JP5277531B2 - Resin composition and molded article comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in injection-molding property, having a high Vicat softening point and capable of imparting flexibility, and a molded article consisting of the same. <P>SOLUTION: This resin composition is obtained by blending (B) 0.1-15 pt./pts.wt. polyalkylene glycol having 1,000-21,000 number-average molecular weight and (C) 0.5-50 pt./pts.wt. ester-based plasticizer expressed by the following formula (a) with (A) 100 pts.wt. polylactic acid resin. The formula (a): -COO-(CH<SB>2</SB>COO)<SB>m</SB>-(R<SP>1</SP>O)<SB>n</SB>-R<SP>2</SP>[wherein, (m) is 0-5 integer; (n) is 0-6 integer; R<SP>1</SP>is a 1-6C alkylene; R<SP>2</SP>is a 1-10C linear or branched alkyl, a 6-12C aryl, a 7-15C arylalkyl or a 7-15C alkylaryl; and provided that (m+n)&ge;1]. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention comprises a polylactic acid resin, a polyalkylene glycol compound having a number average molecular weight of 1000 to 21000, and an ester plasticizer having a specific structure, and has excellent injection moldability, high Vicat softening point, and flexibility. The present invention relates to a resin composition that can be applied, and a molded product comprising the same.

  From the viewpoint of protecting the global environment, biodegradable polymers that are decomposed in the natural environment by the action of microorganisms existing in the soil and water have attracted attention, and various biodegradable polymers have been developed. Among these biodegradable polymers, examples of biodegradable polymers that can be melt-molded include polyhydroxybutyrate, polycaprolactone, aliphatic dicarboxylic acid components such as succinic acid and adipic acid, and ethylene glycol and butanediol. Aliphatic polyester resins such as polyethylene succinate, polybutylene adipate, and polylactic acid resin are known.

  Among the aliphatic polyester resins, polylactic acid resin is particularly expected as a biodegradable polymer that can be melt-molded because it has a relatively low cost and a melting point of about 170 ° C. Recently, lactic acid, which is a monomer, has been manufactured at low cost by fermentation using microorganisms, and it has become possible to produce polylactic acid at a much lower cost. Also, the use as a general-purpose polymer has been studied. However, since polylactic acid has a low crystallization rate, there is a problem that the solidification rate is slow and a long molding time is required at the time of injection molding, and improvement thereof has been desired.

  As a method for improving this problem, Patent Document 1 proposes to use a wax plasticizer as a crystal nucleating agent and a crystallization accelerator in a polylactic acid-based polymer, and in a mold temperature range of 80 ° C. or higher. It has been shown that the modulus rapidly increases and heat resistance can be improved.

Patent Document 2 proposes a resin composition in which polylactic acid and poly-ε-caprolactone are blended with crystalline inorganic powder containing 50% or more of SiO ₂ (talc in the examples) and an ester plasticizer. Yes.

  However, the proposals in Patent Document 1 and Patent Document 2 described above have an effect of increasing the degree of crystallinity, but are not sufficient as a method for shortening the molding time in injection molding.

  As a method for softening a polylactic acid-based polymer, a method for softening by blending a plasticizer and a method for blending rubber have been studied.

  For example, Patent Document 3 discusses a method of blending a specific plasticizer with a polylactic acid polymer.

  Patent Document 4 discusses a method of blending vinyl acetate as a rubber in addition to a plasticizer.

However, the proposals in Patent Document 3 and Patent Document 4 described above have an effect of softening, but because the Vicat softening point is low, the usable temperature range is narrow, and as a method of shortening the molding time at the time of injection molding. Was not enough.
JP-A-11-106628 (page 2-5) JP-A-8-193165 (page 2-3) Japanese Patent No. 3421769 (pages 4-7) JP-A-9-151310 (page 2-3)

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Accordingly, an object of the present invention is to provide a resin composition excellent in injection moldability, having a high Vicat softening point, and capable of imparting flexibility, and a molded product comprising the same.

As a result of intensive studies to solve the above problems, the present inventors have formulated a resin composition comprising a polylactic acid resin, a polyalkylene glycol compound having a number average molecular weight of 8300 to 21000, and an ester plasticizer having a specific structure. The present invention has been found to exhibit excellent characteristics that meet the above-mentioned purpose, and has reached the present invention.

That is, the present invention
(1) (B) 0.1 to 15 parts by weight of a polyalkylene glycol having a number average molecular weight of 8300 to 21000 and ( C) a structure represented by the following formula (a) with respect to 100 parts by weight of (A) polylactic acid resin. A resin composition comprising (D) a styrene copolymer, which is a vinyl resin having an ester plasticizer of 0.5 to 50 parts by weight and a rubber component content of 30 to 80% by weight ,
^{_{-COO- (CH 2 COO) m- (}} R 1 O) n-R 2 (a)
(In formula (a), m represents an integer of 0 to 5, n represents an integer of 0 to 6, R ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ² has 1 to 10 carbon atoms. A linear or branched alkyl group, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, or an alkylaryl group having 7 to 15 carbon atoms, provided that m + n ≧ 1.
(2) The (C) ester plasticizer is at least one selected from methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, benzyl butyl diglycol adipate, and ethoxycarbonylmethyl dibutyl citrate (1) The resin composition according to
(3) The resin composition according to any one of (1) to (2) , further comprising (E) an acid anhydride,
(4) The resin composition according to (3) , wherein the (E) acid anhydride is maleic acid anhydride or succinic acid anhydride,
(5) The resin composition according to any one of (1) to (4) , further comprising (F) an inorganic filler.
(6) The resin composition according to any one of (1) to (5) , further comprising (G) a flame retardant.
(7) The resin composition according to any one of (1) to (6) , further comprising (I) a maleic anhydride-modified polyolefin wax,
(8) A molded article comprising the resin composition according to any one of (1) to (7) ,
(9) the molded article is a casing, packing, the cover, film, molded article according to either of the sheet (8).

  The resin composition of the present invention is a resin composition excellent in injection moldability and Vicat softening point and capable of imparting flexibility. In addition, the molded product obtained from this resin composition can be used for various applications such as civil engineering materials, building materials, furniture members, materials for gaming machines, electrical / electronic parts, automobile parts, various daily necessities, taking advantage of the above characteristics. Can do.

  Hereinafter, the present invention will be described in detail.

  The (A) polylactic acid resin used in the present invention is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. Other monomer units include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentane. Glycol compounds such as erythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid , Isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarbohydrate Acids, dicarboxylic acids such as 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, and caprolactone And lactones such as valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Such a copolymer component is preferably contained in an amount of generally 0 to 30 mol%, preferably 0 to 10 mol%, in all monomer components.

  In the present invention, from the viewpoint of heat resistance, it is preferable to use a polylactic acid resin having a high optical purity of the lactic acid component. That is, among the total lactic acid components of the polylactic acid resin, it is preferable that the L isomer is contained at 80% or more, or the D isomer is contained at 80% or more, the L isomer is contained at 90% or more, or the D isomer is 90% or more. It is particularly preferable that the L-form is contained at 95% or more, or the D-form is more preferably contained at 95% or more, the L-form is contained at 98% or more, or the D-form is contained at 98% or more. Further preferred. Moreover, the upper limit of the content of L-form or D-form is usually 100% or less.

  The melting point of the (A) polylactic acid resin is not particularly limited, but is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 160 ° C. or higher. (A) The melting point of the polylactic acid resin is usually increased by increasing the optical purity of the lactic acid component, and the polylactic acid resin having a melting point of 120 ° C. or higher contains 90% or more of the L form or 90% of the D form. By being contained above, a polylactic acid resin having a melting point of 150 ° C. or higher can be obtained by containing 95% or more of L form or 95% or more of D form. In the present invention, the melting point of (A) polylactic acid resin is a value measured by a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min.

  (A) The molecular weight and molecular weight distribution of the polylactic acid resin are not particularly limited as long as it can be substantially molded, but the weight average molecular weight is usually 10,000 or more, preferably 40,000 or more. Furthermore, it is desirable that it is 80,000 or more. Although there is no restriction | limiting in particular as an upper limit, Preferably it is 500,000 or less from a viewpoint of a moldability. The weight average molecular weight here refers to the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography. Further, polylactic acid resins having different molecular weights may be mixed and used.

  (A) The polylactic acid resin may be modified, for example, by using maleic anhydride-modified polylactic acid resin, epoxy-modified polylactic acid resin, amine-modified polylactic acid resin, etc., not only heat resistance, The mechanical properties tend to be improved, which is preferable.

  (A) As a manufacturing method of a polylactic acid resin, a well-known polymerization method can be used, and the direct polymerization method from lactic acid, the ring-opening polymerization method via a lactide, etc. can be mentioned.

In the present invention, (B) polyalkylene glycol having a number average molecular weight of 8300 to 21000 is polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, bisphenols. Polyalkylene glycols such as ethylene oxide addition polymers, propylene oxide addition polymers of bisphenols, tetrahydrofuran addition polymers of bisphenols, or end-capping compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds , Especially polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) blocks and / or runs Dam copolymers are preferably used, and one or more of them are used. The number average molecular weight here is a number average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography, and polyalkylene glycols having different number average molecular weights may be mixed and used.

The blending amount of (B) polyalkylene glycol having a number average molecular weight of 8300 to 21000 is 0.1 to 15 parts by weight, preferably 0.2 to 12 parts by weight, based on 100 parts by weight of component (A). 0.3 to 10 parts by weight is more preferable, and 0.4 to 5 parts by weight is most preferable. When the blending amount of the (B) polyalkylene glycol having a number average molecular weight of 1000 to 21000 is less than 0.1 parts by weight, the effect of improving the injection moldability and Vicat softening point is small. Since it bleeds out to the surface, it is not preferable.

In the present invention, (C) the ester plasticizer having a structure represented by the following formula (a) is:
^{_{-COO- (CH 2 COO) m- (}} R 1 O) n-R 2 (a)
(In formula (a), m represents an integer of 0 to 5, n represents an integer of 0 to 6, R ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ² has 1 to 10 carbon atoms. A linear or branched alkyl group, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, or an alkylaryl group having 7 to 15 carbon atoms, provided that m + n ≧ 1.

Among them, in the above formula, m is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, further preferably an integer of 0 to 1, and n is an integer of 0 to 5. Preferably an integer of 0 to 4, more preferably 0 to 3, R ¹ is preferably an alkylene group having 2 to 5 carbon atoms, and 2 to 4 carbon atoms. R ² is more preferably a linear or branched alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or a carbon number. It is preferably an alkylaryl group having 7 to 12 carbon atoms, a linear alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 8 carbon atoms, an arylalkyl group having 7 to 9 carbon atoms, or 7 to 9 carbon atoms. An alkylaryl group of It is more preferable.

  In the present invention, as the ester plasticizer having the structure represented by (C) (a), one having at least one structure represented by the above formula can be used. It is more preferable to use one having two or more structures, preferably three or more structures.

  Specific examples of ester plasticizers having such a structure include methyl diglycol butyl diglycol succinate, ethyl diglycol butyl diglycol succinate, propyl diglycol butyl diglycol succinate, benzyl methyl diglycol succinate, Methoxycarbonylmethyl methyl diglycol succinate, ethoxycarbonylmethyl methyl diglycol succinate, benzyl butyl diglycol succinate, methyl diglycol butyl diglycol adipate, ethyl diglycol butyl diglycol adipate, propyl diglycol butyl diglycol adipate, benzyl Methyl diglycol adipate, benzyl butyl diglycol adipate, methoxycarbonylmethyl methyl diglycol a Pete, methoxycarbonylmethyl butyl diglycol adipate, ethoxycarbonylmethyl methyl diglycol adipate, ethoxycarbonylmethyl butyl diglycol adipate, dimethyl diglycol monobutyl diglycol citrate, benzyl dimethyl diglycol citrate, methoxycarbonylmethyl dimethyl citrate, Methoxycarbonylmethyl diethyl citrate, methoxycarbonylmethyl dibutyl citrate, ethoxycarbonylmethyl dimethyl citrate, ethoxycarbonylmethyl dibutyl citrate, ethoxycarbonylmethyl dioctyl citrate, butoxycarbonylmethyl dimethyl citrate, butoxycarbonylmethyl diethyl citrate, butoxy Carbonylmethyldi Tyrsiteate, dimethoxycarbonylmethyl monomethyl citrate, dimethoxycarbonylmethyl monoethyl citrate, dimethoxycarbonylmethyl monobutyl citrate, diethoxycarbonylmethyl monomethyl citrate, diethoxycarbonylmethyl monobutyl citrate, diethoxycarbonylmethyl monooctyl Cytolate, dibutoxycarbonylmethyl monomethyl citrate, dibutoxycarbonylmethyl monoethyl citrate, dibutoxycarbonylmethyl monobutyl citrate, ethoxycarbonylmethyldimethyldiglycol citrate, ethoxycarbonylmethyldibutyldiglycol citrate, diethoxycarbonyl Methyl monomethyl diglycol citrate, diethoxycarbon Methyl diglycol butyl diglycol succinate, benzyl methyl diglycol succinate, benzyl butyl diglycol succinate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol Adipate, benzylbutyl diglycol adipate, methoxycarbonylmethyl dibutyl citrate, ethoxycarbonylmethyl dibutyl citrate, butoxycarbonylmethyl dibutyl citrate, dimethoxycarbonylmethyl monobutyl citrate, diethoxycarbonylmethyl monobutyl citrate, dibutoxycarbonylmethyl Monobutyl citrate is preferred.

  Among the ester plasticizers, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, benzyl butyl diglycol adipate, and ethoxycarbonylmethyl dibutyl citrate are most preferable, and are represented by the above (C) (a). One type or two or more types of ester plasticizers having a structure can be used.

  Moreover, as a commercial item of the said ester plasticizer, Daihachi Chemical Co., Ltd. "DAIFATTY" etc. are mentioned.

  Further, the amount of the ester plasticizer having the structure represented by (C) (a) is not particularly limited, but from the viewpoint of heat resistance, (A) 100 wt. Part is preferably 0.5 to 50 parts by weight, more preferably 0.7 to 45 parts by weight, further preferably 0.9 to 40 parts by weight, and 1 to 30 parts by weight. Most preferred. When the compounding amount of the ester plasticizer having the structure represented by the above (C) (a) is less than 0.1 parts by weight, the effect of improving the injection moldability and Vicat softening point is small. Tends to bleed out on the surface of the molded product.

  Moreover, the number average molecular weight of the ester plasticizer having the structure represented by the above (C) (a) is not particularly limited, but is preferably 200 to 1500, and more preferably 300 to 1000. When the number average molecular weight is less than 200, bleeding out tends to occur, and when it exceeds 1500, the effect of imparting flexibility to the resin composition of the present invention tends to be reduced.

  The resin composition of the present invention may further contain (D) a styrene copolymer. Here, the (D) styrene copolymer is one or more selected from styrene or α-methylstyrene selected from aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, and maleimide monomers. Examples include resins obtained by polymerizing monomers, or those obtained by graft polymerization of these monomers to rubber components such as polybutadiene rubber (hereinafter referred to as “copolymers”). May be collectively called). In the present invention, it is preferable to use a vinyl resin having a rubber component content exceeding 30% by weight as the (D) styrene copolymer. Here, the rubber component content is more preferably 30 to 80% by weight. When the styrene copolymer is a vinyl resin exceeding 30% by weight of the rubber component, it is particularly excellent in elastic recovery and impact resistance, so that injection moldability, Vicat softening point, elastic recovery and Development as a material with impact resistance can be expected.

  Examples of the aromatic vinyl compound include vinyl toluene and divinylbenzene, examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and examples of the (meth) acrylic acid alkyl ester include methyl methacrylate. (Meth) acrylic acid alkyl esters such as ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and stearyl acrylate, and the like. N-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and derivatives thereof. Further, (D) a copolymer with the following component capable of copolymerization with a styrene-based copolymer is also included in the present invention. Specific examples of components capable of such copolymerization include diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, and vinyl alkyl ethers.

  (D) Examples of preferred copolymers of styrene-based copolymers include methyl methacrylate / acrylonitrile / styrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, acrylate / acrylonitrile / styrene resin (AAS resin). ), Chlorinated polyethylene / acrylonitrile / styrene resin (ACS resin), acrylonitrile / ethylene / styrene resin (AES resin), styrene / N-phenylmaleimide resin, styrene / acrylonitrile / N-phenylmaleimide resin, acrylonitrile / butadiene / styrene resin (ABS resin), methyl methacrylate / butadiene / styrene resin (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene resin (MABS resin), high impact Polystyrene resin (HI-PS resin), styrene / butadiene / styrene resin (SBS resin), styrene / isoprene / styrene resin (SIS resin), styrene / ethylene / propylene resin (SEP resin), styrene / ethylene / butylene / styrene resin (SEBS resin) and the like, and these may be used as a mixture of two or more. Among the (D) styrene copolymers, styrene copolymers containing a rubber component are particularly preferred, and acrylonitrile / Butadiene / styrene resin (ABS resin), methyl methacrylate / butadiene / styrene resin (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene resin (MABS resin), high impact polystyrene resin (HI-PS resin), styrene / Ethylene / But Rene / styrene resin (SEBS resin) and the like are preferable. Furthermore, acrylonitrile / butadiene / styrene resin (ABS resin), methyl methacrylate / butadiene / styrene resin (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene resin ( MABS resin), high impact-polystyrene resin (HI-PS resin), styrene copolymer modified with rubbery polymer such as styrene / ethylene / butylene / styrene resin (SEBS resin), and butadiene Such as acrylonitrile / butadiene / styrene resin (ABS resin), methyl methacrylate / butadiene / styrene resin (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene resin (MABS resin) having a content of 30% by weight or more. A styrenic copolymer modified with a modified polymer is particularly preferably used (/ indicates copolymerization). As an example of a method for measuring the amount of the rubbery polymer of the styrenic copolymer, a sample is made into a thin film of about 10 μm using a hot press and an infrared spectrophotometer is used to mix the rubbery polymer and other copolymers. It can be calculated from the wave height ratio with the polymerization component, and when the component of the other copolymerization component is unknown, it is preferable to measure after identifying the other copolymerization component by NMR analysis.

  Further, the (D) styrenic copolymer may be copolymerized with other monomers such as a copolymerizable maleimide monomer within a range not impairing the effects of the present invention.

  In addition, the styrene copolymer obtained by graft polymerization or copolymerization of the above-mentioned (D) styrene copolymer with an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated acid anhydride, or epoxy group-containing vinyl monomer. It may be a polymer. Of these, a styrene copolymer obtained by graft polymerization or copolymerization of an unsaturated acid anhydride or an epoxy group-containing vinyl monomer is preferable.

  Such epoxy group-containing vinyl monomers are compounds that share both radically polymerizable vinyl groups and epoxy groups in one molecule. Specific examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and itacon. Examples include glycidyl esters of unsaturated organic acids such as glycidyl acid, glycidyl ethers such as allyl glycidyl ether, and the above derivatives such as 2-methylglycidyl methacrylate. Among them, glycidyl acrylate and glycidyl methacrylate can be preferably used. These can be used alone or in combination of two or more. Of these, a styrene copolymer obtained by graft polymerization or copolymerization of glycidyl methacrylate is more preferably used.

  Unsaturated acid anhydrides are compounds that share both radically polymerizable vinyl groups and acid anhydrides in one molecule, and preferred examples include maleic anhydride.

  As a method for producing a styrene copolymer obtained by graft polymerization or copolymerization of the unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated acid anhydride or epoxy group-containing vinyl monomer, a generally known method is used. A resin obtained by polymerizing styrene or α-methylstyrene with one or more monomers selected from aromatic vinyl compounds, vinyl cyanide compounds, alkyl (meth) acrylates, and maleimide monomers. And other monomers copolymerizable therewith and unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers, and the styrene copolymer. The polymer may be unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated acid anhydride or epoxy group-containing vinyl. The system monomer and a method of graft polymerization. Such copolymerization and graft polymerization can also be performed by known methods.

  The amount used for graft polymerization or copolymerization of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers is as follows: (A) component and (D) styrene copolymer Although it will not specifically limit if it is effective in improving the compatibility of a coalescence, it is preferable that it is 0.05 weight% or more with respect to (D) styrene-type copolymer. Copolymerization in a large amount tends to decrease fluidity and gelation, and is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less.

  Moreover, the styrene-type copolymer which carried out the epoxy modification | denaturation with epoxidizing agents, such as peroxides, performic acid, peracetic acid, and perbenzoic acid, to the said (D) styrene-type copolymer may be sufficient. In this case, it is preferable that a diene monomer is randomly copolymerized or block copolymerized with the styrene copolymer in order to effectively perform the epoxy modification. As examples of diene monomers, butadiene, isoprene and the like are preferably used. Examples of suitable production methods for these epoxy-modified styrene copolymers are shown in JP-A-6-256417, JP-A-6-220124 and the like.

  In addition, in the epoxy group introduction method using an epoxidizing agent, the amount of the epoxy group introduced into the (D) styrene copolymer is effective to improve the compatibility of the component (A) and the (D) styrene resin. Although not particularly limited, the epoxy equivalent is preferably 100 g / equivalent to 10,000 g / equivalent, more preferably 200 g / equivalent to 5000 g / equivalent, and still more preferably 250 g / equivalent to 3000 g / equivalent. It is. The epoxy equivalent of these resins can be measured by the method described in JP-A-6-256417.

  The (D) styrenic copolymer may be used in any one of the multilayer structure composed of the innermost layer (core layer) and the outer layer (shell layer) covering the innermost layer (core layer). In the case of a multilayer structure, it may be used for the intermediate layer, and the multilayer structure can also be used as the styrenic copolymer of the present invention, and the number of layers constituting the multilayer structure is particularly limited. It may be two or more layers, and may be three or more layers.

  Moreover, as a preferable example of the multilayer structure, the core layer is another resin such as a dimethylsiloxane / butyl acrylate polymer, the outermost layer is (D) a styrene copolymer, and the core layer is (D ) Styrenic copolymer with outermost layer also being (D) styrenic copolymer, and other resin such as (D) styrenic copolymer with core layer and outermost layer being dimethylsiloxane / methacrylic acid polymer And any one of the layers may be modified with glycidyl methacrylate or acid anhydride.

  Further, the particle diameter of the multilayer structure is not particularly limited, but is preferably 0.01 μm to 1000 μm, more preferably 0.02 μm to 100 μm, particularly 0.05 μm to Most preferably, it is 10 μm.

  Further, in the multilayer structure, the weight ratio of the core and the shell is not particularly limited, but the core layer is preferably 10 parts by weight to 90 parts by weight with respect to the entire multilayer structure polymer. 30 parts by weight to 80 parts by weight is more preferable.

  Moreover, as a multilayer structure, the commercial item which satisfy | fills above-described conditions may be used, and it can also produce and use by a well-known method.

  Commercially available multilayer structures include, for example, “Metablene” manufactured by Mitsubishi Rayon Co., “Kane Ace” manufactured by Kaneka Chemical Industry Co., “Paraloid” manufactured by Kureha Chemical Industry Co., Ltd., “Acryloid” manufactured by Rohm and Haas Co., Ltd., Takeda “Staffyroid” manufactured by Yakuhin Kogyo Co., Ltd., “Parapet SA” manufactured by Kuraray Co., Ltd. and the like can be used. These can be used alone or in combination of two or more. You may mix and use the example of a polymer.

  Further, it may be a resin containing the (D) styrene copolymer as a branched chain of the graft copolymer, and examples of the resin serving as the main chain include polyolefin, acrylic resin, and polycarbonate resin. Any of the branched chain and the main chain may be modified with glycidyl methacrylate or acid anhydride.

  Examples of the commercially available product include “Modiper” manufactured by Nippon Oil & Fats Co., Ltd., and are used alone or mixed with the examples of preferred copolymers described in (D) Styrene-based copolymers. Can do.

  The amount of (D) styrene copolymer added is 1 to 150 parts by weight, preferably 5 to 140 parts by weight, more preferably 10 to 120 parts by weight, based on 100 parts by weight of component (A). Most preferred is 15 to 100 parts by weight. When the amount of the (D) styrene copolymer is less than 1 part by weight, the effect of improving the injection moldability and Vicat softening point is small, and when it exceeds 150 parts by weight, the color tone of the molded product is changed by heat drying or heat treatment. Tend to.

  (E) An acid anhydride can be further mix | blended with the resin composition of this invention. (E) An acid anhydride has the effect of improving the impact resistance of the resin composition of the present invention. The (E) acid anhydride of the present invention is a compound having a structure in which water molecules are eliminated from dicarboxylic acid in the molecule. For example, maleic anhydride, itaconic anhydride, citraconic anhydride, anhydrous 5 -Norbornene-2,3-dicarboxylic acid, anhydrous 1-cyclohexene-1,2-dicarboxylic acid, anhydrous cis-4-cyclohexene-1,2-dicarboxylic acid, succinic anhydride, adipic anhydride, anhydrous cyclohexanedicarboxylic acid, anhydrous Examples thereof include phthalic acid. From the viewpoint of impact resistance, one or more of maleic anhydride and succinic anhydride are preferable, and maleic anhydride is more preferable. In the present invention, it is considered that by adding (E) acid anhydride, it reacts with the end of (A) polylactic acid resin, and the impact resistance characteristics are greatly improved.

  Further, the blending amount of (E) acid anhydride is preferably 0.01 to 10 parts by weight, more preferably 0.02 to 5 parts by weight, with respect to 100 parts by weight of (A) polylactic acid resin. The amount is particularly preferably 0.03 to 2 parts by weight, and if it is less than 0.01 part by weight, the effect of increasing the impact resistance is small, and if it exceeds 10 parts by weight, the fluidity at the time of molding is unfavorable.

  The resin composition of the present invention may further contain (F) an inorganic filler. (F) The inorganic filler has the effect of improving the heat resistance and the appearance of the molded product of the resin composition of the present invention. Examples of the inorganic filler (F) include plate-like, needle-like, fibrous or granular materials, and the (A) component, the (B) component, the (C) component and, if necessary, the (D) component, (E) Inorganic fillers that can be uniformly dispersed in the component are preferred, and silicate minerals, silicate minerals, and various minerals that are pulverized by processing such as grinding are preferably used. . Specific examples include bentonite, dolomite, montmorillonite, barlite, finely divided silicic acid, aluminum silicate, silicon oxide, dosonite, shirasu balloon, clay, sericite, feldspar powder, kaolin, zeolite (including synthetic zeolite), talc, Examples include mica, synthetic mica and wollastonite (including synthetic wollastonite), glass flakes, glass beads, hydrotalcite and silica, and talc and silica are preferably used because of the high whiteness of the resulting molded product, It may be modified with an organic substance such as a silane coupling agent. In addition, inorganic fillers such as talc, kaolin, montmorillonite, synthetic mica, clay, zeolite, and silica are also useful as inorganic crystal nucleating agents. By blending an inorganic crystal nucleating agent, (A) polylactic acid There is an effect of promoting the crystallization speed of the resin.

  The average particle size of the plate-like and granular inorganic fillers is preferably 10 μm or less with little decrease in mechanical properties, more preferably 5 μm or less. The lower limit is preferably an average particle size of 0.5 μm or more, more preferably an average particle size of 1 μm or more from the viewpoint of handling properties during production. The average particle diameter is measured by a 50% cumulative distribution average particle diameter measured by a laser diffraction scattering method.

  In addition, the needle-like inorganic filler such as wollastonite and kaolin preferably has an aspect ratio (average length / average diameter) of 3 to 20, and an average diameter of 10 μm or less is more preferable because there is little decrease in mechanical properties. The average diameter is preferably 5 μm or less.

  Glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, slag fiber, gypsum fiber, silica fiber, silica / alumina fiber, zirconia Inorganic fibrous reinforcements such as fiber, boron nitride fiber, silicon nitride fiber and boron fiber, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie, cotton, jute, hemp, sisal, flax, Fibrous inorganic fillers such as organic fibrous reinforcements such as linen, silk, manila hemp, sugar cane, wood pulp, paper scraps, waste paper and wool are effective in increasing heat distortion temperature and are useful for molded products used at high temperatures Is a good filler. In particular, glass fiber and kenaf are preferably used, and kenaf is also useful as a plant-derived fiber.

  In addition, the fibrous inorganic filler may be coated or focused with a resin such as an ethylene / vinyl acetate copolymer, polyurethane, and epoxy resin, and may be a coupling agent such as aminosilane or epoxysilane. It may be processed.

  The blending amount of the (F) inorganic filler is preferably 0.5 to 150 parts by weight, more preferably 0.7 to 100 parts by weight, with respect to 100 parts by weight of the (A) polylactic acid resin. The amount is particularly preferably 1 to 80 parts by weight, and if it is less than 0.5 parts by weight, the effect of increasing the heat resistance is small, and if it exceeds 150 parts by weight, the fluidity at the time of molding is unfavorable.

  Flame retardancy can be imparted to the resin composition of the present invention by blending (G) a flame retardant. (G) A flame retardant is not particularly limited as long as it is a substance added for the purpose of imparting flame retardancy to a resin. Specifically, a brominated flame retardant, a phosphorus flame retardant, a nitrogen compound. -Based flame retardants, silicone-based flame retardants, other inorganic flame retardants, and the like, and at least one or more of them can be selected and used.

  Specific examples of the brominated flame retardant used in the present invention include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromo). Phenoxy) ethane, ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, Tris (2,3-dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobis Enol-A, tetrabromobisphenol-A derivative, tetrabromobisphenol-A-epoxy oligomer or polymer, tetrabromobisphenol-A-carbonate oligomer or polymer, brominated epoxy resin such as brominated phenol novolac epoxy, tetrabromobisphenol-A -Bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, Tris (tribromoneopentyl) phosphate, poly (pentabromobenzylpolyacrylate), octabromotrimethylphenylindane, dibromoneope Chill glycol, pentabromobenzyl polyacrylate, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo phthalic imide. Of these, tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, and brominated epoxy resin are preferable.

  The phosphorus-based flame retardant used in the present invention is not particularly limited, and a generally used phosphorus-based flame retardant can be used. Typically, an organic phosphorus compound such as a phosphate ester or a polyphosphate, Red phosphorus is mentioned.

  Specific examples of the phosphoric acid ester in the above organic phosphorus compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl. Phosphate, tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl Phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acetate Phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid Examples include condensed phosphate esters such as diethyl, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and condensates thereof. be able to. Examples of commercially available condensed phosphate esters include PX-200, PX-201, PX-202, CR-733S, CR-741, and CR747 manufactured by Daihachi Chemical Co., Ltd.

  Moreover, the phosphate and polyphosphate which consist of a salt with phosphoric acid, polyphosphoric acid, a metal of group IA-IVB of the periodic table, ammonia, an aliphatic amine, and an aromatic amine can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts, etc. as metal salts, methylamine salts as aliphatic amine salts, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts, triazine salts, melamine salts, and ammonium salts.

  In addition to the above, halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris (β-chloropropyl) phosphate), and a structure in which a phosphorus atom and a nitrogen atom are connected by a double bond. Examples thereof include phosphazene compounds and phosphoric ester amides.

  Further, as red phosphorus, not only untreated red phosphorus but also red phosphorus treated with one or more compound films selected from the group consisting of thermosetting resin coatings, metal hydroxide coatings, and metal plating coatings. It can be preferably used. The thermosetting resin of the thermosetting resin film is not particularly limited as long as it is a resin capable of coating red phosphorus. For example, phenol-formalin resin, urea-formalin resin, melamine-formalin resin, alkyd resin Etc. The metal hydroxide coating is not particularly limited as long as it can coat red phosphorus, and examples thereof include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. . The metal of the metal plating film is not particularly limited as long as it can coat red phosphorus, and examples thereof include Fe, Ni, Co, Cu, Zn, Mn, Ti, Zr, Al, and alloys thereof. Furthermore, these coatings may be laminated in combination of two or more or in combination of two or more.

  Examples of the nitrogen compound-based flame retardant used in the present invention include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides, aromatic amides, urea, thiourea and the like. . In addition, nitrogen-containing phosphorus flame retardants such as ammonium polyphosphate as exemplified in the above phosphorus flame retardant are not included in the nitrogen compound flame retardant referred to herein. Examples of the aliphatic amine include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane, 1,2-diaminocyclooctane and the like. Examples of the aromatic amine include aniline and phenylenediamine. Examples of nitrogen-containing heterocyclic compounds include uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, and triazine compounds. Examples of the cyan compound include dicyandiamide. Examples of the aliphatic amide include N, N-dimethylacetamide. Examples of aromatic amides include N, N-diphenylacetamide.

  The triazine compounds exemplified above are nitrogen-containing heterocyclic compounds having a triazine skeleton, and are triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, triphenyltriazine, amelin, and amelide. And thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoisopropoxytriazine and the like.

  As melamine cyanurate or melamine isocyanurate, an addition product of cyanuric acid or isocyanuric acid and a triazine compound is preferable, usually an addition having a composition of 1 to 1 (molar ratio) and optionally 1 to 2 (molar ratio). You can list things. Although it is produced by a known method, for example, a mixture of melamine and cyanuric acid or isocyanuric acid is made into a water slurry and mixed well to form both salts into fine particles, and then the slurry is filtered and dried. Later it is generally obtained in powder form. The salt does not need to be completely pure, and some unreacted melamine, cyanuric acid or isocyanuric acid may remain. Moreover, the average particle diameter before blending with the resin is preferably 100 to 0.01 μm, more preferably 80 to 1 μm from the viewpoint of flame retardancy, mechanical strength, and surface property of the molded product.

  Of the nitrogen compound-based flame retardants, nitrogen-containing heterocyclic compounds are preferable, among which triazine compounds are preferable, and melamine cyanurate is more preferable.

  When the dispersibility of the nitrogen compound flame retardant is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent such as polyvinyl alcohol or metal oxide may be used in combination. Good.

Examples of the silicone flame retardant used in the present invention include silicone resins and silicone oils. Examples of the silicone resin include a resin having a three-dimensional network structure formed by combining structural units of SiO ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. In the silicone oil, polydimethylsiloxane, and at least one methyl group at the side chain or terminal of polydimethylsiloxane is a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, or a polyether group. , A modified polysiloxane modified with at least one group selected from a carboxyl group, a mercapto group, a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group, or a mixture thereof Can be mentioned.

  Further, a thermoplastic resin obtained by copolymerizing a siloxane compound such as polydimethylsiloxane may be used, and examples thereof include a thermoplastic resin obtained by copolymerizing a polycarbonate resin with a siloxane compound.

  Other inorganic flame retardants used in the present invention include magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, oxidation Metal of tin salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, calcium borate, ammonium borate, ammonium octamolybdate, tungstic acid Examples thereof include salts, complex oxide acids of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, graphite, and swellable graphite. Among these, aluminum hydroxide, zinc borate, and swellable graphite are preferable, and may be treated with a known surface treatment agent or the like.

  The (G) flame retardant may be used alone or in combination of two or more.

  Among the flame retardants (G), at least one or a combination of two or more selected from phosphorous flame retardants containing no halogen, nitrogen compound flame retardants, silicone flame retardants and other inorganic flame retardants Are preferably used. In the above, when two or more flame retardants are used in combination, it is preferable to use a phosphorus-based flame retardant together with another flame retardant. The nitrogen compound-based flame retardant used in combination with the phosphorus-based flame retardant is preferably a nitrogen-containing heterocyclic compound, more preferably a triazine compound, and further preferably melamine cyanurate. Moreover, as a silicone type flame retardant used together with a phosphorus type flame retardant, a silicone resin is preferable. Moreover, as other inorganic flame retardants used in combination with phosphorus flame retardants, aluminum hydroxide, zinc borate and swellable graphite are preferable. Further, the blending ratio with the phosphorus-based flame retardant can be combined with any amount, and the amount of the phosphorus-based flame retardant in 100% by weight of the flame retardant is particularly preferably 5% by weight or more, and 5 to 95% by weight. It is more preferable that

  More preferable flame retardant is at least one selected from nitrogen compound flame retardants, silicone flame retardants, and other inorganic flame retardants which do not contain any halogen compound and phosphorus compound among the flame retardants (G). It is particularly preferable to use a species or a combination of two or more species.

  Moreover, the compounding quantity of (G) a flame retardant is 1-50 weight part with respect to 100 weight part of (A) polylactic acid resin, Furthermore, 2-45 weight part is preferable, Especially preferably, 3 weight part- The amount is 40 parts by weight, and if it is less than 1 part by weight, the effect of imparting flame retardancy is small, and if it exceeds 50 parts by weight, the mechanical properties decrease, which is not preferable.

  Moreover, by using a specific fluorine-based resin in combination with the above (G) flame retardant, there is an effect of improving drip at the time of combustion, and higher flame retardancy can be obtained. The specific fluorine-based resin is a resin containing fluorine in a substance molecule, and specifically includes polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene. / Perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, hexafluoropropylene / propylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer, etc., among which polytetrafluoro Ethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride Polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymer, more preferably polytetrafluoroethylene, and a polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer. The body is also preferably used. The molecular weight of the fluororesin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, particularly for the extrudability and flame retardancy of the present invention. effective. Commercially available products of polytetrafluoroethylene include “Teflon (registered trademark)” 6-J, “Teflon (registered trademark)” 6C-J, and “Teflon (registered trademark)” 62 manufactured by Mitsui DuPont Fluorochemical Co., Ltd. -J, “Full-on” CD1 and CD076 manufactured by Asahi IC Fluoropolymers Co., Ltd. are commercially available. In addition, as a commercial product of a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, it is commercially available as “Metabrene (registered trademark)” A series from Mitsubishi Rayon Co., Ltd. METABLEN (registered trademark) “A-3000”, “METABBRENE (registered trademark)” A-3800, and the like are commercially available. In addition, polytetrafluoroethylene “Teflon (registered trademark)” 6-J and the like are prone to agglomerate, so if they are mechanically strongly mixed with other resin compositions using a Henschel mixer or the like, agglomeration may occur due to aggregation. There are problems in handling and dispersibility depending on conditions. On the other hand, a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is excellent in handling properties and dispersibility, and is particularly preferably used. The polytetrafluoroethylene-containing mixed powder composed of the polytetrafluoroethylene particles and the organic polymer is not limited, but polytetrafluoroethylene disclosed in Japanese Patent Application Laid-Open No. 2000-226523. Polytetrafluoroethylene-containing mixed powder composed of particles and an organic polymer, and the like. Examples of the organic polymer include aromatic vinyl monomers, acrylate monomers, and vinyl cyanide. An organic polymer containing 10% by weight or more of a monomer, and a mixture thereof may be used. The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder is from 0.1% by weight to 90%. It is preferable that it is weight%. Moreover, the compounding quantity of specific fluororesin is 0.01-5 weight part with respect to 100 weight part of (A) polylactic acid resin, Preferably 0.02-4 weight part is preferable, More preferably 0.03 to 3 parts by weight is preferable, and if the blending amount of the fluororesin exceeds 5 parts by weight, the fluidity and flame retardancy of the present invention are reduced, and if less than 0.01 parts by weight, the flame retardancy is improved. The effect is not recognized.

  As the flame retardancy of the resin composition in which (G) the flame retardant and (G) the flame retardant and a specific fluorine-based resin are blended, the flame retardancy in the US UL standard 94 (UL-94 standard) is 1 thickness. It is possible to obtain a resin composition having flame retardancy of V-2, V-1, and V-0 with a molded product of .6 mm (1/16 inch) or more.

  Here, the flame retardancy of the US UL standard subject 94 (UL-94 standard) will be described. The flame retardancy test method includes a horizontal test and a vertical test, and materials that pass the horizontal test are flame retardancy rank HB. It is evaluated as. In addition, the vertical test, in which the test material is fixed vertically and the flame is applied to the lower part of the material, is more flammable than the horizontal test. -2, V-1, and V-0 are defined, and the smaller the number, the better the flame retardancy. Here, V-0 is the most advanced flame retardance rank.

  In the present invention, (H) a thermoplastic resin other than the styrene copolymer can be blended, and the resin composition is excellent in surface appearance, moldability, mechanical properties, heat resistance, flexibility, toughness, and the like. And a molded product made of the same can be obtained. The thermoplastic resin other than the (H) styrene-based copolymer of the present invention is not particularly limited, and is (A) a polylactic acid resin and (G) a thermoplastic resin other than the styrene-based copolymer. Specific examples include polyester resins other than polylactic acid resins, polyacetal resins, polyamide resins, polyolefin resins such as polyethylene resins and polypropylene resins, acrylic resins, polyurethane resins, chlorinated polyethylene resins, chlorinated polypropylene resins, aromatics and fats Group polyketone resin, polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, thermoplastic starch resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl ester resin, polyurethane resin, polycarbonate resin, polyarylate resin, polysulfone resin , Polyethersulfone resin, phenoxy resin, polyphenylene ether resin, poly-4-methylpentene-1, polyetherimide resin, polyvinyl alcohol resin, and other thermoplastic resins. The above thermoplastic resin is a glycidyl group, It may be a thermoplastic resin modified with one kind of epoxy group or acid anhydride.

  Polyacetal resin, polyester resin other than polylactic acid resin (polybutylene terephthalate resin, polytrimethylene terephthalate resin, polyethylene terephthalate resin, polyester elastomer, polyethylene (terephthalate / succinate) resin, polybutylene succinate resin, polycaprolactone resin, and cellulose acetate) Cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate resins such as cellulose acetate butyrate, cellulose acetate phthalate, etc.), polyamide resins, glycidyl groups, epoxy groups or acid anhydrides are grafted or copolymerized. It is preferable to blend at least one selected from thermoplastic resins.

  Although not limited, specific examples of the thermoplastic resin grafted or copolymerized with one kind of the glycidyl group, epoxy group or acid anhydride are ethylene / glycidyl methacrylate, ethylene / methyl acrylate / Glycicyl methacrylate, ethylene / maleic anhydride, ethylene / maleic anhydride, propylene / maleic anhydride, ethylene / propylene / maleic anhydride, ethylene / butene-1 / maleic anhydride, etc., ethylene / methyl acrylate / Glycicyl methacrylate, ethylene / butene-1 / maleic anhydride and the like can be mentioned, and a resin composition having further flexibility can be obtained while maintaining the performance of the present invention. Moreover, even when the polybutylene succinate resin is used among the polyester resins other than the polylactic acid resin, a resin composition having further flexibility can be obtained while maintaining the performance of the present invention.

  Moreover, when ethylene / maleic anhydride or propylene / maleic anhydride is used, a resin composition having particularly excellent impact resistance is obtained, and commercially available products of ethylene / maleic anhydride and propylene / maleic anhydride are obtained. For example, “Admer” manufactured by Mitsui Chemicals, Inc. can be used. The ethylene of ethylene / maleic anhydride is a general term for low density polyethylene, medium density polyethylene and high density polyethylene.

  (H) The blending amount of the thermoplastic resin other than the styrene-based copolymer is 1 to 100 parts by weight, more preferably 2 to 80 parts by weight with respect to 100 parts by weight of the (A) polylactic acid resin. The amount is preferably 3 to 60 parts by weight, and if it is less than 1 part by weight, the effect of modifying the surface appearance and the like is small, and if it exceeds 100 parts by weight, the mechanical properties may be lowered, which is not preferable.

  In this invention, it is preferable to mix | blend a carboxyl group reactive terminal blocker further. The carboxyl group-reactive end-blocking agent used in the present invention is not particularly limited as long as it is a compound capable of blocking the carboxyl end group of (A) polylactic acid resin. What is used as a blocking agent can be used. In the present invention, the carboxyl group-reactive end-blocking agent not only blocks the end of the polylactic acid resin, but also generates lactic acid, formic acid, etc. produced by thermal decomposition or hydrolysis of the polylactic acid resin or naturally-occurring organic filler. The carboxyl group of the acidic low molecular weight compound can also be blocked. Further, the end-capping agent is more preferably a compound that can also block the hydroxyl end where an acidic low molecular weight compound is generated by thermal decomposition. As such a carboxyl group-reactive end-blocking agent, it is preferable to use at least one compound selected from an epoxy compound, an oxazoline compound, an oxazine compound, a carbodiimide compound, and a carbodiimide-modified isocyanate compound. Or a carbodiimide compound, a carbodiimide compound and / or a carbodiimide-modified isocyanate compound are preferable. The compounding amount of the carboxyl group-reactive end-blocking agent is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and 0.01 parts by weight with respect to 100 parts by weight of the (A) polylactic acid resin. If it is less than 5 parts by weight, it is insufficient as an amount for blocking the carboxyl terminal of the polymer, and if it exceeds 5 parts by weight, the Vicat softening point of the present invention is lowered.

  In the present invention, it is preferable to add a stabilizer. As a stabilizer used by this invention, what is normally used for the stabilizer of a thermoplastic resin can be used. Specific examples include antioxidants and light stabilizers. By blending these, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.

  Examples of the antioxidant used in the present invention include hindered phenol compounds, phosphite compounds, and thioether compounds.

  Examples of hindered phenolic compounds include triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and tetrakis [methylene-3- (3 ′, 5 ′ -Di-t-butyl-4'-hydroxyphenyl) propionate] methane.

  Examples of the phosphite compound include tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6- Di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphonite and the like can be preferably used.

  Specific examples of the thioether compound include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-laurylthiopropionate). Nate), pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis ( 3-stearyl thiopropionate).

  Examples of the light stabilizer used in the present invention include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds and hindered amine compounds.

  In the present invention, the stabilizer may be used alone or in combination of two or more. Further, it is preferable to use a hindered phenol compound and / or a benzotriazole compound in combination as the stabilizer.

  Moreover, the blending amount of the stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight with respect to 100 parts by weight of the (A) polylactic acid resin, and less than 0.01 parts by weight. The amount for obtaining a molded product excellent in mechanical properties, moldability, heat resistance and durability is insufficient, and if it exceeds 3 parts by weight, the mechanical properties are lowered, which is not preferable.

  In this invention, it is preferable to mix | blend a mold release agent. As the mold release agent used in the present invention, those usually used for a thermoplastic resin mold release agent can be used. Specifically, fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, partially aliphatic saponified esters, paraffin, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid lower alcohol esters, fatty acid polyhydric alcohols Examples thereof include esters, fatty acid polyglycol esters, and modified silicones. By blending these, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.

  As the fatty acid, those having 6 to 40 carbon atoms are preferable. Specifically, oleic acid, lauric acid, stearic acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, Examples include stearic acid, montanic acid, and mixtures thereof. As the fatty acid metal salt, an alkali metal salt or an alkaline earth metal salt of a fatty acid having 6 to 40 carbon atoms is preferable, and specific examples include calcium stearate, sodium montanate, and calcium montanate. Examples of the oxy fatty acid include 1,2-oxystearic acid, and examples of the fatty acid ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidic acid ester, and montan. Examples of the acid ester, isostearic acid ester, ester of polymerized acid, and aliphatic partially saponified ester include montanic acid partially saponified ester. As the paraffin, those having 18 or more carbon atoms are preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolatum, and the like, and the low molecular weight polyolefin preferably has a molecular weight of 5000 or less, specifically, polyethylene wax, Oxidized type polyethylene wax, chlorinated polyethylene wax, polypropylene wax and the like are mentioned, and fatty acid amides preferably have 6 or more carbon atoms, and specifically include oleic acid amide, erucic acid amide, behenic acid amide and the like. As the alkylene bis fatty acid amide, those having 6 or more carbon atoms are preferable. Specific examples include methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2-hydroxyethyl) stearic acid amide. Examples of aliphatic ketones include higher aliphatic ketones, and fatty acid lower alcohol esters preferably have 6 or more carbon atoms, such as ethyl stearate butyl stearate, ethyl behenate, rice wax, and the like. Examples of the fatty acid polyhydric alcohol ester include glycerin monostearate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol adipate stearate, dipentaerythritol adipate stearic acid, sorbitan monobehenate and the like. Examples of the fatty acid polyglycol ester include polyethylene glycol fatty acid ester and polypropylene glycol fatty acid ester, and examples of the modified silicone include tilstyryl-modified silicone. Examples thereof include corn, polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.

  Among the above, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, aliphatic amide, alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and / or alkylene bis fatty acid amide are preferred. More preferred.

  Of these, montanic acid ester, montanic acid partially saponified ester, polyethylene wax, oxidized polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferable, and in particular, montanic acid partially saponified ester, maleic anhydride-modified polyethylene wax, Ethylene bis stearamide is preferred.

  In the present invention, the above releasing agents may be used alone or in combination of two or more.

  Moreover, the compounding quantity of a mold release agent is preferable 0.01-3 weight part with respect to 100 weight part of (A) polylactic acid resin, 0.03-2 weight part is more preferable, Less than 0.01 weight part However, the effect as a mold release agent is insufficient, and if it exceeds 3 parts by weight, the mechanical properties deteriorate, which is not preferable.

  The resin composition of the present invention may further contain (I) maleic anhydride-modified polyolefin wax. (I) The maleic anhydride-modified polyolefin wax has the effect of improving the impact resistance of the resin composition of the present invention. The (I) maleic anhydride-modified polyolefin wax of the present invention is a resin composition that is particularly excellent in impact resistance while maintaining the performance of the present invention. Here, the polyolefin wax will be described. The wax includes a natural wax obtained from minerals, animals and plants, and a polyolefin wax which is a synthetic wax made of ethylene, propylene, or the like, and has a molecular weight of about 100 to 1000 measured by the viscosity method of the natural wax. The molecular weight of the synthetic wax, measured by the viscosity method of the polyolefin wax, is about 500 to 30000. If the molecular weight is larger and more than tens of thousands, it is used as a polyolefin resin. The maleic anhydride-modified polyolefin wax of the present invention is a wax obtained by grafting or copolymerizing maleic anhydride on a polyolefin wax such as the aforementioned polyethylene wax or polypropylene wax. As specific examples of (I) maleic anhydride-modified polyolefin wax, maleic anhydride-modified polyethylene wax and maleic anhydride-modified polypropylene wax can be used. Examples of commercially available maleic anhydride-modified polyolefin wax include: “Mitsui High Wax” acid-modified types HW1105A (molecular weight of about 1500), HW2203A (molecular weight of about 2700), HWNP0555A (molecular weight of about 7000), etc. manufactured by Mitsui Chemicals, Inc. can be used. The blending amount of the (I) maleic anhydride-modified polyolefin wax is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight with respect to 100 parts by weight of the (A) polylactic acid resin. If it is less than 0.01 parts by weight, the effect of improving the impact is insufficient, and if it exceeds 3 parts by weight, the mechanical properties are deteriorated, which is not preferable.

  In the present invention, it is preferable to further add an antistatic agent in terms of imparting antistatic properties. As the antistatic agent used in the present invention, any known one can be used, and its ionicity is not particularly limited, and any of cationic, anionic, zwitterionic or nonionic can be used. Although it may be used, (A) zwitterionic and nonionic are preferable, and nonionic is more preferable in that the thermal decomposition of the polylactic acid resin can be suppressed.

  The blending amount of the antistatic agent is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, and less than 0.01 parts by weight with respect to 100 parts by weight of the (A) polylactic acid resin. However, the antistatic effect is insufficient, and if it exceeds 10 parts by weight, the mechanical properties deteriorate, which is not preferable.

  In the present invention, the resin is adjusted to various colors by adding one or more kinds of pigments and dyes of carbon black, titanium oxide, petal, ultramarine blue, calcined yellow, and various colors, and weather resistance (light) The blending amount of the pigment or dye is 0.01 to 10 parts by weight, preferably 0.02 to 9 parts by weight based on 100 parts by weight of the (A) polylactic acid resin. Parts, more preferably 0.03 to 8 parts by weight. If it is less than 0.01 parts by weight, it is insufficient as an amount for improving toning, weather resistance (light), and conductivity, and if it exceeds 10 parts by weight This is not preferable because the mechanical properties are deteriorated.

  Examples of the carbon black include, but are not limited to, channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. The average particle diameter is 500 nm or less, and dibutyl phthalate. Carbon black having an oil absorption of 50 to 400 cm 3/100 g is preferably used, and may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like as a treatment agent.

  Further, as the titanium oxide, titanium oxide having a rutile form or anatase form and having an average particle diameter of 5 μm or less is preferably used, and aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, It may be treated with a polyol, a silane coupling agent or the like. In addition, the above-described carbon black, titanium oxide, and various color pigments and dyes may be used in various thermoplastic resins in order to improve dispersibility with the flame retardant resin composition of the present invention and to improve handling during production. And may be used as a blended material that is melt blended or simply blended. In particular, the thermoplastic resin is preferably a polyester resin such as a polylactic acid resin, and a polylactic acid resin is particularly preferably used.

  In the present invention, within a range that does not impair the effects of the present invention, a slidability improver (graphite, fluororesin for improving slidability, etc.), an organic filler derived from nature (rice husk, okara, waste paper grinding material, Chips such as crushed clothes, paper powder, wood powder, bamboo powder, cellulose powder, rice husk powder, fruit shell powder, chitin powder, chitosan powder, protein, starch, etc.), antibacterial agents, organic crystal nucleating agents ( Sodium benzoate, potassium benzoate, calcium benzoate, magnesium benzoate, lithium terephthalate, sodium terephthalate, calcium oxalate, sodium laurate, sodium stearate, potassium stearate, magnesium stearate, sodium montanate, montanic acid Organic carboxylic acid metal salts such as calcium, sodium p-toluenesulfonate, Organic sulfonic acid salts such as sodium foisophthalate, stearic acid amide, ethylene bislauric acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide) and other organic carboxylic acid amides, ethylene Sodium or potassium salt of a polymer having a carboxyl group such as sodium salt of acrylic acid or methacrylic acid copolymer (so-called ionomer), benzylidene sorbitol and its derivatives, sodium-2,2′-methylenebis (4,6-di-t One or more components such as a phosphorus compound metal salt such as -butylphenyl) phosphate and a plasticizer other than the present invention can be added.

Method for producing a resin composition of the present invention is not particularly limited as long as it satisfies the requirements specified in the present invention, for example, (A) the polylactic acid resin, (B) a number average polyalkylene molecular weight from 8,300 to 21,000 After pre-blending a glycol compound and (C) an ester plasticizer having a specific structure, if necessary (D) a styrene copolymer, (E) an acid anhydride, and other additives as required (A) Above the melting point of the polylactic acid resin, a method of uniformly melting and kneading with a single screw or twin screw extruder, a method of removing the solvent after mixing in a solution, and the like are preferably used.

  When the resin composition of the present invention is produced, the melt-kneading temperature is preferably 170 to 240 ° C, more preferably 175 to 230 ° C, and particularly preferably 180 to 220 ° C.

The resin composition of the present invention is processed into various product shapes by methods such as injection molding, blow molding, extrusion molding, sheet molding, film molding, and spinning into various fibers such as undrawn yarn, drawn yarn, and superdrawn yarn. It can be used as a molded product for various uses such as mechanical mechanism parts, electrical / electronic parts, automobile parts, optical equipment, building members, and daily necessities. In particular, excellent in injection moldability, high Vicat softening point, the feature of flexibility of grant possible, various applications of the injection molded article, a housing, packings, cover, is preferably used due films and sheets.

The present invention also includes (A) a polylactic acid resin, (B) a polyalkylene glycol having a number average molecular weight of 8300 to 21000, (C) an ester plasticizer having a specific structure, and (D) a styrene copolymer. A resin composition containing a coalescence, (E) acid anhydride, and other additives as required is a material excellent in injection moldability and Vicat softening point, and also in elastic recovery, and has elastic recovery. It can also be expected to be used for molded products, and when the styrene copolymer is a vinyl resin exceeding 30% by weight of the rubber component, it is particularly excellent in elastic recovery and impact resistance. Development as a material having moldability, Vicat softening point, elastic recovery and impact resistance can be expected. Furthermore, a resin composition obtained by further blending a polymer such as polybutylene succinate resin of aliphatic polyester resin or ethylene / butene-1 / maleic anhydride resin with the above resin composition maintains excellent injection moldability. A more flexible resin composition can be obtained and can be suitably used as a thermoplastic elastomer that fills the gap between the plastic and rubber.

  The elastic recoverability can be determined by a tensile set test or the like. The value of the tensile set is 0 to 60%, preferably 0 to 50%, more preferably 0 to 40%. A material having a tensile set exceeding 60% is not preferable because of poor elasticity recovery. The measurement method of the tensile permanent strain is shown in JIS-K-6262 (Tensile permanent strain test method).

  Moreover, since the molded article of the present invention has a plant-derived (A) polylactic acid resin as a main component, it can be suitably used as a useful molded article from the viewpoint of protecting the natural environment as compared with petroleum-derived resins.

  In addition, the resin composition in which talc is blended as an inorganic filler (F) is useful as a molded product in which the molded product has gloss and gloss and has an excellent molded product appearance, and the molded product appearance is required. is there. Furthermore, (F) a resin composition containing glass fiber as an inorganic filler can give a molded product having a specifically high Vicat softening point, and is a molded product used in a high temperature atmosphere or a molded product that hardly undergoes thermal deformation at a high temperature. Can be suitably used.

  In addition, since the resin composition further blended with (G) a flame retardant can satisfy the standard of the vertical combustion test of US UL standard subject 94 (UL94), a housing in which flame retardancy is essential It can be suitably used as a molded product such as a casing of an electric product.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, these do not limit this invention.

[Examples 4 to 14, Reference Example 1, Comparative Examples 12 to 13 ], [Comparative Examples 1 to 11], [Examples 15 to 23], [Examples 24 to 29]
The polylactic acid resin is a poly-L-lactic acid resin having a D-form content of 2% and a PMMA-converted weight average molecular weight of 170,000. The styrene copolymers and various polyalkylenes shown in Tables 1 to 3 are used. Glycol and various plasticizers were mixed in the proportions shown in Tables 1 to 3, and melt kneaded with a 30 mm diameter twin screw extruder under conditions of a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm to obtain a resin composition. . B-2 to B-4 used as polyalkylene glycols of (B) number average molecular weight of 8300 to 21000 of the present invention in the examples are polyalkylene glycols having a number average molecular weight within the range of the present invention. B-1 , B-5 and B-6 has a number average molecular weight of polyalkylene glycol which does not belong to the present invention, the number average molecular weight of B-1 to B-6 are listed in the table.

  In addition, C-1 to C-4 used as (C) specific ester plasticizer of the present invention in the examples were obtained by synthesis according to the synthesis method described in Japanese Patent No. 3421769. Yes, the plasticizer of B-5 is a plasticizer other than the specific ester plasticizer of the present invention, and commercially available plasticizers shown in Table 2 were used. Further, D-1 used as the styrene copolymer of the present invention (D) in the examples is a MABS resin having a butadiene content of 30% by weight or more, and is methyl methacrylate (32% by weight) / acrylonitrile (2% by weight) / It was obtained by drying into powder using a known emulsion polymerization method with a charged composition of polybutadiene (55 wt%) / styrene (11 wt%). D-2 to D-4 are shown in Table 1. A commercially available styrene-based copolymer was used, and the rubber component names and contents were described in the table. Further, maleic anhydride and succinic anhydride manufactured by Tokyo Chemical Industry are used as the acid anhydride of the component (E), types E-1 and E-2 of Table 4, and inorganic fillers of the component (F) are shown in Table 3 and Table 3. 4 types F-1 and F-2, (G) component flame retardants are the types G-1 to G-3 of Table 3, and (H) component thermoplastic resins other than styrene copolymers are other resins. Table 3 and Table 4 as types H-1 to H-3, and the component (I) maleic anhydride-modified polyolefin wax is shown as Table 4 type I-1.

  The obtained resin composition was subjected to injection molding at a cylinder temperature of 190 ° C. and a mold temperature of 70 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine, and various injection molded products were obtained. Using the obtained injection molded product, the performance evaluation shown in the following (1) to (7) was performed, and the results are shown in Tables 1 to 4.

(1) Injection moldability The injection time and pressure holding time at the time of injection molding are 20 seconds in total and the test piece for 1.6 mm thickness flame retardant evaluation is injection molded with a cooling time of 20 seconds. For materials that can be molded, the injection moldability was evaluated as ◯ (excellent). For materials that cannot be removed from the mold when the molded product is removed (poor mold releasability), the solidification rate is slow, and the molded product is greatly deformed by the pins (insufficient crystallization). Judgment was made difficult and the determination was x (inferior). Furthermore, among the materials for which the determination of injection moldability is ◯ (excellent), the material excellent in appearance of the molded product having a glossy or glossy molded product is evaluated as ◎ (particularly excellent).

(2) Vicat softening point Using a 3 mm-thick Izod impact test piece produced by injection molding, measurement was performed under the condition of a load of 1 kg in accordance with JIS-K-7206. In addition, the higher the Vicat softening point, the better the heat resistance and the less the heat-denaturing plastic material.

(3) Bleed-out resistance JIS-2 dumbbell produced by injection molding uses the Teranishi Chemical Blue Magic M500-T3 Blue to write the sample name, and using a hot air dryer at 70 ° C for 1 hour It heat-processed and the bleed-out resistance was visually observed using the following determination method.
◎: No bleed-out, no change to blue character M500-T3 blue from Teranishi Chemical ○: No bleed-out, blue magic M500-T3 from Teranishi Chemical bleed ×: There is bleed-out

(4) Flexibility (flexural modulus)
Measurement was performed according to ASTM-D-790 using ASTM No. 1 dumbbell produced by injection molding.

(5) Elastic recovery (tensile permanent set)
Based on JIS-K-6262 (tensile permanent strain test method), the measurement was performed under conditions of an initial strain of 25% and a processing temperature of 23 ° C.

(6) Flame retardancy Using a test piece of 127 mm × 12.7 mm × 1.6 mm (5 inch × 1/2 inch × 1/16 inch) produced by injection molding, US UL standard subject 94 (UL94) A flame test was conducted in accordance with the vertical flame test method, and a flame retardance rank was obtained. Materials that did not pass the flame retardancy rank were out of specification.

(7) Impact resistance An Izod impact test with a notch was conducted according to ASTM D256 to evaluate impact resistance.

  From Examples 1 to 14 in Table 1, it can be seen that the resin composition of the present invention has excellent injection moldability, a high Vicat softening point, and excellent bleed-out resistance and flexibility. Furthermore, it can be seen that a resin composition containing a styrene copolymer is a material excellent in injection moldability, further improving the above performance, and particularly excellent in flexibility and elastic recovery.

  From Comparative Examples 1 to 11 in Table 2, a resin composition not containing a polyalkylene glycol having a number average molecular weight of 1000 to 21000 and a specific ester plasticizer, or not containing any of them, is injection moldability, Vicat softening point, It turns out that it is inferior to the performance of bleed-out property or several performances. In addition, resin compositions using a polyalkylene glycol having a number average molecular weight outside the scope of the present invention or a plasticizer other than a specific ester plasticizer, and resin compositions exceeding the blending quantity within the scope of the present invention are also injection-molded. It can be seen that the performance, vicat softening point, bleed-out resistance or a plurality of performances are inferior.

  Further, from Examples 15 to 23 in Table 3, while maintaining the performance of the present invention, a material excellent in appearance of a molded product is obtained by blending talc of (F) inorganic filler, and (F) inorganic filler It turns out that the resin composition which mix | blended this glass fiber shows a specifically high Vicat softening point.

  Moreover, from Examples 25-27 of Table 3, the resin composition which further mix | blended the polybutylene succinate resin of the aliphatic polyester resin or ethylene / butene-1 / maleic anhydride resin maintained the performance of this invention. It can be seen that a more flexible resin composition can be obtained.

  Moreover, it can be seen that a molded product to which flame retardancy is imparted is obtained by blending (G) the flame retardant, and in particular, when two types of flame retardant are used in combination, higher flame retardancy can be obtained.

  Further, from Examples 24 to 29 in Table 4, (E) maleic anhydride as an acid anhydride, (H) ethylene / maleic anhydride copolymer of a thermoplastic resin other than a styrene copolymer, manufactured by Mitsui Chemicals, Inc. It can be seen that by blending “Admer” and (I) maleic anhydride-modified polyolefin wax, a material excellent in impact resistance can be obtained while maintaining the performance of the present invention. In particular, it can be seen that (E) acid anhydride and (I) maleic anhydride modified polyolefin wax have a large impact resistance improving effect.

Claims (9)

(A) 100 parts by weight of a polylactic acid resin, (B) 0.1 to 15 parts by weight of a polyalkylene glycol having a number average molecular weight of 8300 to 21000 , ( C) an ester system having a structure represented by the following formula (a) A resin composition comprising (D) a styrene copolymer which is a vinyl resin having a plasticizer content of 0.5 to 50 parts by weight and a rubber component content of 30 to 80% by weight .
^{_{-COO- (CH 2 COO) m- (}} R 1 O) n-R 2 (a)
(In formula (a), m represents an integer of 0 to 5, n represents an integer of 0 to 6, R ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ² has 1 to 10 carbon atoms. A linear or branched alkyl group, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, or an alkylaryl group having 7 to 15 carbon atoms, provided that m + n ≧ 1. The (C) ester plasticizer is methyl diglycol butyldiglycol adipate, benzyl methyl diglycol adipate, benzyl butyldiglycol adipate, according to claim 1 is at least one selected from ethoxycarbonylmethyl dibutyl citrate Resin composition. Furthermore, the resin composition of any one of Claims 1-2 formed by mix | blending (E) acid anhydride. The resin composition according to claim 3 , wherein the (E) acid anhydride is maleic anhydride or succinic anhydride. Furthermore, the resin composition of any one of Claims 1-4 formed by mix | blending (F) inorganic filler. Furthermore, the resin composition of any one of Claims 1-5 formed by mix | blending (G) a flame retardant. The resin composition according to any one of claims 1 to 6 , further comprising (I) a maleic anhydride-modified polyolefin wax. Molded article comprising a resin composition according to any one of claims 1-7. The molded article according to claim 8 , wherein the molded article is any one of a housing, a packing, a cover, a film, and a sheet.