WO2011052849A1 - Composition de résine thermoplastique et pièces moulées utilisant une telle composition - Google Patents

Composition de résine thermoplastique et pièces moulées utilisant une telle composition Download PDF

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Publication number
WO2011052849A1
WO2011052849A1 PCT/KR2009/007955 KR2009007955W WO2011052849A1 WO 2011052849 A1 WO2011052849 A1 WO 2011052849A1 KR 2009007955 W KR2009007955 W KR 2009007955W WO 2011052849 A1 WO2011052849 A1 WO 2011052849A1
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Prior art keywords
thermoplastic resin
flame retardant
resin composition
group
weight
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PCT/KR2009/007955
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English (en)
Korean (ko)
Inventor
조진경
정창도
하두한
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제일모직 주식회사
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Publication of WO2011052849A1 publication Critical patent/WO2011052849A1/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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • the present disclosure relates to a thermoplastic resin composition and a molded article using the same.
  • thermoplastic resin may be mixed with a reinforcing agent, and a flame retardant may be mixed and used to impart flame retardancy thereto.
  • a compatibilizer may be added to increase the compatibility between the thermoplastic resin and the reinforcing agent.
  • the physical properties such as rigidity, heat resistance, and flame retardancy may be reduced.
  • thermoplastic resin composition having not only excellent physical properties balance of rigidity, heat resistance, flame retardancy, processability, etc., but also environmental friendliness.
  • Another aspect of the present invention is to provide a molded article prepared from the thermoplastic resin composition.
  • thermoplastic resin composition comprising 5 to 45% by weight of the natural fiber powder pretreated with a phosphorus-based flame retardant.
  • the thermoplastic resin is polycarbonate resin, polylactic acid resin, polyolefin resin, vinyl copolymer resin, polyester resin, acrylic resin, liquid crystal polymer, polyphenylene sulfide resin, polyacetal resin, polyphenylene oxide resin, polysulfone resin , Polyether sulfone resin, polyether ketone resin, polyetherimide resin, and combinations thereof, and may have a melting point (Tm) or a crystallization temperature (Tc) of 230 ° C. or less.
  • Tm melting point
  • Tc crystallization temperature
  • the natural fiber powder is flax, hemp, jute, jute, kenaf, bamboo, ramie, curaua, wood flour, walnut shell and combinations thereof Can be selected.
  • the phosphorus flame retardant may be a liquid, and also a phosphate compound, a phosphinate compound, a phosphonate compound, a phosphonite compound, a phosphite compound, and a combination thereof It may be selected from the group consisting of.
  • the pretreatment may be performed by impregnating the natural fiber powder in the phosphorus flame retardant, and may be performed in an amount of 5 to 40 parts by weight based on 100 parts by weight of the natural fiber powder.
  • the thermoplastic resin composition may further include 1 to 30 parts by weight of (C) a flame retardant based on 100 parts by weight of the thermoplastic resin composition, and the flame retardant may be a phosphorus flame retardant, a nitrogen compound flame retardant, a silicone flame retardant, an inorganic flame retardant, or a combination thereof. It may be selected from the group consisting of.
  • the thermoplastic resin composition may further include 1 to 20 parts by weight of the impact modifier (D) based on 100 parts by weight of the thermoplastic resin composition.
  • the impact modifier may be selected from the group consisting of a core-shell structure copolymer, an olefin copolymer, and a combination thereof.
  • the copolymer of the core-shell structure may be a diene monomer, an acrylic monomer, a silicone monomer, and a combination thereof.
  • an unsaturated compound selected from the group consisting of acrylic monomers, aromatic vinyl monomers, unsaturated nitrile monomers, polymers formed from one or more of these monomers, and combinations thereof is grafted.
  • the olefin copolymer may be a copolymer of an olefin monomer and an acrylic monomer.
  • the thermoplastic resin composition may include an antibacterial agent, a heat stabilizer, an antioxidant, a mold release agent, a light stabilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, an admixture, a colorant, a stabilizer, a lubricant, an antistatic agent, a colorant, a flame retardant, a weather agent, a ultraviolet absorber, (E) additives selected from the group consisting of sunscreens, flame retardants, fillers, nucleators, adhesion aids, pressure-sensitive adhesives and mixtures thereof may be further included.
  • an antibacterial agent a heat stabilizer, an antioxidant, a mold release agent, a light stabilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, an admixture, a colorant, a stabilizer, a lubricant, an antistatic agent, a colorant, a flame retardant, a weather agent, a ultraviolet absorber, (E
  • Another aspect of the present invention provides a molded article prepared from the thermoplastic resin composition.
  • thermoplastic resin composition having not only excellent physical properties such as stiffness, heat resistance, flame retardancy, and workability but also eco-friendliness is provided, it is suitable for molding materials such as automobiles, mechanical parts, battery electronic parts, communication devices, building materials, office equipment, and sundries. It can be usefully applied.
  • (meth) acrylate means that both “acrylate” and “methacrylate” are possible.
  • (meth) acrylic acid alkyl ester means that both “acrylic acid alkyl ester” and “methacrylic acid alkyl ester” are possible, and “(meth) acrylic acid ester” means both “acrylic acid ester” and “methacrylic acid ester”. It means everything is possible.
  • thermoplastic resin composition includes (A) a thermoplastic resin and (B) a natural fiber powder pretreated with a phosphorus-based flame retardant.
  • thermoplastic resin composition according to an embodiment will be described in detail.
  • thermoplastic resin (A) thermoplastic resin
  • thermoplastic resin a resin capable of melt extrusion may be used. Specifically, a resin having a melting point (Tm) or a crystallization temperature (Tc) of 230 ° C. or less, more specifically, 180 to 230 ° C. may be used.
  • Tm melting point
  • Tc crystallization temperature
  • thermoplastic resin examples include polycarbonate resin, polylactic acid resin, polyolefin resin, vinyl copolymer resin, polyester resin, acrylic resin, liquid crystal polymer, polyphenylene sulfide resin, polyacetal resin, polyphenylene oxide resin And polysulfone resins, polyether sulfone resins, polyether ketone resins, polyetherimide resins, and combinations thereof.
  • the polycarbonate resin may be prepared by reacting a compound selected from the group consisting of diphenols, phosgene, halogen formate, carbonate ester, and combinations thereof.
  • the polycarbonate resin may use a weight average molecular weight of 5,000 to 200,000 g / mol, specifically, may be used from 5,000 to 10,000 g / mol for processing at low temperatures.
  • the polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols.
  • the polycarbonate resin may be used a linear polycarbonate resin, branched (branched) polycarbonate resin, polyester carbonate copolymer resin and the like.
  • group polycarbonate resin etc. are mentioned as said linear polycarbonate resin.
  • the branched polycarbonate resins include those produced by reacting polyfunctional aromatic compounds such as trimellitic anhydride, trimellitic acid, and the like with diphenols and carbonates.
  • the polyfunctional aromatic compound may be included in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin.
  • said polyester carbonate copolymer resin what was manufactured by making bifunctional carboxylic acid react with diphenols and a carbonate is mentioned. In this case, as the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate, or the like may be used.
  • the polylactic acid resin is a polyester-based resin prepared by ester reaction using lactic acid obtained by decomposing corn starch as a monomer, and is easily commercially available.
  • the polylactic acid resin may include a repeating unit derived from a lactic acid selected from the group consisting of L-lactic acid, D-lactic acid, L, D-lactic acid, and combinations thereof.
  • the polylactic acid resin may be selected from the group consisting of polylactic acid homopolymers, polylactic acid copolymers, and combinations thereof.
  • the polylactic acid polymer is preferably a polymer produced by ring-opening polymerization of a lactic acid selected from the group consisting of the L-lactic acid, D-lactic acid and combinations thereof.
  • the polyolefin resin is a high density polyethylene (HDPE) resin, linear low density polyethylene (LLDPE) resin, polypropylene resin, ethylene-propylene copolymer resin, ethylene-vinyl alcohol copolymer resin and combinations thereof It may be used selected from the group consisting of, specifically, may be used polypropylene resin.
  • the high density polyethylene resin means that it has a density range of 0.94 to 0.965
  • the linear low density polyethylene resin means that it has a density range of 0.91 to 0.94.
  • the vinyl copolymer resin is a copolymer obtained by graft polymerization of 5 to 95% by weight of a vinyl polymer to 5 to 95% by weight of a rubbery polymer.
  • the vinyl polymer may include 50 to 95 wt% of a first vinyl monomer selected from the group consisting of aromatic vinyl monomers, acrylic monomers, and combinations thereof; And 5 to 50 wt% of a second vinyl monomer selected from the group consisting of unsaturated nitrile monomers, acrylic monomers, and combinations thereof.
  • first vinyl monomer and the second vinyl monomer are different from each other.
  • the aromatic vinyl monomer may be selected from the group consisting of styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, and combinations thereof.
  • alkyl-substituted styrene include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, ⁇ -methyl styrene and the like.
  • the acrylic monomer may be selected from the group consisting of (meth) acrylic acid alkyl esters, (meth) acrylic acid esters, and combinations thereof.
  • the alkyl means C1 to C10 alkyl.
  • Specific examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. Meta) acrylates may be used.
  • the unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof.
  • the rubbery polymers include butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) rubber, polyorganosiloxane / polyalkyl (Meth) acrylate rubber composites and combinations thereof may be used.
  • the rubber-modified vinyl-based graft copolymer is well known to those skilled in the art, and may be any of emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization. Examples include adding the above-mentioned aromatic vinyl monomer in the presence of a rubbery polymer and performing emulsion polymerization or bulk polymerization using a polymerization initiator.
  • polyester resin as the aromatic polyester resin, a resin polycondensed by melt polymerization from a terephthalic acid or a terephthalic acid alkyl ester and a glycol component having 2 to 10 carbon atoms can be used.
  • the alkyl means C1 to C10 alkyl.
  • aromatic polyester resins include polyethylene terephthalate resins, polytrimethylene terephthalate resins, polybutylene terephthalate resins, polyhexamethylene terephthalate resins, polycyclohexane dimethylene terephthalate resins, and some others to these resins. It is possible to use a resin selected from the group consisting of a mixture of monomers and a resin modified by amorphous, and more specifically, among these, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin , Amorphous polyethylene terephthalate resin and the like can be used.
  • thermoplastic resins may be used alone or in combination of two or more thereof. Specifically, when two kinds of thermoplastic resins are mixed and used, they may be mixed and used in a ratio of 1: 9 to 9: 1.
  • the thermoplastic resin may be included in an amount of 55 to 95 wt% based on the total amount of the thermoplastic resin composition, and specifically, 70 to 85 wt%. When the thermoplastic resin is included in the content range, it is excellent in rigidity, heat resistance, processability, and the like.
  • the natural fiber powder is included as a reinforcing agent in the thermoplastic resin, flax, hemp, jute, kenaf, bamboo, ramie, curaua, wood flour, Walnut shells and combinations thereof may be selected from the group consisting of.
  • thermoplastic resin composition which is environmentally friendly and has excellent rigidity and heat resistance.
  • the natural fiber powder is composed of cellulose, lignin, and semicellulose.
  • the lignin contains a large amount of aromatic rings and has a cross-linking structure in which the main chains are connected to each other, so that it is easy to form a char layer upon ignition, so flame retardancy may be expected. Can be.
  • the natural fiber powder may have an average length of 0.01 to 100mm, specifically 0.1 ⁇ to 10 mm.
  • the average length of the natural fiber powder is within the above range mechanical strength, such as tensile strength, flexural strength, flexural modulus and the like, and excellent workability and appearance characteristics may appear.
  • the natural fiber powder may have an average diameter of 0.001 to 50 ⁇ m, specifically 0.01 to 5 ⁇ m. When the average diameter of the natural fiber powder is in the above range is excellent in workability and surface gloss.
  • the natural fiber powder may be pretreated with a phosphorus-based flame retardant.
  • the pretreatment is performed by impregnating the natural fiber powder in the phosphorus-based flame retardant, specifically, the phosphorus-based flame retardant solution so that the phosphorus-based flame retardant is sufficiently penetrated into the natural fiber powder.
  • the phosphorus flame retardant may be used as a liquid.
  • the above-mentioned natural fiber powder is a structure having many pores, and pretreatment is performed while the phosphorus-based flame retardant penetrates into the pores, thereby increasing the flame retardant efficiency.
  • liquid phosphorous flame retardant may be mixed with the natural fiber powder evenly when the solid phase.
  • a phosphorus-based flame retardant is a compound of the cellulose and the phosphorus-based flame retardant component of the natural fiber powder by the intermolecular attraction, the liquid phosphorus-based flame retardant is superior to the binding efficiency than the solid phase.
  • the phosphorus flame retardant is selected from the group consisting of phosphate compounds, phosphinate compounds, phosphonate compounds, phosphonite compounds, phosphite compounds, and combinations thereof Can be used.
  • the phosphate compound examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tricylyl phosphate, tri (2,4,6-trimethylphenyl) phosphate, and tri ( 2,4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate, resorcinolbis (diphenylphosphate), hydroquinonebis (diphenylphosphate), bisphenol A-bis (diphenylphosphate ), Resorcinol bis (2,6-diary butylphenylphosphate), hydroquinone bis (2,6-dimethylphenyl phosphate), etc. can be mentioned, These can be used individually or in mixture of 2 or more types.
  • phosphinate compound examples include aluminum diethylphosphinate, aluminum methylethylphosphinate, and the like, and these may be used alone or in combination of two or more thereof.
  • phosphite compound examples include tris (2,4-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, and the like, and these may be used alone or in combination of two or more thereof.
  • Phosphorus-based flame retardants of this kind fill the pores as they physically bind to cellulose in the constituents of the natural fiber powder during pretreatment, thereby promoting the formation of char in the natural fiber powder and thermoplastic resin upon ignition, and thus flame retardant. Efficiency can be increased. That is, synergistic effects can be expected when using natural fiber powder pretreated with a phosphorus flame retardant.
  • the natural fiber powder without lignin purification may be pretreated with a phosphorus-based flame retardant to increase the flame retardant efficiency.
  • the pretreatment may be performed by mixing the natural fiber powder and the phosphorus flame retardant in an amount of 5 to 40 parts by weight, specifically 10 to 35 parts by weight, based on 100 parts by weight of the natural fiber powder.
  • the content ratio is excellent flame retardancy and does not inhibit other basic physical properties.
  • the natural fiber powder pretreated with the phosphorus-based flame retardant may be included in an amount of 5 to 45 wt% based on the total amount of the thermoplastic resin composition, and specifically, 5 to 25 wt%.
  • the natural fiber powder pretreated with a phosphorus flame retardant is included in the above range, not only flame retardancy but also stiffness, heat resistance and processability are excellent.
  • thermoplastic resin composition according to one embodiment may further include a flame retardant to maximize flame retardancy.
  • the flame retardant is not particularly limited, and specifically, those selected from the group consisting of phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants, inorganic flame retardants, and combinations thereof may be used.
  • phosphorus flame retardant an organophosphorus compound, red phosphorus, etc. are mentioned.
  • the organophosphorus compound may include a phosphate compound, a phosphinate compound, a phosphonate compound, a phosphonite compound, a phosphite compound, a phosphagen compound, and the like. What is selected from the group which consists of these combinations can be used. Specific examples of each compound are as mentioned above.
  • nitrogen compound-based flame retardant examples include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyan compounds, aliphatic amides, aromatic amides, urea and thio urea.
  • aliphatic amine compounds examples include ethyl amine, butyl amine, diethyl amine, ethylene diamine, triethylene tetramine, diamino cyclohexane, diamino cyclooctane, guanine, diamino purine, tripyridine, and triazine compounds. have.
  • the silicone flame retardant may be a silicone resin or silicone oil.
  • the silicone resin may be a resin having a three-dimensional network structure capable of combining units of RSiO 3/2 , RSiO, and RSiO 1/2 .
  • R represents a substituent containing a C1 to C10 alkyl group such as a methyl group, an ethyl group, a propyl group, an aromatic group or a vinyl group in the substituent.
  • the silicone oil is polydimethyl siloxane and at least one methyl group in the side chain or terminal of the polydimethyl siloxane is hydrogen, alkyl group, cyclohexyl group, phenyl group, benzyl group, epoxy group, polyether group, carboxyl group, mercapto group, chloroalkyl group, alkyl Modified polysiloxanes or mixtures thereof which are modified by being selected from the group consisting of alcohol ester groups, alcohol groups, allyl groups, vinyl groups, trifluoro methyl groups and combinations thereof.
  • inorganic flame retardant examples include silicon oxide (SiO 2 ), magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, antimony, sodium carbonate, zinc hydroxy stannate, zinc stannate, metatartrate, zinc sulfate, zinc oxide, ferrous oxide, and oxidation
  • the flame retardant may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin composition, and specifically 5 to 20 parts by weight. When the flame retardant is included in the above range, not only excellent flame retardancy, but also excellent rigidity and heat resistance.
  • thermoplastic resin composition according to one embodiment may further include an impact modifier.
  • the impact modifier may be selected from the group consisting of a core-shell copolymer, an olefin copolymer and a combination thereof.
  • the core-shell copolymer has a core-shell structure by grafting an unsaturated monomer to a rubber core structure to form a hard shell.
  • a rubber compound polymerized with a monomer selected is a copolymer in which an unsaturated compound selected from the group consisting of an acrylic monomer, an aromatic vinyl monomer, an unsaturated nitrile monomer, a polymer formed from one or more of these monomers, and a combination thereof is grafted.
  • diene-based monomers examples include butadiene of C4 to C6, isoprene, and butadiene may be used.
  • Specific examples of the rubbery polymer in which the diene monomer is polymerized include butadiene rubber, acrylic rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, and ethylene-propylene-diene terpolymer (EPDM).
  • acrylic monomers examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and hexyl (meth). ) Acrylate, # 2-ethylhexyl (meth) acrylate, etc. are mentioned.
  • ethylene glycol di (meth) acrylate propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, allyl ( Curing agents such as meth) acrylate and triallyl cyanurate can be used.
  • silicone-based monomers examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decademethylmethylcyclopentasiloxane, decedocamethylcyclohexasiloxane, dectrimethyltriphenylcyclotrisiloxane, tet tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane.
  • curing agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane and tetraethoxysilane can be used.
  • the rubber average particle diameter of the rubbery polymer is preferably 0.4 to 1 ⁇ m in terms of impact resistance and color balance maintenance.
  • the rubber polymer may be included in an amount of 20 to 80 wt% based on the total amount of the copolymer of the core-shell structure.
  • the rubber polymer is included in the range, the impact reinforcing effect and heat resistance may be maximized, and the fluidity may be significantly improved.
  • an acrylic monomer may be selected from the group consisting of (meth) acrylic acid alkyl esters, (meth) acrylic acid esters, and combinations thereof.
  • the alkyl means C1 to C10 alkyl
  • specific examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth).
  • An acrylate etc. are mentioned, Among these, methyl (meth) acrylate can be used.
  • the aromatic vinyl monomer may be selected from the group consisting of styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, and combinations thereof.
  • alkyl substituted styrene include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, ⁇ -methyl styrene, and the like.
  • unsaturated nitrile monomers may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof.
  • Polymethyl methacrylate etc. are mentioned as a polymer formed from these 1 or more types of monomers in the said unsaturated compound.
  • the core-shell copolymer may have an average particle size of 0.1 to 0.5 ⁇ m ⁇ , and when the average particle size is in the above range, is well dispersed in a polyester matrix to facilitate shock absorption when externally impacted. The impact reinforcement effect is increased.
  • the olefin copolymer may be a copolymer of an olefin monomer and an acrylic monomer.
  • Ethylene, propylene, isopropylene, butylene, isobutylene, etc. are mentioned as said olefin monomer, These can be used individually or in mixture.
  • (meth) acrylic acid alkyl ester or (meth) acrylic acid ester is used as the acrylic monomer.
  • the alkyl means C1 to C10 alkyl
  • specific examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth).
  • An acrylate etc. are mentioned, Among these, methyl (meth) acrylate can be used.
  • the olefin copolymer may be prepared using a Ziegler-Natta catalyst which is a general olefin polymerization catalyst, and may be prepared using a metallocene catalyst to make a more selective structure. At this time, in order to improve dispersibility with the thermoplastic resin, a functional group such as maleic anhydride may be grafted to the olefin copolymer.
  • the impact modifier may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the thermoplastic resin composition, and specifically 5 to 15 parts by weight may be included.
  • the impact modifier is included in the above range, it is possible to maximize the impact reinforcement effect and the increase in heat resistance, and the flowability may be improved to improve injection moldability.
  • Thermoplastic resin composition is an antibacterial agent, heat stabilizer, antioxidant, release agent, light stabilizer, inorganic additives, surfactants, coupling agents, plasticizers, admixtures, colorants, stabilizers, lubricants, antistatic agents, colorants, It may further include additives selected from the group consisting of flame retardants, weathering agents, ultraviolet absorbers, sunscreens, flame retardants, fillers, nucleating agents, adhesion aids, pressure sensitive adhesives, and mixtures thereof.
  • the antioxidant a phenol type, a phosphite type, a thioether type, or an amine type antioxidant may be used.
  • the release agent may include a fluorine-containing polymer, a silicone oil, a metal salt of stearic acid, and montanic acid ( metal salts of montanic acid), montanic acid ester waxes or polyethylene waxes may be used.
  • a benzophenone type or an amine type weathering agent may be used as the weathering agent, and a dye or a pigment may be used as the coloring agent.
  • the sunscreen may be titanium oxide (TiO 2 ) or carbon black
  • the filler may be glass fiber, carbon fiber, silica, mica, alumina, clay, calcium carbonate, calcium sulfate, or glass beads.
  • the filler is added as described above, physical properties such as mechanical strength and heat resistance may be improved.
  • talc or clay may be used as the nucleating agent.
  • the additive may be included in 0.1 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin composition.
  • the additive is included in the above range it is possible to obtain the effect of the additive according to each application and to obtain excellent mechanical properties and improved appearance of the surface.
  • thermoplastic resin composition may be prepared by a known method. For example, after mixing the components and additives of the present invention described above, it can be melt-extruded in an extruder and produced in pellet form.
  • thermoplastic resin composition is useful for molding products in fields where rigidity, heat resistance, and flame retardancy are important, for example, molding materials such as automobiles, mechanical parts, battery electronic parts, communication devices, building materials, office equipment, and sundries. Can be applied.
  • thermoplastic resin composition Each component used in the preparation of the thermoplastic resin composition according to one embodiment is as follows.
  • thermoplastic resin (A) thermoplastic resin
  • Wood flour pretreated with a phosphorus flame retardant (manufactured by Daihachi CR-741) was used. At this time, the pre-treatment was performed by impregnating wood powder with 20 parts by weight of phosphorus-based flame retardant solution based on 100 parts by weight of wood powder, and dried for 5 hours in a 50 °C oven.
  • Wood flour pretreated with (B '') silane coupling agent (A-187 SILANE from SILQUEST) was used. At this time, the wood powder was immersed in an aqueous solution of silane coupling agent for 1 minute and then taken out and dried in an oven at 50 ° C for 5 hours.
  • Daihachi CR-741 was used.
  • Ciba Irganox 1076 was used as an antioxidant.
  • thermoplastic resin composition was prepared by mixing a thermoplastic resin composition, and extruded into a pellet form after extruding in a temperature range of 190 to 220 ° C. in a conventional twin screw extruder. .
  • Parts by weight are content units based on 100 parts by weight of (A) and 100 parts by weight of (B), (B ') or (B' ').
  • Comparative Example 1 pre-treatment with natural-phosphorous flame retardant without any treatment Comparative Examples 2 and 3 using the natural fiber powder in an amount outside the range according to one embodiment, Comparative Example 4 using the natural fiber powder pretreated with a silane coupling agent, and no natural fiber powder pretreated with the phosphorus-based flame retardant It can be seen that the flame retardancy is significantly increased while maintaining excellent stiffness and heat resistance compared to the case of Comparative Example 5 that is not.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine thermoplastique comportant: (A) une résine thermoplastique ; et (B) une poudre de fibre naturelle prétraitée avec un agent ignifuge au phosphore, ainsi que des pièces moulées utilisant la composition.
PCT/KR2009/007955 2009-11-02 2009-12-30 Composition de résine thermoplastique et pièces moulées utilisant une telle composition WO2011052849A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2009-0105150 2009-11-02
KR1020090105150A KR20110048377A (ko) 2009-11-02 2009-11-02 열가소성 수지 조성물 및 이를 이용한 성형품

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WO2011052849A1 true WO2011052849A1 (fr) 2011-05-05

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WO2015170803A1 (fr) * 2014-05-07 2015-11-12 삼성에스디아이 주식회사 Composition de résine de polycarbonate et articles moulés préparés à partir de celle-ci
CN105419264A (zh) * 2014-09-12 2016-03-23 韩华道达尔有限公司 阻燃性聚乳酸树脂组合物
CN108976471A (zh) * 2018-06-27 2018-12-11 杭州本松新材料技术股份有限公司 阻燃剂复配体系及包含其的无卤阻燃树脂基复合材料

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KR101464250B1 (ko) * 2011-12-20 2014-11-24 제일모직주식회사 저온에서의 백탁 현상이 개선된 열가소성 수지 조성물
KR101400737B1 (ko) * 2012-03-28 2014-05-29 (주)썬패치테크노 설비 보수보강용 유브이경화형 난연 접착제 조성물
KR101575458B1 (ko) 2014-03-07 2015-12-07 현대자동차주식회사 압출성형용 폴리올레핀-천연섬유 복합재 조성물
KR101583924B1 (ko) * 2014-05-09 2016-01-08 현대자동차주식회사 폴리프로필렌-폴리유산 복합재 조성물 및 이의 제조방법

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KR20080025072A (ko) * 2005-07-08 2008-03-19 도레이 가부시끼가이샤 수지 조성물 및 이것으로 이루어진 성형품

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KR20080025072A (ko) * 2005-07-08 2008-03-19 도레이 가부시끼가이샤 수지 조성물 및 이것으로 이루어진 성형품

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015170803A1 (fr) * 2014-05-07 2015-11-12 삼성에스디아이 주식회사 Composition de résine de polycarbonate et articles moulés préparés à partir de celle-ci
CN105419264A (zh) * 2014-09-12 2016-03-23 韩华道达尔有限公司 阻燃性聚乳酸树脂组合物
CN108976471A (zh) * 2018-06-27 2018-12-11 杭州本松新材料技术股份有限公司 阻燃剂复配体系及包含其的无卤阻燃树脂基复合材料

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