WO2011152371A1 - Composition de résine thermoplastique et produits moulés en cette composition - Google Patents

Composition de résine thermoplastique et produits moulés en cette composition Download PDF

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Publication number
WO2011152371A1
WO2011152371A1 PCT/JP2011/062432 JP2011062432W WO2011152371A1 WO 2011152371 A1 WO2011152371 A1 WO 2011152371A1 JP 2011062432 W JP2011062432 W JP 2011062432W WO 2011152371 A1 WO2011152371 A1 WO 2011152371A1
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Prior art keywords
flame retardant
thermoplastic resin
resin composition
polylactic acid
mass
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PCT/JP2011/062432
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English (en)
Japanese (ja)
Inventor
泰生 上川
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ユニチカ株式会社
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Priority to JP2011544749A priority Critical patent/JP4906981B2/ja
Priority to CN201180011854.4A priority patent/CN102782044B/zh
Publication of WO2011152371A1 publication Critical patent/WO2011152371A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention is a thermoplastic resin composition having excellent flame retardancy, impact resistance, and heat resistance and capable of being used in various versatile products, while using polylactic acid that is less dependent on petroleum products.
  • the present invention relates to a molded body obtained by molding a product.
  • biomass raw material resins such as polylactic acid have attracted attention from the viewpoint of environmental conservation.
  • Polylactic acid is inexpensive because it can be mass-produced, and since it has high heat resistance among biomass-derived resins, its use in various fields including automobile parts and machine parts is being studied.
  • polylactic acid has a problem that it has low flame retardancy and easily burns, and has a drawback that the impact resistance is low and the product is easily cracked by impact.
  • flame retardancy is evaluated based on the US UL standard subject 94 (hereinafter abbreviated as UL94), and is preferably V-1 or higher.
  • V-1 flame retardancy is achieved by adding a fluorine compound to a resin composition comprising polylactic acid, polycarbonate, styrene compatibilizer, monocarbodiimide, polyvalent carbodiimide, and a flame retardant.
  • a fluorine compound is added, a toxic gas is generated during molding or incineration.
  • Patent Document 2 describes a resin composition that is made of polylactic acid and an aromatic polyester and has flame retardancy by having a flame retardant.
  • Patent Document 2 shows that this resin composition can be used for automobile parts, electrical / electronic parts and the like, and that flame retardancy of V-1 and V-0 can be achieved.
  • the resin composition described in Patent Document 2 uses an aromatic polyester, and therefore has an impact resistance performance. It was low and did not have sufficient performance. Further, polylactic acid itself was not modified, and the heat resistance performance was not sufficiently satisfactory.
  • the present invention solves the above-mentioned problems, and is excellent in flame retardancy without using a fluorine-based compound, can achieve at least the performance of V-1, and has excellent impact resistance and heat resistance.
  • a thermoplastic resin composition that can be suitably used for automobile parts and electrical / electronic parts that are excellent in harsh usage environments and that are also environmentally friendly, and a molded body formed by molding the same. is there.
  • the present inventor has used an amorphous thermoplastic resin having a bisphenol group as a resin component together with polylactic acid, an acrylic compatibilizer, and a specific flame retardant. It was found that a resin composition having good flame retardancy and excellent impact resistance and heat resistance can be obtained by using two types in combination, and the present invention has been achieved.
  • the gist of the present invention is as follows. (1) A resin composition containing polylactic acid (A), an amorphous thermoplastic resin (B) having a bisphenol group, an acrylic compatibilizer (C) and a flame retardant (D),
  • the content of the polylactic acid (A) is 25 to 60% by mass
  • the content of the amorphous thermoplastic resin (B) having a bisphenol group is 30 to 60% by mass
  • the content of the acrylic compatibilizer (C) Is 0.5 to 20% by mass
  • the content of the flame retardant (D) is 5 to 30% by mass
  • the flame retardant (D) is a phosphate ester flame retardant (D-1) and a phosphinic acid metal salt type.
  • a flame retardant (D-2), and a mass ratio of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) [(D-1) / (D-2) ] Is a thermoplastic resin composition, characterized in that it is 10/90 to 50/50.
  • the amorphous thermoplastic resin (B) having a bisphenol group is a polycarbonate resin (B-1) and / or a polyarylate resin (B-2) (1) to (3) The thermoplastic resin composition according to any one of the above.
  • the phosphate ester flame retardant (D-1) is an aromatic condensed phosphate ester
  • the phosphinic acid metal salt flame retardant (D-2) is an aluminum phosphinate ( 1)
  • the aromatic carbodiimide compound (E) is an aromatic monocarbodiimide (E-1) and an aromatic polyvalent carbodiimide (E-2), and the aromatic monocarbodiimide (E-1) and the aromatic polyvalent polyvalent
  • the thermoplastic resin composition of the present invention contains a non-crystalline thermoplastic resin having a bisphenol group, which is excellent in flame retardancy and impact resistance, and polylactic acid. Improved low flame resistance and low impact resistance, and excellent in flame retardancy and impact resistance. And since the thermoplastic resin composition of the present invention contains an acrylic compatibilizing agent as a compatibilizing agent, the compatibility between the polylactic acid and the amorphous thermoplastic resin having a bisphenol group is greatly improved, The high flame resistance and impact resistance of the amorphous thermoplastic resin having a bisphenol group are sufficiently exhibited. Further, since a specific flame retardant is used in combination as a flame retardant, further excellent flame retardancy is imparted, and the resin composition can have flame retardancy of V-1 and V-0 levels.
  • the heat resistance of polylactic acid can be improved by using a polylactic acid having a D-form content that satisfies a specific range or using a cross-linked structure. And it becomes possible to improve the heat resistance of resin composition itself, and also to improve a flame retardance. Moreover, it becomes possible to improve the heat-and-moisture resistance of a resin composition by containing an aromatic carbodiimide compound.
  • the thermoplastic resin composition of the present invention is remarkably excellent in flame retardancy, impact resistance, heat resistance, and further heat and moisture resistance, and uses a natural product-derived resin. The dependence on the products is low and the global environment is taken into consideration. And the thermoplastic resin composition of this invention can be made into various molded objects by injection molding etc. Since the molded article of the present invention is formed by molding the resin composition of the present invention as described above, it is suitable for various applications such as various machine parts, electrical / electronic parts, building members, automobile parts, daily necessities, etc. Can be used for
  • thermoplastic resin composition of the present invention [hereinafter sometimes abbreviated as composition (X). ] Contains polylactic acid (A), an amorphous thermoplastic resin (B) having a bisphenol group, an acrylic compatibilizer (C), and a flame retardant (D).
  • polylactic acid (A) refers to poly (L-lactic acid), poly (D-lactic acid), a mixture or a copolymer thereof.
  • Polylactic acid has high heat resistance among aliphatic polyesters, but in order to further improve heat resistance, the D-form content of polylactic acid is 1.0 mol% or less, or 99.0. It is preferably at least mol%. Among them, the D-form content is preferably 0.1 to 0.6 mol% or 99.4 to 99.9 mol%.
  • the polylactic acid (A) having a D-form content satisfying the above range has excellent crystallinity, thereby improving heat resistance and crystallization speed, thereby shortening the molding cycle and excellent moldability. It will be a thing.
  • the D-form content of polylactic acid (A) refers to the proportion (mol%) occupied by D lactic acid units in the total lactic acid units constituting polylactic acid (A). Therefore, for example, in the case of polylactic acid having a D-form content of 1.0 mol%, this polylactic acid has a ratio of D lactic acid units of 1.0 mol% and a ratio of L lactic acid units of 99.0. Mol%.
  • the D-form content of polylactic acid (A) is such that L lactic acid and D lactic acid obtained by decomposing polylactic acid (A) are all methyl esterified, and methyl ester of L lactic acid and methyl ester of D lactic acid are obtained. Is calculated by a method of analyzing with a gas chromatography analyzer.
  • polylactic acid (A) satisfying such specific D-form content commercially available products can be used.
  • lactide which is a cyclic dimer of lactic acid
  • L-lactide having a sufficiently low D-form content or D-lactide having a sufficiently low L-form content is used as a raw material by a known melt polymerization method.
  • those produced by further using a solid phase polymerization method can be used.
  • polylactic acid (A) As a form of crosslinking, polylactic acid molecules may be directly crosslinked, indirectly crosslinked via a crosslinking aid, or may be a mixture of direct crosslinking and indirect crosslinking. By introducing the crosslinked structure, the heat resistance of the polylactic acid (A) is improved.
  • a method for introducing a crosslinked structure into polylactic acid (A) there are known methods such as a method of irradiating an electron beam, a method of using a polyfunctional compound such as a polyvalent isocyanate compound, and a method of using a peroxide. Can be mentioned. In view of crosslinking efficiency, a method using a peroxide is preferred.
  • Peroxides include benzoyl peroxide, bis (butylperoxy) trimethylcyclohexane, bis (butylperoxy) cyclododecane, butylbis (butylperoxy) valerate, dicumyl peroxide, butylperoxybenzoate, dibutyl peroxide, Examples thereof include bis (butylperoxy) diisopropylbenzene, dimethyldi (butylperoxy) hexane, dimethyldi (butylperoxy) hexyne, and butylperoxycumene.
  • the amount of the peroxide used is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polylactic acid (A). Although it can be used even if it exceeds 10 parts by mass, the effect is saturated and it is not economical. In addition, since a peroxide decomposes
  • the content thereof is preferably 1 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the peroxide. Although it can be used even if it exceeds 50 parts by mass, the effect is saturated and it is not economical.
  • the (meth) acrylic acid ester compound includes a compound having two or more (meth) acrylic groups in the molecule, or one or more (meth) acrylic groups and one or more glycidyl groups or vinyl groups. preferable. These compounds have high reactivity with the biodegradable resin, the monomer hardly remains, and the resin is less colored.
  • Specific examples of the (meth) acrylic acid ester compound include, for example, glycidyl (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyloxy polyethylene glycol mono (meth) acrylate, and polyethylene.
  • Examples include glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, or a copolymer of alkylene glycol in which these alkylene glycol portions have different alkylene groups.
  • Examples of the method for causing polylactic acid (A) to undergo a crosslinking reaction using a peroxide and a crosslinking aid include a method of melt-kneading using a general extruder.
  • the peroxide and / or the crosslinking aid may be dissolved or dispersed in the medium in advance.
  • a solution or dispersion of a crosslinking aid may be injected while melting and kneading polylactic acid (A) and a peroxide, and a crosslinking aid and a peroxide may be injected while melting and kneading polylactic acid (A).
  • An oxide solution or dispersion may be injected and melt kneaded.
  • the medium for dissolving or dispersing the peroxide and / or crosslinking aid is not particularly limited, but a plasticizer excellent in compatibility with the resin composition of the present invention is preferable.
  • the plasticizer include aliphatic polyvalent carboxylic acid ester derivatives, aliphatic polyhydric alcohol ester derivatives, aliphatic oxyester derivatives, aliphatic polyether derivatives, aliphatic polyether polyvalent carboxylic acid ester derivatives, and the like. .
  • plasticizer compounds include glycerin diacetomonolaurate, glycerin diacetomonocaprate, polyglycerin acetate, polyglycerin fatty acid ester, fatty acid triglyceride, dimethyl adipate, dibutyl adipate, triethylene glycol diacetate, acetylricinoleic acid Examples include methyl, acetyltributyl citrate, polyethylene glycol, dibutyl diglycol succinate, bis (butyl diglycol) adipate, and bis (methyl diglycol) adipate.
  • the polylactic acid (A) is more preferably a polylactic acid having a D-form content of 1.0 mol% or less, or 99.0 mol% or more and having a crosslinked structure introduced therein. .
  • the heat resistance of polylactic acid (A) is improved, and further the composition (X) Heat resistance is improved.
  • the heat distortion temperature of the composition (X) is set to 110 ° C. or higher by using polylactic acid (A) having a specific D-form content or having a crosslinked structure introduced. Is possible.
  • the heat distortion temperature is 110 ° C. or higher, fields and applications in which the obtained molded body can be used are widened, and can be used for various automobile parts, electric / electronic parts, and the like.
  • the composition (X) using such polylactic acid (A) (X) ) Is formed at a high temperature, or heat treatment is performed after the forming, whereby the crystallinity of the obtained formed body can be further improved.
  • the composition (X) of this invention when using the specific flame retardant (D) mentioned later and using polylactic acid (A) which was excellent in such crystallinity, the molded object obtained will be, The crystallinity is improved and the flame retardancy is also improved.
  • the two specific flame retardants (D-1) and (D-) contained in the composition (X) are changed. It is assumed that the function of 2) is activated and works in a direction in which the flame retardant performance is sufficiently exhibited. That is, in the present invention, the poly (lactic acid) (A) having a specific D-form content or having a cross-linked structure introduced makes it difficult for the composition (X) to have improved heat resistance. The flammability is also improved.
  • the polylactic acid (A) preferably has a melt flow rate (hereinafter abbreviated as MFR) measured by the measurement method described later in the range of 0.1 to 50 g / 10 minutes, preferably 0.2 to 20 g / 10 minutes. Is more preferably 0.5 to 15 g / 10 min. If the MFR exceeds 50 g / 10 min, the melt viscosity is too low and the mechanical properties and heat resistance of the molded product may be inferior. On the other hand, if the MFR is less than 0.1 g / 10 minutes, the load during the molding process is increased, and the operability is lowered.
  • MFR melt flow rate
  • the content of polylactic acid (A) in the composition (X) needs to be 25 to 60% by mass, and preferably 30 to 50% by mass.
  • the content of the polylactic acid (A) is less than 25% by mass, the ratio of using the resin of the biomass raw material in the composition (X) is small, and the merit in the environment is small.
  • the content exceeds 60% by mass, the proportion of the amorphous thermoplastic resin (B) having a bisphenol group decreases, so that the composition (X) is inferior in impact resistance and flame retardancy. become.
  • amorphous thermoplastic resin refers to a thermoplastic resin whose melting point is not observed by the melting point measurement method described below.
  • Measurement method of melting point Using a DSC (Differential Scanning Calorimetry) device (Pyrisl DSC manufactured by PerkinElmer), the temperature was raised from ⁇ 100 ° C. to 300 ° C. at 20 ° C./min, then to ⁇ 100 ° C. at 50 ° C./min, Subsequently, the temperature is raised from ⁇ 100 ° C. to 300 ° C. at a rate of 20 ° C./min. The melting peak in the second temperature raising process is defined as the melting point.
  • Amorphous thermoplastic resin (B) having a bisphenol group [hereinafter abbreviated as amorphous thermoplastic resin (B). ]
  • amorphous thermoplastic resin (B) From the point of being excellent in impact resistance and flame retardancy, polycarbonate resin (B1), polyarylate resin (B2), resin (B3) containing both polycarbonate resin (B1) and polyarylate resin (B2) Is preferred.
  • the polycarbonate resin (B1) will be described.
  • the polycarbonate resin (B1) refers to a resin composed of bisphenol residues and carbonate residues.
  • bisphenols examples include 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter referred to as “bisphenol A”).
  • bisphenol TMC Abbreviated as bisphenol TMC
  • 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane
  • 1,1 -Bis (4-hydroxyphenyl) cyclohexane 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane
  • 1,1-bis (4-hydroxyphenyl) decane 1,3-bis (4- Hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclododecane
  • 4,4'-dihydroxydiph Vinyl ether 4,4'-dithio-diphenol, 4,4'-dihydroxy-3,3'-dichloro-diphenyl ether, 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, and the like.
  • bisphenol A and bisphenol TMC are preferable from the viewpoint of versatility. These may be used alone or in combination of two
  • Polycarbonate resin (B1) can be produced by a known method. For example, a method of reacting bisphenols and phosgene or reacting bisphenols and diphenyl carbonate can be mentioned.
  • the intrinsic viscosity of the polycarbonate resin (B1) is preferably in the range of 0.35 to 0.64.
  • the intrinsic viscosity of the polycarbonate resin (B1) is less than 0.35, the impact strength of the obtained molded product may be insufficient.
  • the intrinsic viscosity exceeds 0.64, the melt viscosity of the resin composition becomes high, and kneading extrusion and injection molding may be difficult.
  • the polyarylate resin (B2) will be described.
  • the polyarylate resin (B2) is a resin composed of an aromatic dicarboxylic acid residue and a bisphenol residue.
  • Bisphenols include bisphenol A, bisphenol TMC, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, , 2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl Examples include ketones, 4,4'-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like. These may be used alone or in combination of two or more. Among these, the combined use of bisphenol A and bisphenol TMC is preferable.
  • aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-dicarboxyphenyl, and the like.
  • terephthalic acid and isophthalic acid are preferable from the viewpoint of melt processability and mechanical properties, and the combined use of both is more preferable.
  • the molar ratio of the two is not particularly limited, but is preferably in the range of 90/10 to 10/90, more preferably in the range of 70/30 to 30/70.
  • 50/50 is more preferable.
  • the degree of polymerization can be sufficiently increased when interfacial polymerization is performed.
  • the production method of the polyarylate resin (B2) is not particularly limited, and examples thereof include an interfacial polymerization method and a melt polymerization method.
  • the intrinsic viscosity of the polyarylate resin (B2) is preferably 0.35 to 0.65.
  • the intrinsic viscosity of the polyarylate resin (B2) is less than 0.35, the impact strength of the obtained molded product may be insufficient.
  • the intrinsic viscosity exceeds 0.65, the melt viscosity becomes high and injection molding may be difficult.
  • the resin (B3) containing both the polycarbonate resin (B1) and the polyarylate resin (B2) will be described.
  • the resin (B3) containing both the polycarbonate resin (B1) and the polyarylate resin (B2) a resin obtained by mixing the polycarbonate resin (B1) and the polyarylate resin (B2), the polycarbonate resin (B1), and the polyarylate resin It contains a resin copolymerized with (B2).
  • the resin obtained by mixing the polycarbonate resin (B1) and the polyarylate resin (B2) may be a simple blend of chips or powders of the polycarbonate resin (B1) and the polyarylate resin (B2).
  • a mixed resin prepared by melt-kneading the polycarbonate resin (B1) and the polyarylate resin (B2) is preferable.
  • the content ratio [(B1) / (B2)] of the polycarbonate resin (B1) and the polyarylate resin (B2) is preferably in the range of 70/30 to 30/70 (mass ratio) from the viewpoint of heat resistance and fluidity. .
  • the intrinsic viscosity of the resin (B3) containing both is preferably 0.55 or less from the viewpoint of compatibility, mechanical properties and heat resistance, and preferably 0.35 or more from the viewpoint of impact strength.
  • the content of the amorphous thermoplastic resin (B) in the composition (X) needs to be 30 to 60% by mass, and preferably 35 to 50% by mass.
  • the content of the amorphous thermoplastic resin (B) is less than 30% by mass, the composition (X) is inferior in impact resistance and flame retardancy.
  • the content of the amorphous thermoplastic resin (B) exceeds 60% by mass, the ratio of the polylactic acid (A) decreases, so that the environmental advantage is reduced.
  • the acrylic compatibilizer (C) will be described.
  • the compatibility between the polylactic acid (A) and the amorphous thermoplastic resin (B) is remarkably improved by containing the acrylic compatibilizing agent (C). And by improving compatibility, the impact resistance, strength, etc. of the composition (X) are improved. Furthermore, by improving the compatibility, the flame retardant performance of the amorphous thermoplastic resin (B) having a higher flame retardant performance than the polylactic acid (A) is exhibited to the maximum. For this reason, the flame retardancy of the composition (X) is greatly improved in comparison with the case of using a compatibilizer that is not an acrylic compatibilizer, in combination with the effect of improving the flame retardancy by adding a specific flame retardant. Improve.
  • Acrylic compatibilizers (C) include (meth) acrylic copolymers, copolymers of styrene monomers and (meth) acrylic monomers, rubber-reinforced acrylic compounds, core-shell acrylic compounds, acrylic olefins Examples thereof include acrylic compounds having an epoxy group. Among them, an acrylic compound having an epoxy group is preferable because compatibility can be remarkably improved.
  • the (meth) acrylic copolymer is obtained by polymerizing a (meth) acrylic monomer alone or by copolymerizing two or more (meth) acrylic monomers.
  • alkyl groups including cycloalkyl groups
  • alkyl groups such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and isobornyl methacrylate have 1 carbon atom.
  • the copolymer of a styrene monomer and a (meth) acrylic monomer is obtained by copolymerizing a styrene monomer and a monomer constituting the (meth) acrylic copolymer.
  • Styrene monomers include styrene, ⁇ -methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, vinyl naphthalene, methoxy styrene, Examples thereof include styrene derivatives of monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene. Of these, styrene, ⁇ -methylstyrene and the like are preferable. These may be used
  • the rubber-reinforced acrylic compound is obtained by copolymerizing a (meth) acrylic monomer in the presence of a rubbery polymer, or by copolymerizing two or more kinds of monomers.
  • rubber-like polymers include polybutadiene, polyisoprene, butadiene / styrene copolymers, isoprene / styrene copolymers, butadiene / acrylonitrile copolymers, butadiene / isoprene / styrene copolymers, diene rubbers such as polychloroprene, Ethylene / propylene copolymers, ethylene / propylene / nonconjugated diene copolymers, ethylene / propylene rubbers such as ethylene / butene / nonconjugated diene copolymers, acrylic rubbers such as polybutyl acrylate, polyorganosiloxane rubber
  • the core-shell type acrylic compound is composed of a layer having a rubber layer as an inner layer and a (meth) acrylic resin as an outer layer.
  • the core (inner layer) is composed of rubber obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component or an ethylene propylene component, and the shell (outer layer)
  • the thing comprised from a methyl methacrylate polymer etc. is mentioned.
  • Examples of commercially available products include METABRENE manufactured by Mitsubishi Rayon, Kaneace manufactured by Kaneka Chemical Co., Ltd., Paraloid manufactured by Kureha Chemical Co., Ltd., Acryloid manufactured by Rohm and Haas Co., Ltd., Staphyloid manufactured by Takeda Pharmaceutical Co., Ltd., and Parapet SA manufactured by Kuraray Co., Ltd. These may be used alone or in combination of two or more.
  • the acrylic olefin compound is a modified olefin compound obtained by graft copolymerization of a (meth) acrylic acid ester polymer.
  • a (meth) acrylic acid ester polymer As a commercial item, Nippon Oil & Fats Modiper etc. are mentioned.
  • An acrylic compound having an epoxy group is a compound having at least one epoxy group and one acrylic group in the molecule.
  • copolymers of (meth) acrylic acid ester monomers having an epoxy group copolymers of (meth) acrylic acid ester monomers having an epoxy group and (meth) acrylic acid ester monomers, (meth) having an epoxy group A copolymer of an acrylate monomer and a styrene monomer, a compound obtained by graft copolymerization of a (meth) acrylate polymer having an epoxy group to a styrene copolymer, and a (meth) acrylate polymer is ethylene / glycidyl A compound copolymerized with a methacrylate copolymer, or a core (inner layer) composed of a rubber obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a
  • the shell has an epoxy group Those such as core-shell structure composed of methyl methacrylate copolymer, and the like.
  • Examples of commercially available products include ARUFON UG-4000 series manufactured by Toagosei Co., Ltd., RESEDA manufactured by Toagosei Co., Ltd., Modiper A4200 manufactured by Nippon Oil & Fats Co., Ltd., and Metabrene S-2200 manufactured by Mitsubishi Rayon Co., Ltd.
  • the content of the acrylic compatibilizer (C) in the composition (X) needs to be 0.5 to 20% by mass, and preferably 3 to 10% by mass.
  • the content of the acrylic compatibilizer (C) is less than 0.5% by mass, the polylactic acid (A) and the amorphous thermoplastic resin (B) cannot be sufficiently compatibilized. And it becomes difficult to produce the effect which arises by making it compatibilize, ie, an impact resistance, intensity
  • content exceeds 20 mass% the problem that the heat resistance and flame retardance of composition (X) fall will arise.
  • the flame retardant (D) will be described.
  • the combustion phenomenon of a polymer material is continued by generating combustion gas by combustion and further burning the combustion gas.
  • a flame retardant it is preferable to select a flame retardant according to the resin.
  • phosphate ester flame retardant (D-1) for amorphous thermoplastic resin (B) Each is particularly effective as a flame retardant.
  • the flame retardance of the resulting composition (X) can be dramatically improved.
  • D-1 and D-2 a phosphate ester flame retardant (D-1) and a phosphinic acid metal salt flame retardant (D-2) in combination
  • D the flame retardant
  • a composition containing specific amounts of polylactic acid (A), amorphous thermoplastic resin (B), and acrylic compatibilizer (C) as described above, these two types of flame retardants are used in a specific ratio.
  • the flame retardancy can be dramatically improved. Therefore, the composition (X) of the present invention can achieve flame retardancy at the V-1 level or V-0 level without adding other additives such as a fluorine-based compound.
  • Examples of the phosphate ester flame retardant (D-1) include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl 2,6-xylenyl phosphate
  • Examples include phosphoric acid esters, condensed phosphoric acid esters, and aromatic condensed phosphoric acid esters. Of these, condensed phosphates are preferable, and aromatic condensed phosphates are more preferable.
  • phosphate ester flame retardant examples include TMP, TEP, TPP, TCP, TXP, CDP, PX-110, etc. manufactured by Daihachi Chemical Industry Co., Ltd.
  • phosphate esters examples include PX-200, PX-201, PX-202, CR-733S, CR-741, and CR-747 manufactured by Daihachi Chemical Co., Ltd.
  • Examples of the phosphinic acid metal salt flame retardant (D-2) include calcium phosphinate, magnesium phosphinate, zinc phosphinate, aluminum phosphinate, and aluminum phosphinate is preferable.
  • Commercially available phosphinic acid metal salts include Clariant's OP series (OP930, OP935, OP1230, OP1312, OP1240, etc.).
  • the phosphinic acid metal salt-based flame retardant (D-2) has improved flame retardancy as the average particle size is smaller.
  • the average particle diameter of the phosphinic acid metal salt flame retardant (D-2) is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, and further preferably 2 to 5 ⁇ m.
  • the average particle diameter of the phosphinic acid metal salt is measured using a laser diffraction / scattering particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.).
  • the content of the flame retardant (D) in the composition (X) needs to be 5 to 30% by mass, and preferably 10 to 25% by mass.
  • the content of the flame retardant (D) in the present invention means the total amount of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2).
  • the content of the flame retardant (D) is less than 5% by mass, sufficient flame retardancy cannot be imparted.
  • content of a flame retardant (D) exceeds 30 mass%, the impact resistance and heat resistance of the composition (X) obtained will fall.
  • the mass ratio of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) added to the composition (X) [(D-1) / (D-2) ] Needs to be 10/90 to 50/50, more preferably 20/80 to 40/60. That is, by using both of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) and using a specific mass ratio, the resulting composition (X) has difficulty. The flammability is dramatically improved. And it can suppress that the heat resistance of composition (X) falls by adding a flame retardant.
  • composition (X) of the present invention it is preferable to further contain an aromatic carbodiimide compound (E). Since polylactic acid (A) has high hygroscopicity and is easily hydrolyzed, the composition (X) containing polylactic acid (A) tends to have low heat and moisture resistance. However, by containing the aromatic carbodiimide compound (E), the heat and humidity resistance can be improved without reducing the flame retardancy of the composition (X), and the versatility and practicality of the composition (X). Can be increased. In addition, when an aliphatic or alicyclic carbodiimide compound is contained as the carbodiimide compound, the heat and humidity resistance can be improved, but the flame retardancy is lowered, which is not preferable.
  • an aromatic carbodiimide compound (E) Since polylactic acid (A) has high hygroscopicity and is easily hydrolyzed, the composition (X) containing polylactic acid (A) tends to have low heat and moisture resistance. However, by containing the aromatic carbodiimide compound
  • the aromatic carbodiimide compound (E) refers to a compound produced by a reaction between a compound having a carbodiimide group represented by (—N ⁇ C ⁇ N—) and an aromatic compound.
  • a compound having one carbodiimide group in the molecule is referred to as an aromatic monocarbodiimide compound (E-1), and a compound having two or more carbodiimide groups in the molecule is referred to as an aromatic polyvalent carbodiimide compound (E-2).
  • an aromatic monocarbodiimide (E-1) and an aromatic polyvalent carbodiimide (E-2) in combination as the aromatic carbodiimide compound (E).
  • the wet heat resistance of the composition (X) obtained can be improved compared with the case where each is used independently. The reason is not clear, but can be estimated as follows.
  • the aromatic monocarbodiimide compound (E-1) has a low molecular weight and is easy to move, so that it has excellent dispersibility and quickly reacts with the carboxylic acid end of the polylactic acid molecule, thus blocking the end of the polylactic acid molecule and suppressing hydrolysis.
  • the aromatic polyvalent carbodiimide compound (E-2) reacts with a carboxylic acid terminal newly generated by hydrolysis of polylactic acid to increase the molecular weight by chain extension, and suppresses a decrease in molecular weight. It is presumed that the two effects are combined to drastically improve the heat and humidity resistance of the composition (X).
  • the mass ratio [(E-1) / (E-2)] of the aromatic monocarbodiimide compound (E-1) and the aromatic polyvalent carbodiimide compound (E-2) is in the range of 10/90 to 90/10. Preferably, it is more preferably in the range of 30/70 to 70/30. By making the mass ratio of the aromatic monocarbodiimide and the aromatic polyvalent carbodiimide within this range, extremely excellent moisture and heat resistance can be obtained.
  • aromatic monocarbodiimide compound examples include N, N′-di-p-chlorophenylcarbodiimide, N, N′-di-o-chlorophenylcarbodiimide, N, N′-di-3,4-dichlorophenylcarbodiimide, N, N'-di-2,5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-di-p-chlorophenylcarbodiimide, Ethylene-bis-diphenylcarbodiimide, N, N'-diphenylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide
  • Aromatic polyvalent carbodiimide compounds include poly (4,4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), and poly (p-phenylene).
  • Carbodiimide poly (m-phenylenecarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (triethylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), poly (1,3,5-triisopropylbenzene) carbodiimide, poly (1,5-diisopropylbenzene) carbodiimide, poly (4,4'-methylenebiscyclohexylcarbodiimide).
  • poly (4,4′-methylenebiscyclohexylcarbodiimide), poly (1,3,5-triisopropylbenzene) carbodiimide, and poly (1,5-diisopropylbenzene) carbodiimide are preferable.
  • the content of the aromatic carbodiimide compound (E) in the composition (X) is preferably 0.1 to 5% by mass, and more preferably 0.5 to 4% by mass.
  • content of the aromatic carbodiimide compound (E) is less than 0.1% by mass, the moisture and heat resistance is hardly improved. On the other hand, if the content exceeds 5% by mass, the heat resistance may decrease, which is not preferable.
  • content in a composition (X) shall be the total amount of all the aromatic carbodiimide compounds.
  • the composition (X) of the present invention can be obtained by adding V-1 or V-0 without adding a fluorine-based compound which is essential for improving flame retardancy in Patent Document 1 described in the Background Art section. A level of flame retardancy can be achieved.
  • the composition (X) of the present invention preferably has a fluorine atom content of 0.1 ppm or less. When the content of fluorine atoms exceeds 0.1 ppm, there is a problem of generation of harmful gases during molding or incineration, which is not preferable.
  • the composition (X) of the present invention may contain a biodegradable resin other than polylactic acid (A) as long as the effect is not impaired.
  • biodegradable resins include, for example, poly (ethylene succinate), poly (butylene succinate), poly (butylene succinate-co-butylene adipate) and other aliphatic polyesters composed of diol and dicarboxylic acid, polyglycol Acid, poly (3-hydroxybutyric acid), poly (3-hydroxyvaleric acid), poly (3-hydroxycaproic acid) and other polyhydroxycarboxylic acids, poly ( ⁇ -caprolactone) and poly ( ⁇ -valerolactone) Poly ( ⁇ -hydroxyalkanoate), poly (butylene succinate-co-butylene terephthalate), poly (butylene adipate-co-butylene terephthalate), polyester amide, polyester And polysaccharides such as carbonate and starch . These may be used alone or in combination of two or more.
  • the heat stabilizer, the antioxidant, the weathering agent, the light-proofing agent, the pigment, the plasticizer, the lubricant, the mold release agent, and the antistatic are within the range not greatly impairing the characteristics.
  • An agent, a filler, a crystal nucleating agent and the like may be contained.
  • heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, vitamin E, and the like.
  • filler for the purpose of improving mechanical strength and heat resistance, it is preferable to use a fibrous reinforcing material such as glass fiber, metal fiber, or carbon fiber, and it is preferable to use glass fiber or the like.
  • fillers other than fibrous reinforcement talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass Balloon, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite and other inorganic fillers, starch, cellulose fine particles, wood powder, okara, fir Organic fillers such as naturally occurring polymers such as shells and bras.
  • composition (X) of the present invention As a method for producing the composition (X) of the present invention, there is a method in which polylactic acid (A), amorphous thermoplastic resin (B), acrylic compatibilizer (C), and flame retardant (D) are melt-kneaded. Can be mentioned. Any of the method of mixing these simultaneously and the method of mixing in order may be sufficient. Even when the aromatic carbodiimide compound (E) is contained, it may be added simultaneously with the polylactic acid (A), the amorphous thermoplastic resin (B), the acrylic compatibilizer (C), and the flame retardant (D). The polylactic acid (A), the amorphous thermoplastic resin (B), the acrylic compatibilizing agent (C), and the flame retardant (D) are first melt-kneaded and then added and kneaded later. Good.
  • the composition (X) of the present invention can be formed into various molded bodies by a molding method such as injection molding, blow molding, extrusion molding, inflation molding, and vacuum molding, pressure molding, and vacuum / pressure molding after sheet processing. .
  • the composition (X) of the present invention is particularly suitable for an injection molding method, and can be used for gas injection molding, injection press molding and the like in addition to general injection molding.
  • the injection molding conditions are appropriately selected according to the type and content ratio of the thermoplastic resin, but the cylinder temperature is preferably 180 to 260 ° C, more preferably 190 to 250 ° C.
  • the mold temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower in consideration of operability.
  • the mold temperature is preferably relatively high, and 80 to 120 ° C. is particularly preferable. If the molding temperature (mold temperature) is too low, a part of the molded body is lost, and a problem of forming an incompletely molded body tends to occur. On the other hand, when the molding temperature is too high, the composition (X) is likely to be decomposed, and there may be a problem that the strength of the resulting molded product is reduced or colored.
  • the molded product of the present invention is formed by molding the composition (X) of the present invention. And what was made into various molded objects by shaping
  • the molded body of the present invention include injection molded products, extrusion molded products, blow molded products, films, fibers, and sheets.
  • an injection molded product can be thinned. Since these molded products have excellent performance in flame retardancy, heat resistance, and impact resistance, they can be used in various applications such as electrical / electronic parts, machine parts, optical equipment, building members, automobile parts, and daily necessities. In particular, it can be suitably used as a casing for electronic devices (cases for notebook computers, projectors, copying machines, printers, etc.).
  • Evaluation item (1) MFR According to JIS standard K-7210 (Test condition 4), the measurement was performed at 190 ° C. and a load of 21.2 N.
  • (3) Intrinsic viscosity The intrinsic viscosity was measured under the conditions of a concentration of 1 g / dl and a temperature of 25 ° C. using 1,1,2,2-tetrachloroethane as a measurement solvent.
  • Heat resistance heat distortion temperature
  • ISO standards 75-1 and 2 the heat distortion temperature was measured with a load of 0.45 MPa using the obtained test piece.
  • Impact strength Charpy impact strength
  • 179-1eA Charpy impact strength was measured using the obtained test piece (with a V-shaped notch).
  • Bending strength According to ISO standard 178, bending strength was measured at a deformation rate of 1 mm / min using the obtained test piece.
  • Flame Retardancy According to the UL94 vertical combustion test method, the obtained test piece (thickness, approximately 1.6 mm) was used to perform a combustion test to evaluate flame retardancy.
  • the flame retardancy is preferably V-1 or V-0 for practical use.
  • thermoplastic resin having bisphenol group> (B-1) Polycarbonate resin / PC 200-13 manufactured by Sumitomo Dow, intrinsic viscosity 0.49 (B-2) Polyarylate resin, PAR Unita, Powder L, intrinsic viscosity 0.54
  • ⁇ (C) Acrylic compatibilizer> (Acrylic compatibilizer having an epoxy group) ⁇ EA-1 Metablene S-2200 manufactured by Mitsubishi Rayon Co., Ltd. ⁇ EA-2 ARUFON UG-40 manufactured by Toa Gosei Co., Ltd. ⁇ EA-3 Modiper A4200 manufactured by NOF Corporation (Acrylic compatibilizer without epoxy group) ⁇ A-1 Metablene C-223A manufactured by Mitsubishi Rayon Co., Ltd. ⁇ A-2 Acrypet VH-001 (polymethyl methacrylate resin) manufactured by Mitsubishi Rayon Co., Ltd. ⁇ Styrene compatibilizer> ⁇ S-TPE Tough Tech H1041 (Styrene-ethylene / butylene-styrene block copolymer) manufactured by Asahi Kasei Chemicals
  • Example 1 Using a twin screw extruder (TEM-37BS manufactured by Toshiba Machine Co., Ltd.), 30 parts by mass of PLA-1 as polylactic acid (A) and 41 parts by mass of PC as amorphous thermoplastic resin (B) are used as the top feeder. 7 parts by weight of EA-1 as an acrylic compatibilizer (C), 5 parts by weight of FR-1 as a phosphate ester flame retardant (D-1), and a phosphinic acid metal salt flame retardant (D-2) ) 15 parts by weight of FR-4, 1 part by weight of HMCD as aromatic monocarbodiimide (E-1), and 1 part by weight of HPCD as aromatic polycarbodiimide (E-2), and melt-kneaded at 230 ° C.
  • EA-1 an acrylic compatibilizer
  • D-1 phosphate ester flame retardant
  • D-2 a phosphinic acid metal salt flame retardant
  • composition (X) was dried with a hot air dryer at 80 ° C. for 5 hours, and then molded with an injection molding machine (IS-80G type manufactured by Toshiba Machine), which was suitable for various performance evaluations. A size specimen was obtained. When obtaining any of the test pieces, it is melted at a cylinder set temperature (injection temperature) of 220 ° C., and filled in a mold of 80 ° C. (mold temperature) at an injection pressure of 100 MPa and an injection time of 15 seconds, for 30 seconds. After holding, it was taken out.
  • injection temperature injection temperature
  • mold temperature 80 ° C.
  • Examples 2 to 41, Comparative Examples 1 to 25 Various test pieces were prepared in the same manner as in Example 1 except that the types and amounts of the components constituting the composition (X) and the production conditions (melt kneading temperature, injection temperature) were changed as shown in Tables 1 to 3. Got.
  • Tables 1 to 3 show the compositions and characteristic values of the compositions (X) obtained in the examples and comparative examples.
  • compositions (X) obtained in Examples 1 to 41 are excellent in flame retardancy, impact resistance, and heat resistance, and use polylactic acid derived from natural products. The dependence on the environment was low and the global environment was taken into consideration.
  • polylactic acid (A) contains a specific D form. Since it was a large amount or a crosslinked structure was introduced, it was excellent in heat resistance (heat deformation temperature) and flame retardancy.
  • the compositions (X) obtained in Examples 18 to 19 and 37 to 38 are excellent in flame retardancy because the phosphinic acid metal salt flame retardant (D-2) has a small average particle size. It became a thing.
  • compositions (X) obtained in Examples 1 to 24 and 27 to 39 contained the aromatic carbodiimide compound (E), they were excellent in heat and heat resistance. Among them, since the compositions (X) obtained in Examples 1 to 23 and 27 to 39 used both the aromatic monocarbodiimide (E-1) and the aromatic polyvalent carbodiimide (E-2), was significantly better.
  • the composition (X) obtained in Comparative Examples 1 to 2 and 24 has a polylactic acid (A) content larger than the amount specified in the present invention, and an amorphous thermoplastic resin ( Since the content of B) was less than the amount specified in the present invention, the effects of the amorphous thermoplastic resin (B) were not sufficiently exhibited, and the flame retardancy, heat resistance and impact resistance were all inferior. It was.
  • the content of the amorphous thermoplastic resin (B) was less than the amount specified in the present invention, so the effect of the amorphous thermoplastic resin (B). Was not fully exhibited, and it was inferior to all of flame retardancy, heat resistance and impact resistance.
  • composition (X) obtained in Comparative Examples 4 and 5 had an acrylic compatibilizer (C) content less than the amount specified in the present invention, polylactic acid (A) and an amorphous thermoplastic resin (B) was not sufficiently compatible, and was inferior in impact resistance, heat resistance and flame retardancy, and also had low bending strength.
  • composition (X) obtained in Comparative Example 6 had a content of the acrylic compatibilizer (C) that was greater than the amount specified in the present invention, the heat resistance, bending strength, and flame retardancy were reduced.
  • composition (X) obtained in Comparative Examples 7 and 8 used a styrene type as a compatibilizing agent, the effect of the acrylic compatibilizing agent (C) was not recognized, and the heat resistance, It was inferior in impact and flame retardancy.
  • the mass ratio of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) is within the range specified by the present invention. Is not satisfied, so the flame retardancy is poor. Furthermore, when the mass ratio of the phosphate ester flame retardant (D-1) was too high, the heat resistance was also lowered.
  • compositions (X) obtained in Comparative Examples 13 and 14 contained only the phosphate ester flame retardant (D-1), they were inferior in flame retardancy.
  • the compositions (X) obtained in Comparative Examples 15 to 16 and 21 were inferior in flame retardancy because they were a combination of the phosphate ester flame retardant (D-1) and the phosphorus flame retardant. It was.
  • the compositions (X) obtained in Comparative Examples 17 to 18 and 22 were a combination of the phosphinic acid metal salt flame retardant (D-2) and the phosphorus flame retardant, they were inferior in flame retardancy. there were.
  • the compositions (X) obtained in Comparative Examples 19 to 20 and 23 contained only the phosphorus flame retardant, they were inferior in flame retardancy.

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Abstract

L'invention porte sur une composition de résine thermoplastique qui est caractérisée en ce qu'elle comprend (A) de l'acide polylactique, (B) une résine thermoplastique non cristalline qui possède des groupes bisphénol, (C) un agent de compatibilisation à base acrylique, et (D) un retardateur de flamme, en des quantités respectivement de 25 à 60 % en masse, de 30 à 60 % en masse, de 0,5 à 20 % en masse et de 5 à 30 % en masse, ledit retardateur de flamme (D) comprenant (D-1) un retardateur de flamme de type ester de l'acide phosphorique, et (D-2) un retardateur de flamme de type phosphinate métallique, selon un rapport en masse [(D-1)/(D-2)] de 10/90 à 50/50.
PCT/JP2011/062432 2010-06-04 2011-05-31 Composition de résine thermoplastique et produits moulés en cette composition WO2011152371A1 (fr)

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