable polymer, an acid or epoxy group-containing polyolefin, the polyolefin forms a matrix, the aliphatic biodegradable polymer forms a domain, and the periphery of the domain A composition having a dispersed structure surrounded by an acid or epoxy group-containing polyolefin is disclosed. Further, Patent Document 7 includes a crystalline propylene polymer, a polylactic acid resin, an ethylene polymer having an epoxy group, and a tensile elongation at break, an impact resistance, and an elastomer different from the ethylene polymer having an epoxy group. A resin composition having excellent gloss is disclosed.

Patent Document 8 includes a specific propylene polymer, polylactic acid resin, an ethylene polymer containing an epoxy group, and an elastomer as necessary, and has an anisotropic mechanical strength and shrinkage of a molded product. A propylene-based resin composition having improved properties, dimensional stability, appearance, and the like is disclosed. Patent Document 9 discloses a modified propylene polymer obtained by grafting a specific propylene polymer, a polylactic acid resin, an ethylene polymer containing an epoxy group and / or an α, β-unsaturated glycidyl ester. A method for producing a molded article that is lightweight, excellent in mechanical strength, and less contaminated with a mold is disclosed, in which thermally expandable microcapsules are added to the resin composition.
Certainly, by adding such a compatibilizing agent component, etc., the dispersion structure (particularly the dispersion diameter) is improved, and mechanical properties such as impact resistance and the appearance of the molded body are improved. However, the performance is still insufficient for materials for automobile parts that require higher quality.
Furthermore, in order to apply to a wide range of fields, in addition to these performances, it is necessary to further improve commercial productivity (manufacturing efficiency), that is, further reduce the manufacturing cost of the molded body.

JP-A-9-169897 JP-A-10-251498 JP 9-316310 A JP-A-6-263892 Japanese Patent Laying-Open No. 2006-70210 (Claims 5 and 6) JP 2006-77063 A JP 2007-277444 A JP 2009-155517 A JP 2009-144064 A

  In view of the above-mentioned problems of the prior art, an object of the present invention is to form a molded body having excellent formability (fluidity) and having excellent physical property balance such as bending elastic modulus and impact strength. An object of the present invention is to provide a polylactic acid-containing masterbatch that is excellent in properties and can improve commercial productivity, a production method thereof, a polylactic acid-containing propylene resin composition, and a molded body thereof.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention contain specific components (A) to (D), and include a specific step (I) and a subsequent step (II). When a polylactic acid-containing masterbatch produced through the process and a polylactic acid-containing propylene resin composition using the same are prepared, it has excellent moldability (fluidity) and excellent physical property balance such as flexural modulus and impact strength. It has been found that a molded body having a high temperature can be formed, has excellent environmental compatibility, and can improve commercial productivity (reducing the manufacturing cost of the molded body).
In addition, due to the method for producing a polylactic acid-containing masterbatch comprising a specific step (I) and the subsequent step (II), it has excellent moldability (fluidity), and excellent physical properties such as flexural modulus and impact strength. A polylactic acid master batch capable of forming a molded body with a balance can be manufactured, and the molded body has excellent environmental compatibility and can improve commercial productivity (reducing the manufacturing cost of the molded body). I found.
These findings have been further studied and the present invention has been completed.

That is, according to the first aspect of the present invention, the following component (A) to component (D) are contained, and the component (C) is added in an amount of 50% with respect to a total of 100% by weight of each component constituting the masterbatch. % Polylactic acid-containing masterbatch,
A polylactic acid-containing masterbatch produced by the kneading step comprising the following step (I) and the following step (II) is provided.
Component (A): Polypropylene resin component (B): Acid-modified polyolefin resin and / or hydroxy-modified polyolefin resin component (C): Polylactic acid resin component (D): Epoxy-modified polyolefin resin Step (I): Step (II) for melt-kneading component (C) and component (D): Step for melt-kneading the product of step (I), component (A) and component (B)

  In addition, according to the second invention of the present invention, there is provided a polylactic acid-containing masterbatch characterized by further comprising a component (E) elastomer and / or a component (F) filler in the first invention. The

  Moreover, according to the third invention of the present invention, in the second invention, the component (E) is contained in an amount of 1 to 30% by weight based on 100% by weight of each component constituting the master batch. A polylactic acid-containing masterbatch is provided.

  According to the fourth invention of the present invention, in the second or third invention, the component (F) is contained in an amount of 1 to 30% by weight based on 100% by weight of each component constituting the masterbatch. A featured polylactic acid-containing masterbatch is provided.

  According to the fifth invention of the present invention, in any one of the second to fourth inventions, the step (II) comprises the product of the step (I), the component (A) and the component (B), and There is provided a polylactic acid-containing masterbatch, which is a step of melt-kneading component (E) and / or component (F).

According to the sixth aspect of the present invention, in any one of the second to fifth aspects, the total amount of the component (C) and the component (D) is 100% by weight in total of each component constituting the master batch. 51 to 90% by weight,
The total amount of the component (A), the component (B) and the component (E) and / or the component (F) is 10 to 49% by weight based on 100% by weight of each component constituting the master batch, and
A polylactic acid-containing masterbatch is provided in which the weight ratio of component (B) / component (A) is less than 0.5.

  According to the seventh invention of the present invention, in any one of the first to sixth inventions, the component (C) contains L-lactic acid or D-lactic acid as a main component. A master batch is provided.

  According to an eighth aspect of the present invention, there is provided a polylactic acid-containing masterbatch characterized in that in any one of the first to seventh aspects, the component (D) is an ethylene-glycidyl methacrylate copolymer. Provided.

  According to the ninth aspect of the present invention, in any one of the first to eighth aspects, the component (B) is an acid-modified polyolefin having an acid amount of 0.05 to 10% by weight in terms of unsaturated carboxylic acid. There is provided a polylactic acid-containing masterbatch characterized by being a resin.

  According to a tenth aspect of the present invention, in any one of the first to ninth aspects, the component (A) has a melt flow rate (230 ° C., 2.16 kg load) of 0.1 g / 10 min or more. A polylactic acid-containing master batch is provided.

According to the eleventh aspect of the present invention, the following component (A) to component (D) are contained, and the component (C) is added in an amount of 50% with respect to a total of 100% by weight of each component constituting the master batch. %, A method for producing a polylactic acid-containing masterbatch containing more than%,
There is provided a method for producing a polylactic acid-containing masterbatch comprising the following step (I) and subsequent step (II).
Component (A): Polypropylene resin component (B): Acid-modified polyolefin resin and / or hydroxy-modified polyolefin resin component (C): Polylactic acid resin component (D): Epoxy-modified polyolefin resin Step (I): Step (II) for melt-kneading component (C) and component (D): Step for melt-kneading the product of step (I), component (A) and component (B)

  According to the twelfth aspect of the present invention, in the eleventh aspect, the step (II) comprises the product of the step (I), the component (A) and the component (B), and further the component (E). Polylactic acid-containing masterbatch comprising a step of blending 1-30% by weight of the elastomer and / or component (F) filler with respect to a total of 100% by weight of each component constituting the masterbatch, and melt-kneading. A manufacturing method is provided.

  According to the thirteenth invention of the present invention, in the eleventh or twelfth invention, the step (I) comprises 50% by weight based on the total of 100% by weight of the component (D) and each component constituting the master batch. There is provided a method for producing a polylactic acid-containing masterbatch, which is a step of melt-kneading the component (C) in excess of.

  According to a fourteenth aspect of the present invention, in any one of the first to thirteenth aspects, the melt kneading temperature in the step (I) and the step (II) is 240 ° C. or less. A method for producing a lactic acid-containing masterbatch is provided.

  According to a fifteenth aspect of the present invention, the polylactic acid-containing masterbatch according to any one of the first to tenth aspects and a component (G) propylene-based polymer are mixed or kneaded. A polylactic acid-containing propylene-based resin composition is provided.

  According to a sixteenth aspect of the present invention, in the fifteenth aspect, the polylactic acid-containing master batch and the component (G) have a weight ratio of 1/9 to 9/1. A propylene-based resin composition is provided.

  According to the seventeenth aspect of the present invention, there is provided a molded article obtained by molding the polylactic acid-containing propylene resin composition of the fifteenth or sixteenth aspect.

  According to the polylactic acid-containing masterbatch, the production method thereof, the polylactic acid-containing propylene resin composition and the molded body thereof according to the present invention, a polylactic acid resin or the like is masterbatched and diluted with a propylene polymer or kneaded.・ By molding, it is possible to form a molded product with excellent physical properties such as flexural modulus and impact strength under good moldability (fluidity), excellent environmental compatibility, and commercial productivity. For example, trim parts, pillars, glove boxes, instrument panels, bumpers, fenders, back doors, various types of housing parts, and other home appliance parts. There is an effect that it can be suitably used in fields such as housing equipment parts, various industrial parts, and building material parts.

  Hereinafter, the polylactic acid-containing master batch, the production method thereof, the polylactic acid-containing propylene-based resin composition and the molded body thereof according to the present invention will be described in detail for each item.

I. 1. Polylactic acid-containing master batch Structure The polylactic acid-containing masterbatch of the present invention (hereinafter, also simply referred to as “masterbatch” or “MB”) contains the following components (A) to (D), and the component (C) constitutes the masterbatch. A polylactic acid-containing masterbatch containing more than 50% by weight with respect to a total of 100% by weight of the components, which is manufactured through a kneading step consisting of the following step (I) and subsequent step (II) It is characterized by.
Component (A): Polypropylene resin component (B): Acid-modified polyolefin resin and / or hydroxy-modified polyolefin resin component (C): Polylactic acid resin component (D): Epoxy-modified polyolefin resin Step (I): Step (II) for melt-kneading component (C) and component (D): Step for melt-kneading the product of step (I), component (A) and component (B)

(1) Component (A): Polypropylene resin The component (A) polypropylene resin (hereinafter also simply referred to as component (A)) used in the present invention is not particularly limited, and any known polypropylene resin may be used. Can also be used. As the polypropylene resin, one or more crystalline polypropylene resins selected from propylene homopolymer resin and propylene / α-olefin copolymer resin (including block copolymer resin and random copolymer resin), or A mixture of a crystalline polypropylene resin and an α-olefin homopolymer resin or copolymer resin other than propylene is preferred. Examples of the copolymer resin include impact-resistant propylene copolymer resin (ICP), for example, propylene-ethylene block copolymer resin.
Here, the component (A) is a propylene homopolymer resin having a melt flow rate (hereinafter referred to as MFR) (230 ° C., 2.16 kg load) of 0.1 g / 10 min or more, and further 4 g / 10 min or more. And a propylene / ethylene block copolymer resin are preferable from the viewpoint of easily improving the physical property balance of the masterbatch of the present invention and a polylactic acid-containing propylene resin composition (hereinafter also simply referred to as a propylene resin composition). Highly crystalline propylene homopolymer resin is more preferred. Here, MFR is a value measured according to JIS-K7210.

The production method of the component (A) is not particularly limited, and is a known method such as slurry polymerization, gas phase polymerization, or liquid phase bulk polymerization using a highly stereoregular catalyst such as a Ziegler catalyst or a metallocene catalyst. What was manufactured can be used. Moreover, as a polymerization method, a conventionally well-known method can be used and either a batch polymerization method or a continuous polymerization method can be adopted.
Moreover, you may use these components (A) in mixture of 2 or more types.

In the masterbatch of the present invention, the lower limit of the content of the component (A) is preferably 9.7% by weight or more, more preferably 9.8%, based on 100% by weight of the total components constituting the masterbatch. % By weight or more, more preferably 9.9% by weight or more. On the other hand, the upper limit is preferably 48.9% by weight or less, more preferably 48.8% by weight or less, and further preferably 48.7% by weight or less. When the component (A) exceeds 48.9% by weight, it is difficult to say that the masterbatch and the propylene-based resin composition of the present invention are environmentally friendly. On the other hand, if it is less than 9.7% by weight, the compatibility with the propylene polymer is deteriorated when it is diluted with the propylene polymer as a master batch, and the physical property balance of the propylene resin composition may be lowered.
In addition, in this invention, "the total amount of each component which comprises a masterbatch" means each component which comprises the masterbatch of this invention, ie, the total amount of the component (F) mentioned later of a component (A). .

(2) Component (B): acid-modified polyolefin resin and / or hydroxy-modified polyolefin resin Component (B) acid-modified polyolefin resin and / or hydroxy-modified polyolefin resin (hereinafter simply referred to as component (B)) used in the present invention Is not particularly limited as long as it is a modified polyolefin containing no epoxy group, and conventionally known polyolefins can be used.
Among the component (B), acid-modified polyolefin resins include, for example, polyethylene, polypropylene, ethylene-α-olefin copolymers, ethylene-α-olefin-nonconjugated diene compound copolymers (EPDM, etc.), ethylene-aromatics. Polyolefin such as monovinyl compound-conjugated diene compound copolymer rubber is modified by graft copolymerization using unsaturated carboxylic acid such as maleic acid or maleic anhydride. This graft copolymerization is performed, for example, by reacting the polyolefin with an unsaturated carboxylic acid in a suitable solvent using a radical generator such as benzoyl peroxide. Moreover, the component of unsaturated carboxylic acid or its derivative can also be introduce | transduced in a polymer chain by random or block copolymerization with the monomer for polyolefin.

  As the unsaturated carboxylic acid used for modification, for example, a carboxyl group such as maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid or the like and a functional group such as a hydroxyl group or an amino group were introduced as required. Examples include compounds having a polymerizable double bond. Examples of unsaturated carboxylic acid derivatives include these acid anhydrides, esters, amides, imides, metal salts, and the like. Specific examples thereof include maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, Butyl acrylate, methyl methacrylate, ethyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, Menimide, N-butylmaleimide, sodium methacrylate and the like can be mentioned. Maleic anhydride is preferred.

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

The hydroxy-modified polyolefin resin is a modified polyolefin resin containing a hydroxyl group. The 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 olefin 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) acrylic acid ester 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.
The amount of modification by the monomer having a hydroxyl group is about 0.1 to 20% by weight, preferably about 0.5 to 10% by weight, based on the olefin resin. The average molecular weight of the hydroxy-modified polyolefin resin is not particularly limited.

The hydroxy-modified polyolefin resin used in the present invention has a hydroxyl value defined by JIS K0070 of 1.0 to 100 mgKOH / g, preferably 5 to 60 mgKOH / g. If the hydroxyl value is less than 1.0 mgKOH / g, impact properties may be deteriorated. On the other hand, when it exceeds 100 mgKOH / g, workability may be deteriorated.
Such a hydroxyl-modified polyolefin resin can be appropriately selected from commercially available products, and for example, commercially available products such as Yumex series (manufactured by Sanyo Chemical Industries, Ltd.) can be used.

Preferred components (B) include those modified by graft polymerization of maleic anhydride onto an olefin polymer containing ethylene and / or propylene as the main polymer structural unit, olefins mainly composed of ethylene and / or propylene, and anhydride. Examples thereof include those modified by copolymerization with maleic acid. Specifically, a combination of polyethylene / maleic anhydride grafted ethylene / butene-1 copolymer or a combination of polypropylene / maleic anhydride grafted polypropylene can be used.
These components (B) may be used in combination of two or more.

In the acid-modified polyolefin-based resin, the acid amount (acid-modified amount) is not particularly limited, but preferably the acid amount is preferably an average in terms of 100% by weight of the acid-modified polyolefin-based resin in terms of unsaturated carboxylic acid such as maleic anhydride. Is 0.05 to 10% by weight, more preferably 0.07 to 5% by weight. Here, as the unsaturated carboxylic acid, maleic anhydride is preferable.
When the amount of the acid group in the component (B) is within this range, the impregnation property and adhesion of the resin to the melt-kneaded composition composed of the component (C) and the component (D) are sufficient, and the impact property is greatly improved. The master batch and the propylene-based resin composition that have been improved are obtained, and the amount of the acid group is not excessive, and the workability is not impaired, and the entire component (B) becomes brittle and the impact property is not lost.

  In the master batch of the present invention, the weight ratio of component (B) / component (A) is preferably 0.5 or less, more preferably 0.45 or less, and still more preferably 0.4 or less. When the weight ratio of component (B) / component (A) exceeds 0.5, the compatibility with the propylene polymer is deteriorated when diluting with the propylene polymer as a master batch, and the propylene resin composition There is a risk that the physical property balance of the product will be reduced, and the economic efficiency will be reduced.

  In the masterbatch of the present invention, the lower limit of the content of the component (B) is preferably 0.1% by weight or more, more preferably 0.2% with respect to 100% by weight of each component constituting the masterbatch. % By weight or more, more preferably 0.3% by weight or more. On the other hand, the upper limit is preferably 5% by weight or less, more preferably 4.5% by weight or less, and still more preferably 4% by weight or less. If the component (B) exceeds 5% by weight, the processability of the masterbatch of the present invention may be impaired, and the masterbatch or the propylene-based resin composition may become brittle and lose impact properties. If it is less than the above, since the impregnation and adhesion of the resin to the melt-kneaded composition comprising the component (C) and the component (D) will be insufficient, the masterbatch and the propylene with greatly improved impact properties There is a possibility that a resin-based resin composition may not be obtained.

(3) Component (C): Polylactic acid resin The component (C) polylactic acid resin used in the present invention (hereinafter also simply referred to as component (C)) contains at least 50 mol% of lactic acid units, preferably 75. What is a polymer composition which has as a main component the polymer which contains mol% or more is preferable.
Such a component (C) 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. It may be a composition obtained by copolymerizing other copolymerizable monomers, or a composition in which other resins and additives are mixed.

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 polyvalent carboxylic acids (eg, succinic acid). Acid, adipic acid, etc.).
When component (C) is a copolymer, the copolymer may be arranged in any manner such as a random copolymer, an alternating copolymer, a block copolymer, and 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, Bifunctional or higher functional groups such as 4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol, glycerin, trimethylolpropane, etc. Polyhydric alcohols; Polyhydric 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) can be obtained by directly dehydrating polycondensation of the raw materials, or by opening a cyclic dimer of the lactic acid or hydroxycarboxylic acid, for example, a cyclic ester intermediate such as lactide or glycolide, or ε-caprolactone. It can be obtained by a ring polymerization method or the like.
When the above raw materials are produced by direct dehydration polycondensation, lactic acids as raw materials, or lactic acids and hydroxycarboxylic acids, or aliphatic dicarboxylic acids and aliphatic diols are organic solvents, preferably phenyl ether Examples of the polymerization method include a method in which azeotropic dehydration condensation is carried out in the presence of a system solvent, and water is removed from the solvent distilled off by azeotropic distillation to return the solvent to a substantially anhydrous state and return it to the reaction system. The weight average molecular weight of the 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, the heat resistance, impact strength, moldability and processability of the masterbatch and the propylene resin composition of the present invention are improved.

  Among such components (C), polylactic acid is preferable. As polylactic acid, the heat resistance and the like are improved when the component of the L-form or D-form is increased, so the amount of the L-form or D-form is 90 mol% or more, more preferably 95 mol% or more, most preferably 98. It is desirable to be at least mol%.

In the component (C) used in the present invention, MFR (190 ° C., 2.16 kg load) is not particularly limited, but is preferably 0.1 to 50 g / 10 minutes, more preferably 0.5 to 20 g / 10 minutes, More preferably, it is 1-10 g / 10min. When the MFR is less than 0.1 g / 10 minutes, the moldability and physical property balance of the masterbatch and the propylene-based resin composition of the present invention tend to decrease. When the MFR exceeds 50 g / 10 minutes, physical properties such as impact strength. The balance tends to decrease. Here, MFR is a value measured according to JIS-K7210.
Moreover, you may use these components (C) in mixture of 2 or more types.

The lower limit of the content of the component (C) used in the present invention is more than 50% by weight, preferably 60% by weight or more, with respect to the total of 100% by weight of each component constituting the masterbatch. On the other hand, the upper limit is preferably 89% by weight or less.
When the component (C) exceeds 89% by weight, the compatibility with the component (A) of the masterbatch of the present invention is lowered, and the physical property balance of the masterbatch and the propylene-based resin composition may be lowered. If it is 50% by weight or less, it is difficult to say that it is a master batch and a propylene resin composition that are environmentally friendly.

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

Such a component (D) can be preferably 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.
Among ethylene and α-olefin having 3 to 20 carbon atoms, ethylene and propylene are preferable. That is, as component (D), epoxy-modified polyethylene and epoxy-modified polypropylene are preferable.
The MFR (ASTM D1238, 190 ° C., 2.16 kg load) of the epoxy-modified polyethylene or epoxy-modified polypropylene is preferably 0.01 to 100 g / 10 minutes, more preferably 0.1 to 20 g / 10 minutes. When the MFR is within this range, a master batch and a propylene resin composition having higher fluidity and better moldability can be obtained.

  Examples of the epoxy group-containing monomer include glycidyl esters of α, β-unsaturated acids. The α, β-unsaturated glycidyl ester is a compound represented by the following general formula (1) (wherein R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). Examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl methacrylate is particularly preferable. The content of the structural unit based on the glycidyl ester of α, β-unsaturated acid is 1 to 50% by weight, preferably 3 to 40% by weight per 100% by weight of the epoxy group-containing polyolefin.

The copolymer obtained by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms and an epoxy group-containing monomer further includes vinyl acetate, methyl acrylate, and the like corresponding to the acid in the acid-modified polyolefin resin. However, in the present invention, the polymer is classified as an epoxy-modified polyolefin as long as an epoxy group-containing monomer is contained.
Epoxy-modified polyolefin can also be produced by grafting polyolefin with an epoxy group-containing compound.

As an example of a commercial item, the ethylene-glycidyl methacrylate copolymer (E-GMA copolymer) marketed by names, such as "Bond First (trademark)" by Sumitomo Chemical Co., Ltd., is mentioned. 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 masterbatch of the present invention, the lower limit of the content of component (D) is preferably 1% by weight or more, more preferably 1.5% by weight, with respect to the total of 100% by weight of each component constituting the masterbatch. More preferably, it is 2% by weight or more. On the other hand, the upper limit is preferably 20% by weight or less, more preferably 19% by weight or less, and still more preferably 18% by weight or less. If the component (D) exceeds 20% by weight, the molding processability and rigidity of the masterbatch and the propylene-based resin composition may be lowered. If the component (D) is less than 1% by weight, the impact resistance is dramatically improved. And there exists a possibility that a propylene-type resin composition may not be obtained.

(5) Component (E): Elastomer The component (E) elastomer (hereinafter also simply referred to as component (E)) used as necessary in the present invention is not particularly limited, and various elastomers, specifically known. Ethylene-based elastomers and styrene-based elastomers can be used.
Two or more of these components (E) may be used in combination.

Examples of the ethylene elastomer include an ethylene / α-olefin copolymer elastomer and an ethylene / α-olefin / diene terpolymer elastomer.
Specific examples include an ethylene / propylene copolymer elastomer (ethylene propylene rubber; EPR), an ethylene / butene copolymer elastomer (EBR), an ethylene / hexene copolymer elastomer (EHR), an ethylene / octene copolymer elastomer ( EOR), ethylene / propylene / diene copolymer elastomer (EPDM) and the like.
The method for producing these ethylene elastomers is not particularly limited, and is appropriately selected from known methods and conditions.

As the styrene-based elastomer, a styrene-butadiene copolymer, a styrene-isoprene copolymer, or a hydrogenated product 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 exhibiting an ethylene / butylene or ethylene / propylene structure A block copolymer having a structure represented by the following formula can be used.
A-B or A-B-A
If the content of the A segment exceeds 80% by weight, impact properties may be 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-ethylene / butylene-styrene block copolymer (SEBS) and styrene / ethylene / propylene / styrene block copolymer (SEPS).
The elastomer copolymer having the block structure may be a mixture of a triblock structure and a diblock structure as shown in the above structural formula. These block copolymers can be produced by a general anion living polymerization method. This includes a method of sequentially polymerizing styrene, butadiene and styrene to produce a triblock, followed by hydrogenation (SEBS production method), a styrene-butadiene diblock copolymer, and a cup after There is a method in which a triblock body is made using a ring agent and then hydrogenated. Moreover, the hydrogenated product (SEPS) of a styrene-isoprene-styrene triblock body can also be manufactured by using isoprene instead of butadiene.

  Among these components (E), ethylene-butene copolymer elastomer (EBR), ethylene-octene copolymer elastomer (EOR), styrene-ethylene-butylene-styrene block copolymer (SEBS), and styrene-ethylene Propylene / styrene block copolymer (SEPS) is preferable.

  In the master batch of the present invention, the content of the component (E) used as necessary is preferably 1% by weight or more, more preferably, the lower limit with respect to the total of 100% by weight of each component constituting the master batch. It is 2% by weight or more, more preferably 3% by weight or more. On the other hand, the upper limit 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) exceeds 30% by weight, the rigidity of the masterbatch and the propylene-based resin composition tends to decrease, and when it is less than 1% by weight, the impact property tends to decrease.

(6) Component (F): Filler The component (F) filler (hereinafter also simply referred to as component (F)) used as necessary in the present invention is not particularly limited, and various known inorganic and organic fillers are used. Can be used.
Specific examples include silica, diatomaceous earth, magnesium hydroxide, calcium carbonate, talc, clay, mica, wollastonite, carbon black, wood flour, basic magnesium sulfate fiber (magnesium oxysulfate fiber), and potassium titanate fiber. , Carbon fibers, glass fibers, natural fibers such as cotton, and synthetic fibers.
Among these, talc, glass fiber, basic magnesium sulfate fiber (magnesium oxysulfate fiber) is preferable, and talc is excellent in the physical property balance of the masterbatch and the propylene resin composition of the present invention, economical efficiency, More preferred.
The manufacturing method of these components (F) is not specifically limited, It selects suitably from well-known methods and conditions.
Moreover, you may use these components (F) in mixture of 2 or more types.

  In the masterbatch of the present invention, the lower limit of the content of the component (F) used as needed is preferably 1% by weight or more, more preferably, with respect to the total of 100% by weight of each component constituting the masterbatch. It is 2% by weight or more, more preferably 3% by weight or more. On the other hand, the upper limit is preferably 30% by weight or less, more preferably 25% by weight or less, and still more preferably 20% by weight or less. If the component (F) exceeds 30% by weight, the impact properties of the masterbatch and the propylene-based resin composition and the appearance of the molded product tend to decrease. If the component (F) is less than 1% by weight, the rigidity and dimensional stability tend to decrease. There is.

(7) Other optional components In addition to the above-mentioned components (A) to (F), the master batch of the present invention may include other optional components within the range where the effects of the present invention are not significantly impaired, if necessary. Ingredients may be blended. Such other optional components include pigments and other colorants, phenolic, sulfur and phosphorous antioxidants, antistatic agents, light stabilizers such as hindered amines, ultraviolet absorbers, nucleating agents and dispersants. , Neutralizers, foaming agents, metal deactivators, lubricants, flame retardants, thermoplastic resins other than components (A) to (E), and the like.

(8) The amount of each component In this invention, the total amount of a component (C) and a component (D) is 51-90 weight% with respect to the total of 100 weight% of each component which comprises a masterbatch, a component (A ), The component (B), and the total amount of the component (E) and / or the component (F) are preferably 10 to 49% by weight with respect to 100% by weight of each component constituting the master batch. If it exceeds this range, it is difficult to say that the masterbatch and the propylene resin composition of the present invention are environmentally friendly.
Furthermore, as described above, the weight ratio of component (B) / component (A) is preferably less than 0.5. By satisfying all of these simultaneously, the masterbatch and the propylene-based resin composition become environmentally compatible, and when the masterbatch is diluted with the propylene-based polymer, the compatibility with the propylene-based polymer becomes good, This is preferable because the physical property balance of the propylene-based resin composition is improved and the economic efficiency is also improved.

(9) Kneading process The masterbatch of this invention is manufactured through the kneading | mixing process which consists of the following process (I) and the following process (II) using the above-mentioned component.
Step (I): Step of melt-kneading component (C) and component (D) Step (II): Step of melt-kneading the product of step (I), component (A) and component (B)

Step (I) is a step of melt-kneading component (C) and component (D), and step (II) involves the product of step (I), component (A), component (B), and necessary. Depending on the process, the component (E) and / or the component (F) is melt-kneaded.
Here, in the step (I), the component (C) and the component (D) are preferably melt-kneaded in the absence of the component (B). This is because the presence of the component (B) may adversely affect the kneading effect such as the kneading compatibility of the component (C) and the component (D).
Further, when the component (E) is melt-kneaded as necessary, it must be performed in the step (II). This is because when the component (E) is melt-kneaded with the component (C) and the component (D) in the step (I), the master of the present invention is compared with the case where the component (E) is melt-kneaded in the step (II). This is because physical properties, particularly impact properties, of the batch and the propylene resin composition may be lowered.
The component (F) is basically preferably performed in the step (II), but can be melt-kneaded in the step (I). In addition, you may add another arbitrary component in any step of process (I) and process (II).

2. The manufacturing method of a masterbatch The manufacturing method of the masterbatch of this invention contains the following component (A) -component (D), and a component (C) is 100 weight% with respect to the sum total of each component which comprises a masterbatch. A method for producing a polylactic acid-containing masterbatch containing more than 50% by weight,
It includes the following step (I) and subsequent step (II).
Component (A): Polypropylene resin component (B): Acid-modified polyolefin resin and / or hydroxy-modified polyolefin resin component (C): Polylactic acid resin component (D): Epoxy-modified polyolefin resin Step (I): Step (II) for melt-kneading component (C) and component (D): Step for melt-kneading the product of step (I), component (A) and component (B) Further, optional component (E) and / or Alternatively, when component (F) is contained, step (II) comprises the product of step (I), component (A) and component (B), and further component (E) elastomer and / or component (F). The filler is preferably a step of blending 1 to 30% by weight with respect to a total of 100% by weight of each component constituting the master batch, and melt-kneading.
Furthermore, the step (I) is preferably a step in which the component (D) and the component (C) exceeding 50% by weight are melt-kneaded with respect to a total of 100% by weight of each component constituting the master batch.

  Specifically, the master batch of the present invention can be produced by melt-kneading each compounding component in the specific step. Each component is compounded using a conventionally known melt kneading apparatus such as a single screw extruder, a twin screw extruder, a Banbury mixer, a stirring (blade) mixer, a roll kneader, a kneader, etc. For example, a twin screw extruder is most preferably used. As the twin screw extruder, for example, TEX30α manufactured by Nippon Steel Works can be used for melt kneading.

  Step (I) and step (II) may be performed intermittently, but a method of continuously performing is preferable from the viewpoint of further improving the production efficiency (commercial productivity) of the masterbatch. For example, component (C) and component (D) are melt-kneaded (that is, step (I)) at the front stage of a single extruder, and component (A) and component (B) are continuously fed by side feed as necessary. There can be mentioned a method of supplying a component (E) and / or component (F) and then melt-kneading (that is, step (II)) at a later stage to obtain a master batch. Also, as the step (I), instead of the above side feed and melt kneading, the component (C) and the component (D) are melt kneaded in advance with an extruder attached to the extruder, and the step (II) is performed. The melt-kneaded product is supplied to the main extruder with the component (A), the component (B) and, if necessary, the component (E) and / or the component (F), and the method is carried out by melt-kneading. Can be mentioned. This method tends to further improve the physical property balance of the masterbatch and the propylene-based resin composition of the present invention.

Here, step (I) was once performed using the entire single extruder (kneading component (C) and component (D)), and then the kneaded product, component (A), and component (B). If necessary, component (E) and / or component (F) is again supplied to the same extruder from the previous stage to perform step (II) (that is, one of the above intermittent methods). ) Tends to improve the balance of physical properties of the masterbatch and the propylene resin composition of the present invention, but the production efficiency (commercial productivity) of the masterbatch is rather low compared to the above-described continuous method. It tends to be inferior.
In addition, using the whole single extruder, component (C) and component (D) used in step (I), component (A) and component (B) used in step (II), component (E) used as necessary ) And / or component (F) and other additives, that is, all the components necessary for production of the master batch of the present invention are melt-kneaded in a single step at a time. Since the physical property balance of a resin composition is reduced, it is not preferable.

In the melt kneading in the step (I) and the step (II), the resin temperature is preferably 240 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 185 ° C. or lower. If the resin temperature is within the above range, physical properties such as high-speed surface impact strength of the masterbatch and the propylene resin composition of the present invention are reduced by suppressing the orientation of the polylactic acid resin in the masterbatch. Tend to prevent.
The shape of the masterbatch is not particularly limited, and is usually used in the form of pellets due to work / workability during mixing / kneading with other materials, but in the form of granules, powders, etc. Also good.

II. Application 1. Polylactic acid-containing propylene-based resin composition The master batch of the present invention is a polylactic acid-containing propylene-based resin composition by mixing or kneading a propylene-based polymer (component (G)) as an example of its use. be able to.
That is, by diluting the master batch of the present invention with a relatively inexpensive component (G), as a propylene-based resin composition, expression of a wider range of physical properties, application to a wider range of application fields, and It is possible to reduce the manufacturing cost of the molded body and the like.

(1) Component (G): Propylene-based polymer The propylene-based polymer (component (G), hereinafter also simply referred to as component (G)) for diluting the masterbatch of the present invention is not particularly limited and is publicly known. The propylene-based polymer can be used. For example, propylene homopolymer, copolymer of propylene and α-olefin such as propylene / ethylene random copolymer and propylene / ethylene block copolymer, copolymer of propylene and vinyl compound, propylene and vinyl ester And a copolymer of propylene and an unsaturated organic acid or a derivative thereof, a copolymer of propylene and a conjugated diene, a copolymer of propylene and a non-conjugated polyene, and a mixture thereof.
Of these, propylene homopolymers, propylene / ethylene random copolymers, propylene / ethylene block copolymers, and so-called composite propylene polymers containing fillers such as talc and elastomers, etc. The propylene-based resin composition is preferable from the viewpoint of easily improving the balance of physical properties, and among them, a propylene / ethylene block copolymer and a propylene homopolymer (particularly high crystallinity) are more preferable.

Here, the component (G) has an MFR (230 ° C., 2.16 kg load) of 0.1 g / 10 min or more from the viewpoint of easy improvement of moldability and physical property balance of the propylene-based resin composition of the present invention. The thing of 4 g / 10min or more is more preferable, and the thing of 15-100 g / 10min is still more preferable.
Here, MFR is a value measured according to JIS-K7210.
In addition, the shape of the component (G) is not particularly limited, and is usually used in the form of pellets due to work / mixing / kneading properties, etc. during mixing / kneading with the master batch. It may be.
Component (G) may be a mixture and kneaded of two or more.

(2) Manufacture As a method for producing a polylactic acid-containing propylene resin composition containing the master batch of the present invention, the master batch and the component (G) are blended in a desired ratio and hand blended, etc. Examples thereof include dry blending and mixing (dilution) using various blenders such as a V blender and a tumbler mixer, and a mixer.
As another method, the master batch and the component (G) are blended in a desired ratio, and a single screw extruder, a twin screw extruder, a Banbury mixer, a stirring (blade) mixer, a roll kneader, Examples thereof include a method of kneading (granulating) using a kneading (extruding) machine such as a kneader.
In these methods, the mixture of MB and component (G) may be mixed or kneaded (granulated) at the same time, and each component is divided, for example, to improve performance. Part or all and part or all of component (G) may be mixed or kneaded (granulated), and then the remaining components may be mixed or kneaded (granulated).

Here, in the polylactic acid-containing propylene resin composition of the present invention, the mixed pellet composition obtained by mixing (diluting) the pellet-shaped master batch and the pellet-shaped component (G) has a wider range of moldability and physical properties. This is preferable from the viewpoints of manifestation of balance, application to a wider range of application fields, and a greater effect of reducing the manufacturing cost of molded articles and the like.
In this case, the mixing ratio of the master batch pellet and the component (G) pellet is preferably 1/9 to 9/1, more preferably 1/9 to 4/6, and further preferably 2/8 to 5/5. preferable.
If the mixing ratio exceeds 9/1, the moldability of the polylactic acid-containing propylene-based resin composition of the present invention, the effect of reducing the appearance of the molded body and the production cost of the molded body, etc. tend to be reduced, and less than 1/9 When it is, there exists a tendency for a physical-property balance to fall.

2. Molded Product The polylactic acid-containing propylene resin composition of the present invention can be formed into a molded product by various known molding methods.
For example, injection molding (including gas injection molding), injection compression molding (press injection), extrusion molding, hollow molding, calendar molding, inflation molding, uniaxially stretched film molding, biaxially stretched film molding, etc. As a result, various molded bodies can be obtained. Of these, injection molding, injection compression molding, and extrusion molding are preferable.

  The polylactic acid-containing propylene-based resin composition of the present invention can form a molded product having an excellent balance of physical properties such as flexural modulus and impact strength under good moldability (fluidity). In addition, it has excellent environmental compatibility and can improve commercial productivity (reduces the manufacturing cost of molded products), so various industrial parts fields that are used every year, such as trims, pillars, glove boxes, etc. Performance sufficient for practical use as molding materials for automotive interior / exterior parts such as instrument panels, bumpers, fenders, back doors, various housings, home appliance parts, housing equipment parts, various industrial parts, building material parts, etc. have. The propylene-based resin composition is a thermoplastic resin and can be used repeatedly. It can be said that the propylene resin composition is a material suitable for material recycling, including the fact that it promotes recycling activities for protecting the global environment. Target value is great.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto without departing from the gist thereof.
In addition, various physical properties and the like in the examples were measured according to the following procedures.

1. Measurement Evaluation Method (1) Masterbatch Production Efficiency Regarding the production efficiency of the masterbatch, whether the balance of physical properties of the masterbatch and the propylene resin composition of the present invention is expressed at a good level above a certain level. From the following evaluation.
○: The required number of melt kneading is only one in a single extruder, which is good.
Δ: The required number of melt kneading is twice in a single extruder or a plurality of extruders, which is considerably good.
X: The required number of melt kneadings is at least 3 times in a single extruder or a plurality of extruders.
(2) MFR
Conforms to JIS-K7210 (however, component (D) is ASTM-D1238) and 230 ° C and 2.16 kg load (however, component (C) and component (D) are 190 ° C and 2.16 kg load) To measure.
Here, MFR shown in the evaluation column of an Example and a comparative example is measured using the cut-out pellet from the test piece for a postscript (5) high-speed surface impact strength measurement.

(3) Flexural modulus Measured according to ISO 178 (JIS-K7171) at a measurement atmosphere temperature of 23 ° C. and a bending speed of 2 mm / min.
(4) Charpy impact strength (notched)
Measured at a measurement ambient temperature of 23 ° C. in accordance with JIS-K7111.
Here, the above-mentioned test pieces (3) and (4) were molded by using an injection molding machine (IS80G manufactured by Toshiba Machine Co., Ltd.) with a clamping pressure of 80 tons, conditions of a molding temperature of 200 ° C. and a mold temperature of 40 ° C. Molded with

(5) High-speed surface impact strength (high rate, HRIT (breaking energy))
Tester: Servo pulsar high-speed impact tester EHF-2H-20L type-with thermostatic chamber (manufactured by Shimadzu Corporation)
Shape of test piece: sheet (120 mm × 120 mm × 2 mmt)
Test piece preparation method: An injection molding machine (IS170 manufactured by Toshiba Machine Co., Ltd.) with a clamping pressure of 170 tons is used, and molding is performed under conditions of a molding temperature of 200 ° C. and a mold temperature of 40 ° C.
Test method: Dirt (diameter 1/2 inch) as a load sensor is made to collide with a test piece placed on a support base (hole diameter 3 inches) at a speed of 1 m / sec. The impact energy absorbed up to the crack initiation point in the obtained impact pattern is calculated and used as the surface impact strength of the material.

2. Material (1) Polymerized using component (A) polypropylene resin / Ziegler Natta catalyst, MFR (230 ° C., load 2.16 kg) is 5.9 g / 10 min, flexural modulus is 2350 MPa, Charpy impact strength (23 ° C) is 2.5 kJ / m ² , a highly crystalline propylene homopolymer resin (manufactured by Nippon Polypro)
(2) Component (B) acid-modified polyolefin resin / maleic anhydride-modified polypropylene having a maleic anhydride graft ratio of 0.8% by weight (manufactured by Arkema, OREVAC CA100)

(3) Polylactic acid resin (manufactured by Unitika Ltd., TP-4000) having a component (C) polylactic acid resin / MFR (190 ° C., load 2.16 kg) of 3 g / 10 min.
(4) Component (D) Epoxy-modified polyolefin resin / ethylene-glycidyl methacrylate (E-GMA) copolymer having a glycidyl methacrylate (GMA) content of 12% by weight (manufactured by Sumitomo Chemical Co., Ltd., Bond First E)

(5) Styrene-ethylene-butylene-styrene block copolymer (SEBS) having a component (E) elastomer / MFR (230 ° C., load 2.16 kg) of 13 g / 10 min and a styrene content of 13% by weight.
An ethylene-butene copolymer elastomer (EBR) having an MFR (230 ° C., load 2.16 kg) of 7 g / 10 min and a butene content of 32% by weight
(6) Component (F) Filler-Talc with an average particle size of 5.5 µm

(7) Propylene / ethylene block copolymer (Nippon Polypro Co., Ltd.) polymerized using a component (G) propylene-based polymer / Ziegler-Natta catalyst and having an MFR (230 ° C., load 2.16 kg) of 30 g / 10 min. Manufactured by Novatec BC03B)
A propylene homopolymer (Novatech MA1B, manufactured by Nippon Polypro Co., Ltd.), polymerized using a Ziegler-Natta catalyst and having an MFR (230 ° C., load 2.16 kg) of 21 g / 10 min.

3. Examples and Comparative Examples (1) Example 1
(A) Manufacture of masterbatch First, as process (I), polylactic acid resin (component (C), TP-4000) 20 weight part (component (A)-(D) total 90.9 with respect to 100 weight%). And 2 parts by weight of an ethylene-glycidyl methacrylate copolymer (component (D), bond first E) (9.1% by weight relative to the total of 100% by weight of components (A) to (D)), As a stabilizer with respect to 100 parts by weight of the combination of component (C) and component (D), 0.1 parts by weight of a phenolic antioxidant (IRGANOX 1010 manufactured by Ciba Specialty Chemicals), phosphorus antioxidant (Ciba Specialty) A blend of 0.05 parts by weight of IRGAFOS 168 manufactured by Chemicals Co., Ltd. is supplied from the front stage of the extrusion unit of the same-direction rotating twin-screw extruder (manufactured by Nippon Steel Works: TEX30α). -Menu rotational speed 300 rpm, extrusion rate 10 kg / H, and melt-kneaded under conditions of a kneading temperature 180 ° C. (see Table 1).

As a step (II), 10 parts by weight of highly crystalline propylene homopolymer resin (component (A)) (30.3% by weight with respect to 100% by weight of the total of components (A) to (D)), anhydrous male 1 part by weight of acid-modified polypropylene (component (B), OREVAC CA100) (3% by weight based on 100% by weight of the total of components (A) to (D)), and a combination of component (A) and component (B) 100 parts by weight of phenol-based antioxidant (IRGANOX1010) 0.1 part by weight and phosphorus-based antioxidant (IRGAFOS168) 0.05 part by weight using a side feeder in the middle of the kneading part of the extruder Together with the melt-kneaded composition (component (C) + component (D)) 22 parts by weight (66.7% by weight relative to the total of 100% by weight of components (A) to (D)) , Melt kneading under the above conditions To obtain a melt-kneaded composition (masterbatch). At this time, these blending ratios were adjusted by adjusting the side feed discharge amount and the discharge amount of the extruder.
In addition, the content rate of the component (C) with respect to a total of 100 weight% of a component (A)-(D) is 60.6 weight% (refer Table 1).

(B) Production and evaluation of polylactic acid-containing propylene-based resin composition 33% by weight (polylactic acid-containing propylene-based resin composition) of master batch (pellet-like) obtained by the above-mentioned step (I) and the subsequent step (II) 100% by weight) and 67% by weight of component (G) propylene polymer (Novatec BC03B pellets) (100% by weight of polylactic acid-containing propylene resin composition) are sufficiently mixed in a V-blender. And this mixture was shape | molded and evaluated by the said method. The evaluation results are shown in Table 1.

(2) Example 2
In the step (II), the component (A) is changed to 5 parts by weight (15.15% by weight with respect to the total of 100% by weight of the components (A) to (E)), and the component (E) is styrene-ethylene. The same procedure as in Example 1 was conducted except that 5 parts by weight of butylene-styrene block copolymer (SEBS) was blended (15.15% by weight relative to the total of 100% by weight of components (A) to (E)). It was. The evaluation results are shown in Table 1.
(3) Example 3
Production and evaluation of the polylactic acid-containing propylene resin composition were performed in the same manner as in Example 2 except that Novatec MA1B pellets were used as the component (G). The evaluation results are shown in Table 1.

(4) Example 4
In the step (I), the blending of the component (C) and the component (D) is 30 parts by weight (89.6% by weight relative to the total of 100% by weight of the components (A) to (E)), 3.5% by weight. Parts (components (A) to (E) are 10.4% by weight relative to the total of 100% by weight), and in step (II), component (A) is 10.5 parts by weight (components (A) to (E) 21 parts by weight relative to the total of 100% by weight), 1 part by weight of component (B) (2% by weight with respect to 100% by weight of the total of ingredients (A) to (E)), and further, a polylactic acid-containing propylene resin In the production and evaluation of the composition, the same procedure as in Example 2 was performed, except that the mixing ratio of MB and component (G) was 50/50 by weight. The evaluation results are shown in Table 1.
(5) Example 5
In step (II), 5 parts by weight of ethylene / butene copolymer elastomer (EBR) (15.15% by weight relative to the total of 100% by weight of components (A) to (E)) was blended as component (E). Except for this, the same procedure as in Example 2 was performed. The evaluation results are shown in Table 1.

(6) Example 6
In step (II), talc (component (F)) is further blended in an amount of 5 parts by weight (13.15% by weight based on 100% by weight of components (A) to (F)), and further contains polylactic acid. Production and evaluation of the propylene-based resin composition were performed in the same manner as in Example 2 except that the mixing ratio of MB and component (G) was 38/62 by weight. The evaluation results are shown in Table 1.
(7) Example 7
Once the part corresponding to step (I) of Example 1, that is, 20 parts by weight of component (C) (90.9% by weight relative to the total of 100% by weight of components (A) to (D)) and component (D) 2 A blend of a weight part (9.1% by weight with respect to 100% by weight of the total of components (A) to (D)) and an additive is used in the same direction rotating twin-screw extruder (TEX30α) (first stage) Through the latter stage, melt-kneading was performed.
Thereafter, 22 parts by weight of the melt-kneaded composition (component (C) + component (D)) (66.7% by weight relative to the total of 100% by weight of components (A) to (D)) and component (A) 10 parts by weight (30.3% by weight relative to the total of 100% by weight of components (A) to (D)) and 1 part by weight of component (B) (to a total of 100% by weight of components (A) to (D)) 3% by weight) and an additive were fed again from the same front part of the extruder and melt-kneaded using the whole extruder. That is, the portion corresponding to step (I) of Example 1 and the portion corresponding to step (II) were separately performed twice using the same extruder. Except this point, the same procedure as in Example 1 was performed. The evaluation results are shown in Table 1.

(8) Comparative Example 1
In step (II), component (B) was not blended, but component (A) was blended in an amount of 11 parts by weight (33.3% by weight based on 100% by weight of components (A) to (D)). Performed as in Example 1. The evaluation results are shown in Table 2.
(9) Comparative Example 2
In step (I), component (D) was not blended, but component (C) was blended in an amount of 22 parts by weight (66.7% by weight relative to the total of 100% by weight of components (A) to (D)). Performed as in Example 1. The evaluation results are shown in Table 2.

(10) Comparative Example 3
In the step (I), the blending of the component (A) and the component (B) is 10 parts by weight (90.9% by weight with respect to the total of 100% by weight of the component (A) and the component (B)), 1 part by weight. (9.1% by weight relative to 100% by weight of the total of component (A) and component (B)), and in step (II), 20 parts by weight (component (C) A) to (D) with a total of 100% by weight of 60.6% by weight) and 2 parts by weight (components (A) to (D) with a total of 100% by weight of 6.1% by weight). Example 1 except that the composition (component (A) + component (B)) was 11 parts by weight (33.3% by weight relative to the total of 100% by weight of components (A) to (D)) and melt-kneaded. Went to.
That is, the order of the kneading step of the component (A) and the component (B) and the kneading step of the component (C) and the component (D) was performed in the reverse order of Example 1. Except this point, the same procedure as in Example 1 was performed. The evaluation results are shown in Table 2.

(11) Comparative Example 4
10 parts by weight of highly crystalline propylene homopolymer resin (component (A)) (30.3% by weight based on 100% by weight of components (A) to (D)) and maleic anhydride-modified polypropylene (component (B ), OREVAC CA100) 1 part by weight (3% by weight relative to the total of 100% by weight of components (A) to (D)) and 20 parts by weight of polylactic acid resin (component (C), TP-4000) (component ( A) to (D) of 60.6% by weight based on the total of 100% by weight) and ethylene-glycidyl methacrylate copolymer (component (D), bond first E) 2 parts by weight (components (A) to (D) And 0.1 weight percent of a phenolic antioxidant (IRGANOX1010) as a stabilizer with respect to 100 weight parts of the blend of the components (A) to (D). Part, phosphorus antioxidant ( IRGAFOS 168) A blend of 0.05 part by weight was supplied from the preceding stage of the extrusion part of the extruder (TEX30α) and melt-kneaded using the whole extruder. That is, all the components shown in Example 1 were melt-kneaded all at once in step (I). Except this point, the same procedure as in Example 1 was performed. The evaluation results are shown in Table 2.

4). Evaluation From the results shown in Table 1, the master batches shown in Examples 1 to 7 and the polylactic acid-containing propylene-based resin composition using the master batches satisfying the respective requirements in the essential constituent requirements of the present invention are both master batch production efficiencies. In addition to being good or considerably good, the moldability (fluidity, MFR), flexural modulus, Charpy impact strength, and high-speed surface impact strength (breaking energy) are improved.
In addition to the various performances mentioned above, these products have excellent environmental compatibility and can improve commercial productivity (reduce manufacturing costs), so automobile interior and exterior parts, home appliance parts, housing equipment parts, It has become clear that it has performance suitable for industrial parts and building material parts.

On the other hand, from the results shown in Table 2, the master batches shown in Comparative Examples 1 to 4 and the polylactic acid-containing propylene-based resin composition using the same are poor in performance balance.
For example, in the polylactic acid-containing propylene-based resin composition using the masterbatch of Comparative Example 1 in which the component (B) is not blended in the step (II), the production efficiency of the masterbatch is good, but the high-speed surface impact The strength (breaking energy, hereinafter also simply referred to as surface impact) was significantly different from Example 1. This indicates that the effect of improving the surface impact is remarkably different depending on the presence or absence of the component (B) in the step (II), and it is essential that the component (B) satisfies the requirements of the present invention.
Moreover, in the polylactic acid containing propylene-type resin composition using the masterbatch of the comparative example 2 which does not mix | blend a component (D) in process (I), although the manufacturing efficiency of a masterbatch is favorable, surface impact is A significant difference from Example 1 occurred.
This shows that the effect of improving the surface impact is remarkably different depending on the presence or absence of the component (D) in the step (I), and it is essential that the component (D) satisfies the requirements of the present invention.

In the step (I), the component (A) and the component (B) are blended and kneaded, and in the step (II), the component (C) and the component (D) are blended and kneaded, that is, the component (A ) And component (B) kneading step, and component (C) and component (D) kneading step in the order reverse to that of Example 1, containing polylactic acid using the master batch of Comparative Example 3 In the propylene-based resin composition, the production efficiency of the masterbatch was good, but the surface impact was significantly different from that in Example 1. This is because the effect of improving the surface impact is remarkably different depending on the component contents to be blended and kneaded in step (I) and the component contents to be blended and kneaded in step (II), and the blending and kneading in step (I) and step (II) is performed. The content of each component indicates that it is essential to satisfy the requirements of the present invention.
Moreover, in the polylactic acid containing propylene-type resin composition using the masterbatch of the comparative example 4 which melt-kneaded all the components shown in Example 1 collectively only by process (I), the manufacturing efficiency of a masterbatch is Although good, the surface impact was significantly different from Example 1. This indicates that it is essential that the melt-kneading process satisfies the requirements of the present invention.
From the results of the above examples and comparative examples, the rationality and significance of the configuration and requirements of the present invention are demonstrated, and the superiority of the present invention over the prior art is also apparent.

The polylactic acid-containing masterbatch of the present invention, the production method thereof, the polylactic acid-containing propylene resin composition and the molded body thereof have excellent physical property balance such as flexural modulus and impact strength under good moldability (fluidity). In addition to being environmentally friendly, it also has excellent economic efficiency such as excellent manufacturing efficiency.
For this reason, for example, interior and exterior parts of automobiles such as trims, pillars, glove boxes, instrument panels, bumpers, fenders, back doors, various housings, home appliance parts, housing equipment parts, various industrial parts, building materials It can be suitably used for parts and the like.

Claims (17)

A polylactic acid-containing masterbatch containing the following components (A) to (D) and containing more than 50% by weight of component (C) with respect to a total of 100% by weight of each component constituting the masterbatch. And
A polylactic acid-containing masterbatch produced by a kneading step comprising the following step (I) and subsequent step (II).
Component (A): Polypropylene resin component (B): Acid-modified polyolefin resin and / or hydroxy-modified polyolefin resin component (C): Polylactic acid resin component (D): Epoxy-modified polyolefin resin Step (I): Step (II) for melt-kneading component (C) and component (D): Step for melt-kneading the product of step (I), component (A) and component (B)   Furthermore, the polylactic acid containing masterbatch of Claim 1 containing a component (E) elastomer and / or a component (F) filler.   The polylactic acid-containing masterbatch according to claim 2, wherein the component (E) is contained in an amount of 1 to 30% by weight with respect to a total of 100% by weight of each component constituting the masterbatch.   The polylactic acid-containing masterbatch according to claim 2 or 3, wherein the component (F) is contained in an amount of 1 to 30% by weight based on a total of 100% by weight of each component constituting the masterbatch.   Step (II) is a step of melt-kneading the product of step (I), component (A) and component (B), and component (E) and / or component (F). The polylactic acid containing masterbatch of any one of Claims 2-4. The total amount of the component (C) and the component (D) is 51 to 90% by weight with respect to 100% by weight of each component constituting the master batch,
The total amount of the component (A), the component (B) and the component (E) and / or the component (F) is 10 to 49% by weight based on 100% by weight of each component constituting the master batch, and
The polylactic acid-containing masterbatch according to any one of claims 2 to 5, wherein the weight ratio of component (B) / component (A) is less than 0.5.   The polylactic acid-containing masterbatch according to any one of claims 1 to 6, wherein the component (C) contains L-lactic acid or D-lactic acid as a main component.   The polylactic acid-containing masterbatch according to any one of claims 1 to 7, wherein the component (D) is an ethylene-glycidyl methacrylate copolymer.   The polylactic acid according to any one of claims 1 to 8, wherein the component (B) is an acid-modified polyolefin resin having an acid amount of 0.05 to 10% by weight in terms of unsaturated carboxylic acid. Contains masterbatch.   The polylactic acid-containing master according to any one of claims 1 to 9, wherein the component (A) has a melt flow rate (230 ° C, 2.16 kg load) of 0.1 g / 10 min or more. batch. Production of a polylactic acid-containing masterbatch containing the following components (A) to (D) and containing component (C) in an amount exceeding 50% by weight with respect to a total of 100% by weight of each component constituting the masterbatch A method,
The manufacturing method of the polylactic acid containing masterbatch characterized by including the following process (I) and the following process (II).
Component (A): Polypropylene resin component (B): Acid-modified polyolefin resin and / or hydroxy-modified polyolefin resin component (C): Polylactic acid resin component (D): Epoxy-modified polyolefin resin Step (I): Step (II) for melt-kneading component (C) and component (D): Step for melt-kneading the product of step (I), component (A) and component (B)   In step (II), the product of step (I), component (A) and component (B), and further component (E) elastomer and / or component (F) filler, each component constituting a master batch The method for producing a polylactic acid-containing masterbatch according to claim 11, which is a step of blending 1 to 30% by weight with respect to 100% by weight in total and melt-kneading.   The step (I) is a step of melt-kneading the component (D) and the component (C) exceeding 50% by weight with respect to 100% by weight of each component constituting the masterbatch. Or the manufacturing method of the polylactic acid containing masterbatch of 12.   The method for producing a polylactic acid-containing masterbatch according to any one of claims 11 to 13, wherein the melt-kneading temperature in step (I) and step (II) is 240 ° C or lower.   A polylactic acid-containing propylene-based resin composition obtained by mixing or kneading the polylactic acid-containing masterbatch according to any one of claims 1 to 10 and the component (G) propylene-based polymer.   The polylactic acid-containing propylene-based resin composition according to claim 15, wherein the weight ratio of the polylactic acid-containing master batch to the component (G) is 1/9 to 9/1. A molded article obtained by molding the polylactic acid-containing propylene-based resin composition according to claim 15 or 16.