WO2011155119A1 - Composition de résine d'acide polylactique et article moulé à partir de celle-ci - Google Patents

Composition de résine d'acide polylactique et article moulé à partir de celle-ci Download PDF

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WO2011155119A1
WO2011155119A1 PCT/JP2011/002599 JP2011002599W WO2011155119A1 WO 2011155119 A1 WO2011155119 A1 WO 2011155119A1 JP 2011002599 W JP2011002599 W JP 2011002599W WO 2011155119 A1 WO2011155119 A1 WO 2011155119A1
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Prior art keywords
polylactic acid
acid resin
mass
resin composition
compound
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PCT/JP2011/002599
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English (en)
Japanese (ja)
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幸浩 木内
直樹 森下
正年 位地
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日本電気株式会社
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Priority to JP2012519214A priority Critical patent/JP5796577B2/ja
Publication of WO2011155119A1 publication Critical patent/WO2011155119A1/fr

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    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals

Definitions

  • the present invention relates to a polylactic acid resin composition and a molded body thereof.
  • Polyhydroxycarboxylic acid including polylactic acid resin has relatively excellent moldability, toughness, rigidity and the like.
  • polylactic acid resin can be synthesized from natural raw materials such as corn, and has excellent molding processability, biodegradability, etc., and therefore is being developed as an environmentally friendly resin in various fields.
  • the polylactic acid resin has excellent physical properties, but is easily combusted. Therefore, the polylactic acid resin needs to be made flame retardant in order to be used for an exterior material for an electric / electronic device that requires high flame retardancy.
  • Patent Document 1 discloses a resin composition in which biodegradable polyester, that is, polylactic acid and polybutylene succinate adipate lactide are mixed with at least a polyfunctional monomer, crosslinked with radiation, and various flame retardants are blended. ing.
  • biodegradable polyester that is, polylactic acid and polybutylene succinate adipate lactide
  • at least a polyfunctional monomer crosslinked with radiation
  • various flame retardants are blended.
  • high flame retardancy is achieved by adding 11 parts by mass or more of a phosphate ester to 100 parts by mass of the total value of the polylactic acid resin.
  • Patent Document 2 discloses a resin composition in which an aromatic polyester is blended with an aliphatic polyester as a flame retardant.
  • this resin composition as described in Examples 19 and 20, sufficient flame retardancy is obtained by adding 15 parts by mass of the aromatic phosphate to 100 parts by mass of the aliphatic polyester. ing.
  • Patent Document 3 discloses a polylactic acid resin containing a polylactic acid resin, a metal hydrate having an alkali metal content of 0.2% by mass or less, and a phosphazene derivative that is one of phosphorus compounds. A composition is disclosed.
  • the present invention provides a polylactic acid resin composition excellent in the balance between flame retardancy and bleed resistance, and a molded product thereof.
  • a molded product obtained from the polylactic acid resin composition is provided.
  • a polylactic acid resin composition having excellent balance between flame retardancy and bleed resistance and a molded product thereof can be obtained.
  • the present inventors diligently studied a method for imparting high flame retardancy and bleed resistance to a polylactic acid resin composition mainly composed of polylactic acid resin (A).
  • polylactic acid resin (A), metal hydroxide (B), phosphorus compound (C), and volatile compound (D) other than phosphorus compound (C) are used in combination, and phosphorus compound (C) is contained.
  • phosphorus compound (C) is contained.
  • the polylactic acid resin composition of the present invention comprises a polylactic acid resin (A) and volatile compounds (D) other than the metal hydroxide (B), the phosphorus compound (C) and the phosphorus compound (C) as three flame retardants. )including.
  • the polylactic acid resin (A) according to the present invention is, for example, a resin having a lactic acid skeleton.
  • the polylactic acid resin (A) for example, an extract of polylactic acid resin obtained from a biomass raw material or a derivative or modified product thereof, or a monomer or oligomer of a lactic acid compound obtained from a biomass raw material, or a derivative thereof or
  • segments of polylactic acid resin synthesized from materials other than biomass materials can be mentioned.
  • the polylactic acid resin (A) according to the present invention is represented, for example, by the following general formula (1).
  • R 17 represents, for example, an alkyl group having 18 or less carbon atoms
  • a and c are integers greater than 0, and b ′ represents an integer of 0 or more.
  • a is preferably an integer of 500 or more and 13000 or less, more preferably an integer of 1500 or more and 4000 or less.
  • b ′ is preferably an integer of 5000 or less including 0, and
  • c is preferably an integer of 1 to 50.
  • the repeating units represented by the number of repeating units a and b ′ are alternately repeated even when the same type of repeating units are continuously connected. May be.
  • polylactic acid resin (A) represented by the general formula (1) examples include L-lactic acid, D-lactic acid, polymers of these derivatives, and copolymers containing these as main components.
  • the copolymer examples include L-lactic acid, D-lactic acid, and derivatives thereof, for example, glycolic acid, polyhydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate, polybutylene adipate terephthalate, polybutylene succinate terephthalate. And copolymers obtained from one or more of polyhydroxyalkanoates. Of these, from the viewpoint of saving petroleum resources, those derived from plants are preferable.
  • poly (L-lactic acid), poly (D-lactic acid) and their co-products are preferred.
  • Polymers are particularly preferred.
  • the melting point of polylactic acid mainly composed of poly (L-lactic acid) varies depending on the ratio of the D-lactic acid component, but considering the mechanical properties and heat resistance of the molded product, the melting point is 160 ° C. or higher. What has is preferable.
  • the weight average molecular weight of the polylactic acid resin (A) is preferably 30,000 to 1,000,000, more preferably 100,000 to 300,000.
  • the weight average molecular weight of the polylactic acid resin (A) can be measured by GPC.
  • the content of the polylactic acid resin (A) is preferably 20 parts by mass or more and 60 parts by mass or less, more preferably 25 parts by mass with respect to 100 parts by mass of the total value of the polylactic acid resin composition of the present invention. Part to 50 parts by weight.
  • the polylactic acid resin (A) reacts with the polylactic acid resin such as a carbodiimide compound, a compound having an epoxy group, a compound having an amino group, a compound having an aliphatic unsaturated double bond, etc. You may use what was bridge
  • the compound having an epoxy group, the compound having an amino group, and the compound having an aliphatic unsaturated double bond include siloxane compounds having these functional groups.
  • Examples of the metal hydroxide (B) according to the present invention include aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate hydrate, hydrated gypsum, calcium hydroxide, zinc borate, barium metaborate, and boron.
  • Examples include sand and kaolinite.
  • the mixture of at least 1 sort (s) or 2 or more types chosen from aluminum hydroxide, magnesium hydroxide, and calcium hydroxide is preferable, and aluminum hydroxide is more preferable.
  • a metal hydroxide (B) is an alkali metal substance and an alkali with respect to the whole metal hydroxide (B) from a viewpoint of suppressing hydrolysis of a polylactic acid resin (A) or a phosphorus compound (C).
  • the content of the earth metal is preferably 0.2% by mass or less.
  • the alkali metal substances and alkaline earth metals contained in the metal hydroxide include oxides of alkali metals such as lithium, sodium and potassium, alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium, or Examples include salts such as chlorides.
  • the content of the alkali metal substance can be measured by atomic absorption spectrometry or ICP emission spectroscopy.
  • the metal hydroxide (B) is preferably composed of granules having an average particle size of 10 ⁇ m or less, and more preferably composed of granules having an average particle size of 0.1 ⁇ m to 5 ⁇ m.
  • the average particle diameter of the metal hydroxide can be determined by measuring the volume-based median diameter by a diffraction / scattering method.
  • a laser diffraction particle size distribution measuring device SALD-3100 (trade name) manufactured by Shimadzu Corporation can be used.
  • the metal hydroxide (B) can be used, for example, in a state of being surface-treated with a silane coupling agent.
  • the method for surface-treating the metal hydroxide with a silane coupling agent is not particularly limited.
  • a solution obtained by dissolving a silane coupling agent in a solvent such as acetone, ethyl acetate, toluene, or the like is used. Examples include a method of removing the solvent by spraying or coating on the surface and then drying.
  • Flame retardance can be increased by adding metal hydroxide (B).
  • This flame retardant improvement effect is considered to be due to the endothermic effect during the thermal decomposition of the metal hydroxide (B), the endothermic effect caused by the water generated during the thermal decomposition, and the diluting effect of the combustible gas.
  • the addition amount of the metal hydroxide is such that the compounding amount of the metal hydroxide (B) that does not inhibit the effect of diluting the flammable gas by the phosphorus compound (C) and volatile compound (D) described later is the polylactic acid resin (A)
  • the total amount of the metal hydroxide (B), the phosphorus compound (C), and the volatile compound (D) can be set in the range of 30 to 150 parts by mass with respect to the total value of 100 parts by mass. From the viewpoint of obtaining a sufficient addition effect of the metal hydroxide (B), the content of the metal hydroxide (B) is 10 parts by mass or more with respect to 100 parts by mass of the total value of the polylactic acid resin (A).
  • 15 parts by mass or more is more preferable, 20 parts by mass or more is more preferable, and from the viewpoint of sufficiently securing the fluidity and mechanical strength of the polylactic acid resin (A), 150 parts by mass or less is more preferable, and 120 parts by mass or less. Is more preferable.
  • a phosphazene derivative and an aromatic phosphate are preferable because they have an excellent flame retardant effect.
  • a phosphazene derivative as a cyclic cyclophosphazene compound, for example, the following general formula (2): (wherein n represents an integer of 3 or more, and R1 and R2 each represents an organic group).
  • n is preferably in the range of 3 to 25, and for example, n is more preferably in the range of 3 to 5.
  • the cyclophosphazene compound can independently have, for example, a substituted or unsubstituted phenoxy group or a substituted or unsubstituted naphthoxy group (for example, ⁇ -naphthoxy) as R1 and R2.
  • Examples of the phosphazene derivative that is one of the phosphorus compounds (C) according to the present invention include, for example, a cyclophosphazene compound having a phenoxy group, a cyclophosphazene compound having a cyanophenoxy group, a cyclophosphazene compound having an aminophenoxy group, substituted or non- Examples thereof include a cyclophosphazene compound having a substituted naphthoxy group and a cyclophosphazene compound having a phenolic hydroxyl group, and one or a mixture of two or more thereof can be used.
  • the phenolic hydroxyl group does not contain a phenolic hydroxyl group because it easily forms a quinone structure that causes coloring when oxidized. That is, the cyclophosphazene compound has a cyclophosphazene compound having a phenoxy group, a cyclophosphazene compound having a cyanophenoxy group, a cyclophosphazene compound having an aminophenoxy group, or a substituted or unsubstituted naphthoxy group from the viewpoint of resistance to discoloration. At least one compound selected from the group consisting of cyclophosphazene compounds is preferred.
  • Such a cyclophosphazene compound is preferably a cyclotriphosphazene, cyclotetraphosphazene or cyclopentaphosphazene having a substituted or unsubstituted phenoxy group or a substituted or unsubstituted naphthoxy group, and a cyclophosphazene compound having a substituted or unsubstituted phenoxy group.
  • Triphosphazene can be preferably used.
  • hexaphenoxycyclotriphosphazene (the phenoxy group may have a substituent) is mentioned.
  • Examples of the aromatic phosphate ester that is one of the phosphorus compounds (C) according to the present invention include resorcinol bisdiphenyl phosphate, bisphenol A-bisdiphenyl phosphate, resorcinol-bis-2,6-xylenyl phosphate. Resorcinol-bis-2,6-bisdiphenyl phosphate, biphenol-bisdiphenyl phosphate, 4,4′-bis (diphenylphosphoryl) -1,1′-biphenyl, triphenyl phosphate, torus (isopropylphenyl) phosphate, etc. are preferred . Such phosphorus compounds (C) may be used alone or in combination.
  • the lower limit of the compounding amount of the phosphorus compound (C) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the total value of the polylactic acid resin.
  • the upper limit of the compounding amount of the phosphorus compound (C) is preferably 10 parts by mass or less, more preferably 9 parts by mass or less, further preferably 8 parts by mass or less, and particularly preferably 7 parts by mass or less.
  • Examples of the volatile compound (D) according to the present invention include volatile compounds excluding the phosphorus compound (C) described above.
  • This volatile compound (D) is represented by the following mass reduction index, for example. This mass reduction index indicates that the temperature range in which the mass is reduced by 10% by mass with respect to the mass at 25 ° C. is 300 ° C. or more and 500 ° C. or less.
  • the volatile compound (D) include, for example, melamine cyanurate and phosphaphenanthrene derivatives.
  • the molecular weight of the phosphaphenanthrene derivative is preferably from 30,000 to 15,000.
  • An example of such a high molecular weight phosphaphenanthrene derivative is ME-P8 manufactured by Sanko Co., Ltd.
  • the lower limit of the content of the volatile compound (D) is preferably 6 parts by mass or more, more preferably 7 parts by mass or more, with respect to 100 parts by mass of the total value of the polylactic acid resin (A). More preferably, it is 8 parts by mass or more.
  • the upper limit of the content of the volatile compound (D) is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, with respect to 100 parts by mass of the total value of the polylactic acid resin (A). Yes, more preferably 40 parts by mass or less.
  • the metal hydroxide (B), the phosphorus compound (C), and the volatile compound (D) other than the phosphorus compound (C) are used in combination.
  • the endothermic effect of the metal hydroxide (B) suppresses ignition of the molded body.
  • a non-combustible component is generated in a wide temperature range by the phosphorus compound (C) and the volatile compound (D).
  • the polylactic acid resin composition of the present invention and this molded product can satisfy the performance required for a housing of an electric / electronic device such as a computer, a personal computer and a portable terminal for the first time.
  • an electric / electronic device such as a computer, a personal computer and a portable terminal for the first time.
  • components that can be added to the polylactic acid resin composition of the present invention include hydrolysis inhibitors, fibers, and fluorine-containing resins.
  • a carbodiimide compound is preferable.
  • a carbodiimide compound is a compound having at least one carbodiimide group in the molecule.
  • Such carbodiimides include dicyclohexylcarbodiimide, diisopropylcarbodiimide, diphenylcarbodiimide, bis (methylphenyl) carbodiimide, bis (methoxyphenyl) carbodiimide, bis (nitrophenyl) carbodiimide, bis (dimethylphenyl) carbodiimide, bis (diisopropyl) carbodiimide, Examples thereof include bis (t-butyl) carbodiimide, N-ethyl-N ′-(3-dimethylaminopropyl) carbodiimide, bis (triphenylsilyl) carbodiimide, and N, N′-di-2,6-diisopropylphenylcarbodi
  • carbodiimide compound (polycarbodiimide) having two or more carbodiimide groups examples include aliphatic polycarbodiimides such as poly (4,4′-dicyclohexylmethanecarbodiimide); poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylene) Carbodiimide), poly (m-phenylenecarbodiimide), poly (methylphenylenecarbodiimide), poly (diisopropylphenylenecarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (1,3,5-triisopropylphenylenecarbodiimide), poly ( And aromatic polycarbodiimides such as 1,3,5-triisopropy
  • an aliphatic polycarbodiimide having an alicyclic structure such as a cyclohexane ring is preferable.
  • examples thereof include polycarbodiimides in which the organic linking group R of the above general formula includes at least an alicyclic divalent group such as a cyclohexylene group.
  • poly (4,4′-dicyclohexylmethanecarbodiimide) can be preferably used.
  • Carbodilite LA-1 (trade name) manufactured by Nisshinbo Chemical Co., Ltd. can be used.
  • aromatic polycarbodiimide examples include polycarbodiimide having an aromatic ring structure such as a benzene ring.
  • aromatic polycarbodiimide it is possible to use, as a commercial product, stabaxol P (trade name, poly (1,3,5-triisopropylphenylenecarbodiimide)) or stavaxol P-100 (trade name) manufactured by Rhein Chemie. it can.
  • the compounding amount of the carbodiimide compound is set to 0.1 parts by mass or more with respect to a total value of 100 parts by mass of the polylactic acid resin (A) from the viewpoint of obtaining a sufficient flame retardancy improving effect, and 0.5 parts by mass.
  • the above is preferable, and 1 part by mass or more is more preferable.
  • the amount of the aromatic carbodiimide is preferably 0.1 parts by mass or more, and 0.5 parts by mass with respect to the total carbodiimide compound from the viewpoint of obtaining a sufficient addition effect.
  • the above is more preferable, and 1 part by mass or more is more preferable.
  • the blending ratio (mass ratio) of aliphatic carbodiimide and aromatic carbodiimide can be set, for example, in the range of 1/9 to 9/1, preferably in the range of 3/7 to 7/3, and in the range of 4/6 to 6/4. Can be set to a range.
  • the total value of 100 parts by mass of the polylactic acid resin (A) can be set to 20 parts by mass or less. From the viewpoint of resin moldability, bleed resistance, production cost, etc., 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable.
  • the polylactic acid resin composition of the present invention may contain fibers such as inorganic fibers, organic synthetic fibers, and plant-derived natural fibers.
  • Inorganic fibers are preferable from the viewpoint of heat resistance and the like, and examples of the inorganic fibers include inorganic fibers such as metal fibers, glass fibers, metal silicate fibers, inorganic oxide fibers, and inorganic nitride fibers.
  • a fiber may be used individually by 1 type, and 2 or more types may be mixed and used for it. Two or more kinds of inorganic fibers, organic synthetic fibers and plant-derived natural fibers may be mixed and used, and preferably contain at least inorganic fibers.
  • the fiber may have a circular fiber cross section, but may have a polygonal shape, an indeterminate shape, or an uneven shape. From the viewpoint of increasing the bonding area with the resin, those having irregularities with a high aspect ratio and those having a small fiber diameter are desirable.
  • the fibers can be subjected to a surface treatment in order to increase the affinity with the resin serving as the base material or the entanglement between the fibers.
  • a coupling agent such as silane or titanate, ozone or plasma treatment, or treatment with an alkyl phosphate type surfactant is effective.
  • the treatment method is not particularly limited, and a treatment method that can be generally used for surface modification of the filler can be used.
  • the average fiber length of the fibers (number average fiber length of fibers excluding crushed pieces) is preferably in the range of 0.1 mm to 20 mm, and more preferably in the range of 0.1 mm to 10 mm. Further, it preferably contains fibers having a fiber length of 300 ⁇ m to 20 mm.
  • Resin composition From the viewpoint of sufficiently securing the moldability and mechanical strength of the product, it is preferably 50% by mass or less, more preferably 30% by mass or less, for example, 1% by mass to 10% by mass. Furthermore, polyamide fiber or polyarylate fiber can be used as the organic synthetic fiber.
  • the polylactic acid resin composition of the present invention may contain a fluorine-containing resin.
  • the fluorine-containing resin is preferably a fiber-forming type (one that forms a fibril-like structure), and is a fluorinated polyethylene such as polytetrafluoroethylene or a tetrafluoroethylene copolymer (for example, tetrafluoroethylene / hexafluoropropylene copolymer). Coalesced).
  • the content of the fluorine-containing resin is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, based on the whole polylactic acid resin composition, from the viewpoint of obtaining a sufficient addition effect.
  • it is preferably 5% by mass or less, more preferably 2% by mass or less, based on the whole polylactic acid resin composition.
  • crystal nucleating agents impact resistance improvers, plasticizers, other resins, antioxidants, lubricants, and the like may be added as long as the function of the polylactic acid resin composition of the present invention is not impaired.
  • a crystal nucleating agent may be used in the molding of a molded body in order to further promote crystallization of an amorphous component having a low flow initiation temperature.
  • Crystal nucleating agents themselves become crystal nuclei during molding of the molded body, and act to arrange the resin's constituent molecules in a regular three-dimensional structure, so that the moldability of the molded body, shortening of molding time, mechanical strength The heat resistance can be improved.
  • by promoting crystallization of the amorphous content deformation of the molded body is suppressed even when the mold temperature during molding is high, and mold release after molding is facilitated. The same effect can be obtained even when the mold temperature is higher than the glass transition temperature Tg of the resin.
  • examples of inorganic crystal nucleating agents include talc, calcium carbonate, mica, boron nitride, synthetic silicic acid, silicate, silica, kaolin, carbon black, zinc white, montmorillonite, clay mineral, and basic carbonic acid.
  • Magnesium, quartz powder, glass fiber, glass powder, diatomaceous earth, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, boron nitride and the like can be used.
  • organic crystal nucleating agents include: (1) Organic carboxylic acids: octylic acid, toluic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid , Montanic acid, mellicic acid, benzoic acid, p-tert-butylbenzoic acid, terephthalic acid, terephthalic acid monomethyl ester, isophthalic acid, isophthalic acid monomethyl ester, rosin acid, 12-hydroxystearic acid, cholic acid, etc.
  • Organic carboxylic acids octylic acid, toluic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid , Montanic acid, mellicic acid, benzoic acid, p-tert-butylbenzoic acid, tere
  • sorbitol derivatives such as bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, (8) cholesteryl stearate And cholesterol derivatives such as cholesteryloxysystemaramid, (9) thioglycolic anhydride, p-toluenesulfonic acid, p-toluenesulfonic acid amide and metal salts thereof.
  • a crystal nucleating agent composed of a neutral substance that does not promote polyester hydrolysis is preferable because the polylactic acid resin composition of the present invention can be prevented from being hydrolyzed to lower the molecular weight.
  • an ester or amide compound that is a derivative thereof is preferable to a crystal nucleating agent having a carboxy group, and similarly, a hydroxy group
  • An ester or ether compound which is a derivative thereof is preferable to a crystal nucleating agent having
  • the crystal nucleating agent a layered compound such as talc, which is compatible or finely dispersed with a resin in a high-temperature molten state in injection molding or the like, precipitates or phase-separates in a molding cooling step in a mold, and acts as a crystal nucleus.
  • a layered compound such as talc, which is compatible or finely dispersed with a resin in a high-temperature molten state in injection molding or the like, precipitates or phase-separates in a molding cooling step in a mold, and acts as a crystal nucleus.
  • these crystal nucleating agents an inorganic crystal nucleating agent and an organic crystal nucleating agent may be used in combination, or a plurality of types may be used in combination.
  • the content of the crystal nucleating agent is preferably 0.1 to 20% by mass in the polylactic acid resin composition.
  • ⁇ Flexible components can be used as impact resistance improvers.
  • a polymer block (copolymer) selected from the group consisting of a polyester segment, a polyether segment, and a polyhydroxycarboxylic acid segment, a polylactic acid segment, an aromatic polyester segment, and a polyalkylene ether segment are bonded to each other.
  • a block copolymer comprising a polylactic acid segment and a polycaprolactone segment, a polymer comprising an unsaturated carboxylic acid alkyl ester unit as a main component, polybutylene succinate, polyethylene succinate, polycabrolactone, Aliphatic polyester such as polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexene adipate, polybutylene succinate adipate, polyethylene glycol And its esters, polyglycerin acetate, epoxidized soybean oil, epoxidized linseed oil, epoxidized linseed oil fatty acid butyl, adipic acid aliphatic polyester, acetyl citrate tributyl, acetyl ricinoleate, sucrose fatty acid ester, sorbitan Examples thereof include plasticizers such as fatty acid ester, adipic acid dialkyl ester, and alkylphthal
  • a plasticizer can be used as necessary.
  • the plasticizer those generally used as a plasticizer for polylactic acid resins and ester resins, such as diester compounds consisting only of fatty chains and diester compounds having an aromatic group, can be used. Specific examples include benzyl-2- (2-methoxyethoxy) ethyl adipate and a copolymer of triethylene glycol monomethyl ether and succinic acid.
  • thermoplastic resins for example, polypropylene, polystyrene, ABS, nylon, polyethylene terephthalate, polybutylene terephthalate or polycarbonate, and alloys of these thermoplastic resins can be used. Further, it is preferable to use crystalline thermoplastic resins such as polypropylene, nylon, polyethylene terephthalate, polybutylene terephthalate, alloys with these polylactic acid resins, and the like.
  • thermosetting resins such as curable polyimide, thermosetting polyamide, styrylpyridine resin, nitrile terminal resin, addition curable quinoxaline, addition curable polyquinoxaline resin, and plant materials such as lignin, hemicellulose, and cellulose were used.
  • Thermosetting resins can also be used.
  • the polylactic acid resin composition of the present invention may contain an antioxidant such as a hindered phenol or a phosphite compound, and a lubricant such as a hydrocarbon wax or an anionic surfactant.
  • the content of each of the antioxidant and the lubricant is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total value of the polylactic acid resin (A).
  • the polylactic acid resin composition of the present invention includes an antistatic agent, an antifogging agent, a light stabilizer, an ultraviolet absorber, a pigment, a colorant, an antifungal agent, an antibacterial agent, a foaming agent, a heat stabilizer, if necessary.
  • a weathering agent, a release agent, and a filler can be contained in a range that does not interfere with a desired effect according to the object of the present invention.
  • any method such as injection molding, injection / compression molding, extrusion molding, mold molding and the like can be used. It is preferable to promote crystallization during the manufacturing process or after molding because a molded body excellent in impact resistance and mechanical strength can be obtained.
  • a method for promoting crystallization a method of using the above crystal nucleating agent in the above range can be mentioned.
  • Such a molded body is excellent in flame retardancy and is prevented from being deteriorated by bleeding, and is suitable for various parts such as electric, electronic, and automobiles.
  • Polylactic acid resin (A) Polylactic acid resin 1: Terramac TE-4000N (melting point: 170 ° C.) manufactured by Unitika Ltd.
  • Metal hydroxide 1 HP-350 (average particle size 3 ⁇ m) manufactured by Showa Denko KK
  • Phosphorus compound (C) Table 1 shows the phosphorus compounds used. Any of phosphazene derivatives and aromatic phosphates may be used for the phosphorus compound (C) of the present invention.
  • Phosphorus compound 1 (phosphazene derivative), sps-100 manufactured by Otsuka Chemical Phosphorus compound 2: (aromatic phosphate ester), PX-200 manufactured by Daihachi Chemical Phosphorus compound 3: (aromatic phosphate ester), ADK STAB FP-800
  • Volatile compounds (D) Table 2 shows the volatile compounds used.
  • the volatile compound (D) of the present invention either melamine cyanurate or a high molecular weight phosphaphenanthrene derivative may be used.
  • Volatile compound 3 (phosphaphenanthrene derivative: molecular weight 10,000), Sanko ME-P8
  • Hydrolysis-resistant inhibitor 1 Stabaxol P, aromatic polycarbodiimide, manufactured by Rhein Chemie
  • Hydrolysis-resistant inhibitor 2 Stubbuxol I, bis (dipropylphenyl) carbodiimide, main component, manufactured by Rhein Chemie
  • Fiber Glass fiber 1 03JAFT592, manufactured by Owens Corning Japan Co., Ltd. Fiber length 3mm, fiber diameter 10 ⁇ m ⁇
  • Fluorine-containing resin Fluorine-containing resin 1 Daikin Industries, Ltd. FA-500, PTFE
  • Crystal nucleating agent Crystal nucleating agent 1: Eco-Promote manufactured by Nissan Chemical Co., Ltd., zinc phenylphosphonate Crystal nucleating agent 2: ITOWAX J-530, manufactured by Ito Oil Co., Ltd., N, N'-ethylene-bis-12-hydroxy Stearylamide
  • Plasticizer Plasticizer 1 Daihachi Chemical Co., Ltd. DAIFATTY-101, benzyl-2- (2-methoxyethoxy) ethyl adipate
  • Combustion test was performed as a set of five test pieces. Each test piece was supported vertically, burner flame was applied to the lower end and kept for 10 seconds, and then the burner flame was released from the test piece. When the flame disappeared, the burner flame was applied for another 10 seconds and then the burner flame was released.
  • V-0, V-1, V-2, and Not is the flaming combustion duration after the first flame contact (first afterflame time: t1), the flame after the second flame contact Sum of combustion duration (second afterflame time: t2), flammable combustion duration (second afterflame time: t2) and flameless combustion duration (residual time: t3) after the second flame contact (T2 + t3) Judgment was made based on the total (T) of the flammable combustion time (residual flame time) of the five test pieces and whether or not cotton was ignited by the combustion drop (drip).
  • V-0 t1 and t2 are both within 10 seconds, t2 + t3 is within 30 seconds, T is within 50 seconds, cotton is not ignited by drip, no burnout;
  • the determination of the drip property was as follows. ⁇ : No ignition of cotton by drip in all five test pieces; ⁇ : One to two of the five test pieces had cotton ignited by drip; ⁇ : 3 to 5 of the 5 test pieces, and cotton was ignited by drip.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine d'acide polylactique qui contient une résine d'acide polylactique (A), un hydroxyde métallique (B), un composé phosphoreux (C) et un composé volatil (D) autre que le composé phosphoreux (C) précité. La teneur du composé phosphoreux (C) précité n'est pas supérieure à 10 masses pour une valeur totale de 100 masses de la résine d'acide polylactique (A) précitée.
PCT/JP2011/002599 2010-06-09 2011-05-10 Composition de résine d'acide polylactique et article moulé à partir de celle-ci WO2011155119A1 (fr)

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WO2013180120A1 (fr) 2012-05-30 2013-12-05 花王株式会社 Composition de résine acide polylactique
US8841367B2 (en) 2012-05-24 2014-09-23 Sabic Innovative Plastics Ip B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US9023922B2 (en) 2012-05-24 2015-05-05 Sabic Global Technologies B.V. Flame retardant compositions, articles comprising the same and methods of manufacture thereof
WO2015079754A1 (fr) * 2013-11-29 2015-06-04 花王株式会社 Composition de résine contenant de l'acide polylactique
JP2015218329A (ja) * 2014-05-21 2015-12-07 富士ゼロックス株式会社 樹脂組成物及び樹脂成形体
JP2016060908A (ja) * 2014-09-12 2016-04-25 ハンファ トータル ペトロケミカルズ カンパニー リミテッド 難燃性ポリ乳酸樹脂組成物

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WO2010053167A1 (fr) * 2008-11-05 2010-05-14 帝人化成株式会社 Compositions d'acide polylactique et articles moulés à partir de celles-ci
JP2010111735A (ja) * 2008-11-05 2010-05-20 Teijin Chem Ltd ポリ乳酸組成物およびその成形品

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JP2009114458A (ja) * 2002-11-29 2009-05-28 Toray Ind Inc 樹脂組成物
WO2010053167A1 (fr) * 2008-11-05 2010-05-14 帝人化成株式会社 Compositions d'acide polylactique et articles moulés à partir de celles-ci
JP2010111735A (ja) * 2008-11-05 2010-05-20 Teijin Chem Ltd ポリ乳酸組成物およびその成形品

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9023922B2 (en) 2012-05-24 2015-05-05 Sabic Global Technologies B.V. Flame retardant compositions, articles comprising the same and methods of manufacture thereof
US9023923B2 (en) 2012-05-24 2015-05-05 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US8841367B2 (en) 2012-05-24 2014-09-23 Sabic Innovative Plastics Ip B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US8895649B2 (en) 2012-05-24 2014-11-25 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US8927661B2 (en) 2012-05-24 2015-01-06 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US9018286B2 (en) 2012-05-24 2015-04-28 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
US9394483B2 (en) 2012-05-24 2016-07-19 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
WO2013180120A1 (fr) 2012-05-30 2013-12-05 花王株式会社 Composition de résine acide polylactique
JP2014005453A (ja) * 2012-05-30 2014-01-16 Kao Corp ポリ乳酸樹脂組成物
US9725593B2 (en) 2012-05-30 2017-08-08 Kao Corporation Polylactic acid resin composition
JP2015127387A (ja) * 2013-11-29 2015-07-09 花王株式会社 ポリ乳酸樹脂組成物
WO2015079754A1 (fr) * 2013-11-29 2015-06-04 花王株式会社 Composition de résine contenant de l'acide polylactique
JP2015218329A (ja) * 2014-05-21 2015-12-07 富士ゼロックス株式会社 樹脂組成物及び樹脂成形体
JP2016060908A (ja) * 2014-09-12 2016-04-25 ハンファ トータル ペトロケミカルズ カンパニー リミテッド 難燃性ポリ乳酸樹脂組成物

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