JP5124951B2 - Resin composition and molded article comprising the same - Google Patents

Description

  The present invention includes a thermoplastic resin composition excellent in hydrolyzability and mechanical properties obtained by blending a carbodiimide-modified isocyanate compound with a polylactic acid resin, and further blending a thermoplastic resin having a glass transition temperature higher than that of the polylactic acid resin. The present invention relates to a thermoplastic resin composition excellent in hydrolyzability, mechanical properties, and heat resistance, and a molded article 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 above aliphatic polyester resins, polylactic acid resin is particularly expected as a plant-derived 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, a monomer, has been produced at low cost by fermentation using microorganisms, and it has become possible to produce polylactic acid resin at a much lower cost. However, the use as a general-purpose polymer derived from plants has been studied. However, on the other hand, polylactic acid resin is inferior in hydrolyzability, and therefore has a problem in durability as a general-purpose polymer, and improvement thereof has been desired.

  As a method for improving this problem, Patent Document 1 proposes using polyisocyanate for biodegradable plastics.

  Patent Document 2 proposes using a carbodiimide compound for biodegradable plastics.

  However, the proposals in Patent Document 1 and Patent Document 2 described above have an effect of improving hydrolyzability, but have a problem of reducing mechanical properties.

  Furthermore, by improving the heat resistance of the polylactic acid resin, it can be used as a general-purpose polymer molded product having a wide range of applications such as automobile parts, casings and parts of electric / electronic devices.

As a method for improving this problem, Patent Document 3 proposes using an amorphous resin selected from polycarbonate, polystyrene, and polyethylene terephthalate as the polylactic acid resin and polyisocyanate. However, although the proposal of the above-mentioned Patent Document 3 has an effect of improving heat resistance and an effect of improving hydrolyzability, there is a problem that mechanical properties are deteriorated because polyisocyanate is blended.
JP 11-80522 A (page 2-3) Republished patent W099 / 21915 (page 2-4) JP 2000-17038 A (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 polylactic acid resin composition excellent in hydrolyzability and mechanical properties, a polylactic acid resin composition excellent in hydrolyzability, mechanical properties, and heat resistance, and a molded article comprising the same. To do.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polylactic acid resin composition having excellent hydrolyzability and mechanical properties by blending a carbodiimide-modified isocyanate compound with the polylactic acid resin, and further polylactic acid resin It has been found that a polylactic acid resin composition excellent in hydrolyzability, mechanical properties and heat resistance can be obtained by blending a thermoplastic resin having a higher glass transition temperature, and has reached the present invention.

That is, the present invention
(1) L-lactic acid and D- lactic acid component (percentage% molar ratio) is 100 to 95 / 0-5 or 0-5 / 100 to 95 (A) polylactic acid resin 100 parts by weight of a carbodiimide (B) a resin composition comprising 0.1 to 10 parts by weight of a carbodiimide-modified isocyanate compound having a group / isocyanate group molar ratio in the range of 0.01 to 0.5 ,
(2) The resin composition according to (1) , further comprising (C) 1 to 200 parts by weight of a thermoplastic resin having a glass transition temperature higher than that of component (A) with respect to 100 parts by weight of component (A). object,
(3) Component (C) is polycarbonate resin, styrene copolymer, polytrimethylene terephthalate resin, polyethylene terephthalate resin, polycyclohexane terephthalate resin, polyphenylene ether resin, polyphenylene sulfide resin, polymethyl methacrylate resin and cellulose ester resin. The resin composition according to any one of (1) to (2) , which is at least one thermoplastic resin selected from:
(4) The resin composition according to any one of (1) to (3) , further comprising (D) an inorganic filler.
(5) The resin composition according to any one of (1) to (4) , further comprising (E) a flame retardant.
(6) A molded article comprising the resin composition according to any one of (1) to (5) ,
(7) The molded article, molded article according to a housing or parts of automotive parts or electrical and electronic equipment (6).

  The resin composition of the present invention is a resin composition excellent in hydrolyzability and mechanical properties or hydrolyzability, mechanical properties and heat resistance. In addition, the molded product obtained from this resin composition is a general-purpose molded product such as civil engineering materials, building materials, furniture members, materials for gaming machines and various daily necessities, taking advantage of the hydrolyzability and mechanical properties described above, Utilizing hydrolyzability, mechanical properties, and heat resistance, it can be used for automobile parts, casings and parts of electric / electronic devices, and the like.

  Hereinafter, the present invention will be described in detail.

The (A) polylactic acid resin used in the present invention, is a polymer composed of L- lactic acid and D- lactic acid, from the viewpoint of heat resistance and moldability, optical purity of lactic acid component is Ru having a high polylactic acid resin . Ie, L- lactic acid and D- lactic acid component (molar ratio of percent) used 100 to 95 / 0-5 or 0-5 / 100 to 95 from the viewpoint of the injection moldability.

  Further, as the component of the (A) polylactic acid resin, other copolymer components may be included. 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.

  The melting point of the (A) polylactic acid resin is not particularly limited, but is 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 150 ° C. or higher contains 95% or more of L-lactic acid or contains D-lactic acid. It can be obtained by containing 95% or more. 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.

The (B) carbodiimide-modified isocyanate compound in the present invention is a compound obtained by carbodiimidizing a part of the isocyanate compound, and a carbodiimide group / isocyanate group molar ratio in the range of 0.01 to 0.5 is used. By using a carbodiimide group / isocyanate group molar ratio of 0.01 or more, hydrolysis of the resin composition can be suppressed, and by using a carbodiimide group / isocyanate group of 0.5 or less, the resin composition Mechanical properties can be maintained. In addition, as an example of a method for measuring a carbodiimide group / isocyanate group, an infrared spectrophotometer was used to prepare a calibration curve for the wave height ratio of a known sample of carbodiimide group / isocyanate group, and carbodiimide in a carbodiimide-modified isocyanate compound. And a method of measuring group / isocyanate group. Further, as a method for measuring carbodiimide group / isocyanate group in the resin composition, a carbodiimide-modified isocyanate compound in the resin composition is extracted using a solvent such as methanol, and the carbodiimide group / isocyanate group is extracted by the same method as described above. The method of measuring is mentioned.

  As the isocyanate compound, known aromatic, alicyclic and aliphatic isocyanates can be used. Specifically, tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate. Isocyanate, dimethylbiphenylene diisocyanate, dimethoxybiphenylene diisocyanate, naphthalene diisocyanate, tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene isocyanate Range isocyania Over DOO, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyl dicyclohexylmethane diisocyanate and the like, used in one or a mixture. Of the above, an isocyanate compound containing 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) as a main component is preferably used. Further, as a method of carbodiimidizing a part of the isocyanate compound, a known method can be used, for example, it can be produced by the method described in JP-A No. 61-111318, pages 3 and 7, It is different from a mixture of simply an isocyanate compound and polycarbodiimide. The carbodiimide-modified isocyanate compound thus obtained is “Millionate” MTL, “Millionate” MTL-C, “Coronate” 69 from Nippon Polyurethane Kogyo Co., Ltd. Or commercially available from Mitsui Takeda Chemical Co., Ltd. under the names “Cosmonate” LK and “Cosmonate” LL, and the molar ratio of the carbodiimide group / isocyanate group of the commercial product is 0.1 to 0.2. It is a compound in the range.

  MDI has a solidification point of about 38 ° C., and is solid at room temperature of 25 ° C. However, the commercial product of the above carbodiimide-modified isocyanate compound is different from a mixture of an isocyanate compound and polycarbodiimide, so it is liquid at room temperature. Yes, it is also called liquid MDI.

  Moreover, the compounding quantity of (B) carbodiimide modification isocyanate compound is 0.1-10 weight part with respect to 100 weight part of (A) component, Preferably it is 0.2-8 weight part, More preferably, it is 0.3. ~ 6 parts by weight, most preferably 0.4 to 5 parts by weight. When the amount is less than 0.1 part by weight, the effect of suppressing hydrolysis is small, and when it exceeds 10 parts by weight, the mechanical properties are lowered. It is not preferable.

  In order to improve the hydrolyzability, it is possible to use a known hydrolysis inhibitor in addition to the (B) carbodiimide-modified isocyanate compound, and the known hydrolysis inhibitor is an epoxy compound or an oxazoline compound. , An oxazine compound, a carbodiimide compound, a polyisocyanate compound, and the like. Among them, an epoxy compound is preferable, and the amount used in combination is preferably an amount that does not exceed (B) a carbodiimide-modified isocyanate compound. , The deterioration of mechanical properties can be kept low.

  The resin composition of the present invention can further contain a thermoplastic resin having a glass transition temperature (hereinafter abbreviated as Tg) higher than the components (C) and (A).

  The thermoplastic resin having a glass transition temperature (hereinafter abbreviated as Tg) higher than the component (C) (A) in the present invention means that the Tg of the polylactic acid resin of the present invention (A) is 60 ° C. Specific examples of the thermoplastic resin having a Tg of: polycarbonate resin, styrene copolymer, polytrimethylene terephthalate resin, polyethylene terephthalate resin, polycyclohexane terephthalate resin, polyphenylene ether resin, polyphenylene sulfide resin, polymethacrylate Acid methyl resin, polyvinyl chloride resin, polystyrene resin, polyarylate resin, polyetherimide resin, nylon 46, polyetheretherketone, polyimide resin, polyamideimide resin, cellulose acetate resin, cellulose diacetate resin, cellulose Examples include styrene acetate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, cellulose acetate phthalate resin, and liquid crystal aromatic polyester resin. Polycarbonate resin, styrene copolymer, polytrimethylene terephthalate resin, polyethylene terephthalate resin , Polycyclohexane terephthalate resin, polyphenylene ether resin, polyphenylene sulfide resin, polymethyl methacrylate resin, and cellulose acetate resin, cellulose diacetate resin, cellulose triacetate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, cellulose acetate phthalate Cellulose ester resins such as resins are preferred, It is needed. Further, it may be a copolymer of a substance copolymerizable with the resin, or a molten or non-melted mixture with another resin. In the present invention, the Tg of the thermoplastic resin having a higher Tg than the components (C) and (A) is measured by a differential scanning calorimeter (DSC) at a temperature rising rate of 20 ° C./min. Is calculated using the midpoint method.

  Moreover, the compounding quantity of the thermoplastic resin which has Tg higher than (C) (A) component is 1-200 weight part with respect to 100 weight part of (A) component, Preferably it is 2-180 weight part, More preferably Is 3 to 160 parts by weight, most preferably 4 to 150 parts by weight. When the amount is less than 1 part by weight, the effect of improving the heat resistance is small, and when it exceeds 200 parts by weight, the plant-derived (A) polylactic acid resin Since the component ratio becomes extremely small, it is not preferable from the viewpoint of global environmental conservation.

  Examples of the aromatic polycarbonate resin preferably used include aromatic polycarbonates such as aromatic homo- or copolycarbonates obtained by reacting aromatic dihydric phenol compounds with phosgene or carbonic acid diesters. Aromatic dihydric phenol compounds include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3) 5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, etc. can be used, and these can be used alone or as a mixture. it can.

  The styrenic copolymer preferably used is one or more monomers selected from styrene or α-methylstyrene, aromatic vinyl compounds, vinyl cyanide compounds, alkyl (meth) acrylates, 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 referred to).

  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. Furthermore, the copolymer with the following component which can be copolymerized with a styrene-type copolymer is also contained in this 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. Further, a styrene copolymer obtained by graft polymerization or copolymerization of an unsaturated acid anhydride or an epoxy group-containing vinyl monomer is also included in the present invention.

Examples of preferred copolymers of styrenic copolymers include methyl methacrylate / acrylonitrile / styrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, acrylonitrile / butadiene / styrene resin (ABS 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, methyl methacrylate / butadiene / styrene resin (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene resin (MABS resin) and high impact- Restyrene resin (HI-PS resin) and the like may be used, and these may be used as a mixture of two or more, acrylonitrile / butadiene / styrene resin (ABS resin), methyl methacrylate / butadiene / styrene resin (MBS resin), Methyl methacrylate / acrylonitrile / butadiene / styrene resin (MABS resin) and high impact polystyrene resin (HI-PS resin) are preferably used (/ indicates copolymerization).

The (D) inorganic filler in the present invention has an effect of improving the appearance and heat resistance of the molded product of the resin composition of the present invention. Examples of the inorganic filler (D) include plate-like, needle-like, fibrous or granular materials, and can be uniformly dispersed in the component (A), the component (B) and, if necessary, the component (C). Inorganic fillers are preferred, and silicate minerals, silicate minerals, and various minerals, which are finely divided 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 useful as inorganic crystal nucleating agents, and (A) have the effect of promoting the crystallization rate of polylactic acid 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. In addition, the average particle size was defined as a 50% value obtained from a volume-based cumulative distribution measured with a particle size distribution measuring apparatus of a laser diffraction scattering method. In addition, it is the value calculated | required by the said method also about the (E) component as described below and the average particle diameter of the component which can be mix | blended as needed.

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 (D) inorganic filler is preferably 1 to 100 parts by weight, more preferably 2 to 80 parts by weight, particularly preferably 3 to 60 parts by weight with respect to 100 parts by weight of the (A) polylactic acid resin. If the amount is less than 1 part by weight, the effect of increasing the appearance or heat resistance of the molded product is small, and if it exceeds 100 parts by weight, the fluidity at the time of molding is not preferable.

  The (E) flame retardant in the present invention is not particularly limited as long as it is a substance added for the purpose of imparting flame retardancy to the resin. Specifically, brominated flame retardants and phosphorus flame retardants are used. , Nitrogen compound-based flame retardants, silicone-based flame retardants, and other inorganic flame retardants. These may be used by selecting at least one of them.

  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 and the like 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, phosphoric ester amides, and melamine polyphosphates.

  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. The silicone resin _may be mentioned a resin having _{SiO 2, RSiO 3/2,} R 2 SiO, a three-dimensional network structure formed by combining structural units of 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 Or a resin in which these are copolymerized.

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

  Among the flame retardants (E), at least one or two or more selected from phosphorus-based flame retardants containing no halogen, nitrogen compound-based flame retardants, silicone-based flame retardants, and other inorganic flame retardants are combined. 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

  Further preferred flame retardants are 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 (E). It is particularly preferable to use a species or a combination of two or more species.

  Moreover, the compounding quantity of (E) flame retardant is 1-100 weight part with respect to 100 weight part of (A) polylactic acid resin, Furthermore, 2-90 weight part is preferable, Especially preferably, it is 3-80 weight If the amount is less than 1 part by weight, the effect of imparting flame retardancy is small, and if it exceeds 100 parts by weight, the mechanical properties deteriorate, which is not preferable.

  Moreover, by using a specific fluorine-based resin in combination with the flame retardant (E), 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 3 parts by weight, the fluidity and flame retardancy of the present invention are decreased, 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 (E) flame retardant and the resin composition in which the (E) flame retardant and a specific fluorine-based resin are blended, the flame retardance 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, a thermoplastic resin other than the component (C) can be further blended as long as the performance of the present invention is not impaired, and is excellent in impact resistance, surface appearance, moldability, mechanical properties, flexibility, and the like. A resin composition and a molded product comprising the same can be obtained. Specific examples of the thermoplastic resin other than the component (C) include polyester resins other than the polylactic acid resin of the component (A), polyolefin resins such as polyacetal resins, polyamide resins, polyethylene resins and polypropylene resins, and polyolefin copolymers. Acrylic resin, polyurethane resin, chlorinated polyethylene resin, chlorinated polypropylene resin, thermoplastic starch resin, polyethersulfone resin, phenoxy resin, thermoplastic phenol resin, poly-4-methylpentene-1 resin, core shell rubber and polyvinyl alcohol A thermoplastic resin such as a resin can be mentioned. The thermoplastic resin may be a glycidyl group, an epoxy group, an acid anhydride, or a thermoplastic resin obtained by grafting or copolymerizing one of different polymers.

  Among them, polyacetal resins, polyester resins other than polylactic acid resins such as polybutylene terephthalate resins, polyester elastomers, polyethylene terephthalate / succinate resins, polybutylene succinate resins, aliphatic aromatic polyester resins and polycaprolactone resins, polyamide resins, It is preferable to blend at least one selected from a core-shell rubber and a glycidyl group, an epoxy group, an acid anhydride, or a thermoplastic resin obtained by grafting or copolymerizing one of different polymers.

  The core shell rubber is a multilayer structure composed of an outermost shell layer and two or more inner core layers. For example, the core layer is made of a soft resin such as dimethylsiloxane / butyl acrylate polymer and is the outermost layer. Is a multilayer structure in which any layer is modified with glycidyl methacrylate or acid anhydride. The particle diameter of the multilayer structure is not particularly limited, but is preferably 0.01 μm or more and 1000 μm or less, more preferably 0.02 μm or more and 100 μm or less, and particularly Most preferably, it is 0.05 μm or more and 10 μm or less. 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 or more and 90 parts by weight or less with respect to the multilayer structure. 30 parts by weight or more and 80 parts by weight or less 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 Examples thereof include “STAPHYLOID” manufactured by Yakuhin Kogyo Co., Ltd. and “Parapet SA” manufactured by Kuraray Co., Ltd.

  Specific examples of the thermoplastic resin in which the glycidyl group, epoxy group, acid anhydride or one of different polymers is grafted or copolymerized include ethylene / glycidyl methacrylate, ethylene / methyl acrylate / glycidyl methacrylate, ethylene / anhydrous Maleic acid, ethylene / propylene / maleic anhydride, ethylene / butene-1 / maleic anhydride, ethylene / ethyl acrylate-g-polystyrene, ethylene / glycicyl methacrylate-g-polystyrene, ethylene / glycicyl methacrylate-g-polymethacrylic Methyl acid, ethylene / ethyl acrylate maleic anhydride-g-polymethyl methacrylate, ethylene / glycisyl methacrylate-g-polystyrene / polyacrylonitrile, polycarbonate-g-polystyrene Ethylene / ethyl acrylate / maleic anhydride-g-polystyrene, polycarbonate-g-polystyrene / polyacrylonitrile, polycarbonate-g-maleic anhydride / polystyrene, polycarbonate-g-maleic anhydride / polystyrene / polyacrylonitrile, etc. A resin composition having excellent impact resistance while maintaining the performance of the invention can be obtained (/ represents copolymerization, -g- represents graft).

  Further, among the polyester resins other than the above-mentioned polylactic acid resin, the polybutylene succinate resin particularly provides a resin composition excellent in impact resistance while maintaining the performance of the present invention, and further a resin composition containing a flame retardant. Provides a resin composition that is further excellent in impact resistance and flame retardancy while maintaining the performance of the present invention without reducing flame retardancy.

  Examples of commercially available thermoplastic resins obtained by grafting or copolymerizing the above glycidyl group, epoxy group, acid anhydride or one of different polymers include “Bond First” manufactured by Sumitomo Chemical Co., Ltd. and Mitsui Petrochemical Co., Ltd. “Admer” and “N-Toughmer” manufactured by Co., Ltd., “Modiper” manufactured by Nippon Oil & Fats Co., Ltd. and the like can be mentioned.

  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 aging 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. Moreover, it is preferable to use a hindered phenol compound and / or a benzotriazole compound as the stabilizer. The blending amount of the stabilizer is 0.01 to 3 parts per 100 parts by weight of the (A) polylactic acid resin. Part by weight is preferred, 0.03 to 2 parts by weight is more preferred, and if it is less than 0.01 part by weight, there is no effect of the stabilizer, and if it exceeds 3 parts by weight, the mechanical properties are lowered, which is not preferred.

  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, Maleic anhydride-modified polyethylene wax, oxidation type polyethylene wax, chlorinated polyethylene wax, polypropylene wax and the like can be mentioned. Fatty acid amides preferably have 6 or more carbon atoms, specifically oleic acid amide, erucic acid amide, Behenic acid amides and the like, and the alkylene bis fatty acid amide is preferably one having 6 or more carbon atoms. Specifically, methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2 -Hydroxyethyl) stearamide and the like, examples of the aliphatic ketone include higher aliphatic ketones, and the fatty acid lower alcohol ester preferably has 6 or more carbon atoms, ethyl stearate butyl stearate, Examples include fatty acid polyhydric alcohol esters such as glycerin monostearate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol adipate stearate, dipentaerythritol adipate stearic acid, sorbitan Monobehenate and the like, and examples of the fatty acid polyglycol ester include polyethylene glycol fatty acid ester and polypropylene glycol fatty acid ester. Examples of silicone include tilstyryl-modified silicone, 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 partial saponified ester, polyethylene wax, oxidized polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bis stearic acid amide are preferable, and particularly, montanic acid partial saponified ester and ethylene bis stearic acid amide are preferable. . 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 Then, there is no effect of a release agent, and if it exceeds 3 parts by weight, the mechanical properties are lowered, 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 30 parts by weight, more preferably 0.5 to 25 parts by weight, and less than 0.1 parts by weight with respect to 100 parts by weight of the (A) polylactic acid resin. Then, there is no antistatic effect, and if it exceeds 30 parts by weight, the mechanical properties are deteriorated.

  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, there is no effect of improving the toning, weather resistance (light) and conductivity, and mechanical properties exceeding 10 parts by weight. Is not preferable.

  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 Phosphorus compound metal salts such as -butylphenyl phosphate.

  In the present invention, a layered silicate can be further blended, and the formability can be improved. The layered silicate is more preferably blended with a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions. In the present invention, the layered silicate in which the exchangeable cation existing between the layers is exchanged with the organic onium ion is the exchange of the exchangeable cation of the layered silicate having the exchangeable cation between the layers with the organic onium ion. Inclusion compound.

  A layered silicate having an exchangeable cation between layers has a structure in which plate-like materials having a width of 0.05 to 0.5 μm and a thickness of 6 to 15 angstroms are laminated. Has a cation. The cation exchange capacity is 0.2 to 3 meq / g, and preferably the cation exchange capacity is 0.8 to 1.5 meq / g.

Specific examples of the layered silicate include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate. Examples thereof include swelling mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, and the like, which may be natural or synthesized. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable.
In the present invention, a plasticizer can be further blended. As the plasticizer used in the present invention, known ones generally used as polymer plasticizers can be used without particular limitation, for example, polyester plasticizer, glycerin plasticizer, polyvalent carboxylic ester plasticizer, Examples include polyalkylene glycol plasticizers and epoxy plasticizers.

  Although the manufacturing method of the resin composition of this invention is not specifically limited as long as the requirements prescribed | regulated by this invention are satisfy | filled, For example, (A) polylactic acid resin, (B) carbodiimide modified isocyanate compound, as needed (C) A thermoplastic resin having a glass transition temperature higher than that of the component (A), (D) an inorganic filler, (E) a flame retardant, and, if necessary, other additives are blended in advance, and (A) poly A method of uniformly melting and kneading with a single-screw or twin-screw extruder or a method of removing the solvent after mixing in a solution is preferably used at a melting point or higher of the lactic acid resin.

  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 a general-purpose polymer having excellent hydrolyzability, such as injection molding, blow molding, extrusion molding, sheet molding, film molding, and spinning on various fibers such as undrawn yarn, drawn yarn, and super-drawn yarn. Can be processed into various product shapes and used as molded products for various purposes such as mechanical mechanism parts, electrical / electronic parts, automobile parts, optical equipment, building members, and daily necessities. In particular, the resin composition obtained from the (A) polylactic acid resin of the present invention, (B) a carbodiimide-modified isocyanate compound, and (C) a thermoplastic resin having a glass transition temperature higher than the component (A) is hydrolyzable and heat resistant. Therefore, it is preferably used as an automobile part or an electric / electronic equipment casing or part that requires more durability.

  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, (D) a resin composition containing talc as an inorganic filler 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. Further, (D) a resin composition containing glass fiber as an inorganic filler can be used to obtain a molded product having a specific high heat distortion temperature, and a molded product that is used in a high temperature atmosphere or hardly undergoes thermal deformation at a high temperature. Can be suitably used.

  In addition, since the resin composition further blended with (E) a flame retardant can satisfy the standard of the vertical combustion test of US UL standard subject 94 (UL 94), 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 1-14], [Comparative Examples 1-11], [Examples 15-23]
The polylactic acid resin is a carbodiimide-modified isocyanate compound shown in Tables 1 to 3 using a poly-L-lactic acid resin having a D-form content of 2% and a weight average molecular weight in terms of PMMA of 170,000, component (A) A thermoplastic resin having a higher glass transition temperature, an inorganic filler, and a flame retardant are mixed in the proportions shown in Tables 1 to 3, and a 30 mm diameter twin-screw extruder is used with a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm. And kneaded to obtain a resin composition. In addition, the material which mix | blended the thermoplastic resin which has a glass transition temperature higher than (A) component was melt-kneaded at the cylinder temperature of 260 degreeC. The carbodiimide-modified isocyanate compound used in the present invention is obtained by carbodiimidizing 4,4 ′ diphenylmethane diisocyanate, and has a carbodiimide group / isocyanate group molar ratio of 0.12 to 0.16.

The obtained resin composition was subjected to injection molding at a cylinder temperature of 190 ° C. and a mold temperature of 40 ° 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 (6) was performed, and the results are shown in Tables 1 to 3. In addition, the material which mix | blended the thermoplastic resin which has a glass transition temperature higher than (A) component was injection-molded at the cylinder temperature of 250 degreeC.
(1) Mechanical properties ASTM No. 1 dumbbell produced by injection molding was measured for tensile yield stress and tensile elongation at break according to ASTM D-638.
(2) Hydrolyzability ASTM No. 1 dumbbell produced by injection molding was put into Tabei Espec Humidi cabinet LHL-112 controlled at a temperature of 60 ° C. and a humidity of 90% for 300 hours, and tensile breaking elongation of mechanical properties was achieved. Was measured.
(3) Heat resistance Using a bending test piece having a thickness of about 3.17 mm produced by injection molding, the heat distortion temperature was measured under a load of 0.45 MPa in accordance with ASTM D-648.
(4) External appearance of molded product The external appearance of the ASTM No. 1 dumbbell produced by injection molding was visually observed, and it was determined that the external appearance of the molded product was good with respect to the glossy or glossy molded product.
(5) Flame retardancy US UL standard described in the specification 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 A flame test was conducted in accordance with the vertical combustion test method of Subject 94 (UL94), and a flame retardance rank was determined. Materials that did not pass the flame retardancy rank were out of specification.
(6) Impact resistance Izod impact was measured according to ASTM D-256 using an Izod impact test piece not having a notch of about 3.17 mm thickness produced by injection molding.

  From Examples 1 to 7 in Table 1, it can be seen that the resin composition containing the carbodiimide-modified isocyanate compound of the present invention is excellent in hydrolyzability and mechanical properties. Furthermore, it turns out that the resin composition which mix | blended the thermoplastic resin which has a glass transition temperature higher than (A) component is a material excellent in hydrolyzability, mechanical property, and heat resistance.

  From Comparative Examples 1 to 10 in Table 2, a resin composition containing no carbodiimide-modified isocyanate compound, a resin composition containing a known hydrolysis inhibitor epoxy compound, oxazoline compound and carbodiimide compound instead of a carbodiimide-modified isocyanate compound It can be seen that a material excellent in hydrolyzability and mechanical properties cannot be obtained.

  Further, from Examples 8 to 16 in Table 3, while maintaining the performance of the present invention, a material excellent in the appearance of a molded product is obtained by blending talc of (D) inorganic filler, and (D) inorganic filler It can be seen that the resin composition containing the glass fiber exhibits a particularly high heat distortion temperature.

  In addition, (E) A molded product imparted with flame retardancy can be obtained by adding a flame retardant, and in particular, when a flame retardant and a fluororesin are used in combination, a molded product exhibiting a higher level of flame retardancy can be obtained. I understand.

  Moreover, the resin composition which further blended polybutylene succinate resin, ethylene / glycidyl methacrylate resin and ethylene / butene-1 / maleic anhydride resin of aliphatic polyester resin of thermoplastic resin other than the component (C) of the present invention, It can be seen that a resin composition having high impact strength can be obtained while maintaining the performance of the present invention. In particular, it can be seen that a polybutylene succinate resin of an aliphatic polyester resin can provide a resin composition having a high impact strength while maintaining the performance of the present invention without reducing the flame retardancy.

Claims (7)

The carbodiimide group / isocyanate with respect to 100 parts by weight of the polylactic acid resin (A) in which the component of L-lactic acid and D-lactic acid (molar ratio%) is 100 to 95/0 to 5 or 0 to 5/100 to 95. The resin composition formed by mix | blending 0.1-10 weight part of (B) carbodiimide modified isocyanate compounds whose group molar ratio is the range of 0.01-0.5 . Further (C) (A) to the thermoplastic resin having a glass transition temperature higher than the component (A) 100 parts by weight of component a resin composition according to claim 1 comprising by blending 1 to 200 parts by weight. The component (C) is selected from polycarbonate resin, styrene copolymer, polytrimethylene terephthalate resin, polyethylene terephthalate resin, polycyclohexane terephthalate resin, polyphenylene ether resin, polyphenylene sulfide resin, polymethyl methacrylate resin and cellulose ester resin. at least one is a thermoplastic resin according to claim 1 resin composition according to any one of 2. Furthermore, (D) The resin composition of any one of Claims 1-3 formed by mix | blending an inorganic filler. Furthermore, the resin composition of any one of Claims 1-4 formed by mix | blending (E) a flame retardant. A molded article comprising the resin composition according to any one of claims 1 to 5 . The molded article according to claim 6 , wherein the molded article is an automobile part or a casing or part of an electric / electronic device.