WO2011052849A1 - Thermoplastic resin composition and moldings using same - Google Patents

Thermoplastic resin composition and moldings using same 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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WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
flame retardant
resin composition
group
weight
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Application number
PCT/KR2009/007955
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French (fr)
Korean (ko)
Inventor
조진경
정창도
하두한
Original Assignee
제일모직 주식회사
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Publication of WO2011052849A1 publication Critical patent/WO2011052849A1/en

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Classifications

    • 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.

Abstract

Provided is a thermoplastic resin composition including: (A) a thermoplastic resin; and (B) a natural fiber powder pretreated with a phosphorous flame retardant, as well as moldings using the composition.

Description

열가소성 수지 조성물 및 이를 이용한 성형품 Thermoplastic resin composition and molded article using same
본 기재는 열가소성 수지 조성물 및 이를 이용한 성형품에 관한 것이다. The present disclosure relates to a thermoplastic resin composition and a molded article using the same.
열가소성 수지에 강성, 내열성 등을 향상시키기 위해 보강제를 혼합하여 사용할 수 있으며, 여기에 난연성을 부여하고자 난연제를 혼합하여 사용할 수 있다.In order to improve rigidity, heat resistance, and the like, the thermoplastic resin may be mixed with a reinforcing agent, and a flame retardant may be mixed and used to impart flame retardancy thereto.
이때 열가소성 수지와 보강제의 상용성을 높이기 위하여 상용화제를 첨가하기도 하는데, 이 경우 강성, 내열성, 난연성 등의 기본 물성의 저하를 가져올 수 있다. In this case, a compatibilizer may be added to increase the compatibility between the thermoplastic resin and the reinforcing agent. In this case, the physical properties such as rigidity, heat resistance, and flame retardancy may be reduced.
본 발명의 일 측면은 강성, 내열성, 난연성, 가공성 등이 우수한 물성 밸런스를 가질 뿐만 아니라 친환경성도 가지는 열가소성 수지 조성물을 제공하기 위한 것이다. One aspect of the present invention is to provide a thermoplastic resin composition having not only excellent physical properties balance of rigidity, heat resistance, flame retardancy, processability, etc., but also environmental friendliness.
본 발명의 다른 일 측면은 상기 열가소성 수지 조성물로부터 제조된 성형품을 제공하기 위한 것이다.Another aspect of the present invention is to provide a molded article prepared from the thermoplastic resin composition.
본 발명의 일 측면은 (A) 열가소성 수지 55　내지 95　중량%; 및 (B) 인계 난연제로 전처리된 천연섬유 분말 5 내지 45 중량%를 포함하는 열가소성 수지 조성물을 제공한다. One aspect of the invention (A) 55 to 95% by weight of the thermoplastic resin; And (B) provides a thermoplastic resin composition comprising 5 to 45% by weight of the natural fiber powder pretreated with a phosphorus-based flame retardant.
상기 열가소성 수지는 폴리카보네이트 수지, 폴리유산 수지, 폴리올레핀 수지, 비닐계 공중합체 수지, 폴리에스테르 수지, 아크릴계 수지, 액정 고분자, 폴리페닐렌술파이드 수지, 폴리아세탈 수지, 폴리페닐렌옥사이드 수지, 폴리술폰 수지, 폴리에테르 술폰 수지, 폴리에테르케톤 수지, 폴리에테르이미드 수지 및 이들의 조합으로 이루어진 군에서 선택될 수 있고, 용융점(Tm) 또는 결정화온도(Tc)가 230℃ 이하일 수 있다.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.
상기 천연섬유 분말은 아마(flax), 대마(hemp), 황마(jute), 양마(kenaf), 대나무, 모시풀(ramie), 쿠라우아(curaua), 목분, 호두껍질 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.The natural fiber powder is flax, hemp, jute, jute, kenaf, bamboo, ramie, curaua, wood flour, walnut shell and combinations thereof Can be selected.
상기 인계 난연제는 액상일 수 있으며, 또한 포스페이트(phosphate) 화합물, 포스피네이트(phosphinate) 화합물, 포스포네이트(phosphonate) 화합물, 포스포나이트(phosphonite) 화합물, 포스파이트(phosphite) 화합물 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. 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.
상기 전처리는 상기 인계 난연제에 상기 천연섬유 분말을 함침하여 수행될 수 있으며, 또한 상기 천연섬유 분말 100 중량부에 대하여 상기 인계 난연제 5 내지 40 중량부로 수행될 수 있다. 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.
상기 열가소성 수지 조성물은 상기 열가소성 수지 조성물 100 중량부에 대하여 (C) 난연제 1 내지 30 중량부를 더 포함할 수 있고, 상기 난연제는 인계 난연제, 질소 화합물계 난연제, 실리콘계 난연제, 무기계 난연제 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.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.
상기 열가소성 수지 조성물은 상기 열가소성 수지 조성물 100 중량부에 대하여 (D) 충격보강제 1 내지 20 중량부를 더 포함할 수 있다. 　상기 충격보강제는 코어-쉘 구조의 공중합체, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택될 수 있으며, 상기 코어-쉘 구조의 공중합체는 디엔계　단량체,　아크릴계　단량체,　실리콘계　단량체 및 이들의 조합으로 이루어진 군에서 선택되는 단량체를 중합한 고무질 중합체에, 아크릴계 단량체, 방향족 비닐 단량체, 불포화 니트릴 단량체, 이들 1종 이상의 단량체로부터 형성되는 중합체 및 이들의 조합으로 이루어진 군에서 선택되는 불포화 화합물이 그라프트된 공중합체이고, 상기 올레핀계 공중합체는 올레핀계 단량체 및 아크릴계 단량체의 공중합체일 수 있다.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. In the rubbery polymer obtained by polymerizing a monomer selected from the group consisting of combinations, 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.
상기 열가소성 수지 조성물은 항균제, 열안정제, 산화방지제, 이형제, 광안정제, 무기물 첨가제, 계면활성제, 커플링제, 가소제, 혼화제, 착색제, 안정제, 활제, 정전기방지제, 조색제, 방염제, 내후제, 자외선 흡수제, 자외선 차단제, 난연제, 충전제, 핵 형성제, 접착 조제, 점착제 및 이들의 혼합물로 이루어진 군에서 선택되는 (E) 첨가제를 더 포함할 수 있다.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.
본 발명의 다른 일 측면은 상기 열가소성 수지 조성물로부터 제조된 성형품을 제공한다.Another aspect of the present invention provides a molded article prepared from the thermoplastic resin composition.
기타 본 발명의 측면들의 구체적인 사항은 이하의 상세한 설명에 포함되어 있다.Other details of aspects of the invention are included in the following detailed description.
강성, 내열성, 난연성, 가공성 등이 우수한 물성 밸런스를 가질 뿐만 아니라 친환경성도 가지는 열가소성 수지 조성물이 제공됨에 따라, 자동차, 기계 부품, 전지전자 부품, 통신기기, 건축재, 사무기기, 잡화 등과 같은 성형품 재료에 유용하게 적용될 수 있다. As a 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.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 　다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다.　Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.
본 명세서에서 특별한 언급이 없는 한, "(메타)아크릴레이트"는 "아크릴레이트"와 "메타크릴레이트" 둘 다 가능함을 의미한다. 　또한 "(메타)아크릴산 알킬 에스테르"는 "아크릴산 알킬 에스테르"와 "메타크릴산 알킬 에스테르" 둘 다 가능함을 의미하며, "(메타)아크릴산 에스테르"는 "아크릴산 에스테르"와 "메타크릴산 에스테르" 둘 다 가능함을 의미한다. Unless otherwise specified herein, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible. Also, "(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.
일 구현예에 따른 열가소성 수지 조성물은 (A) 열가소성 수지 및 (B) 인계 난연제로 전처리된 천연섬유 분말을 포함한다.The thermoplastic resin composition according to one embodiment includes (A) a thermoplastic resin and (B) a natural fiber powder pretreated with a phosphorus-based flame retardant.
　
이하, 일 구현예에 따른 열가소성 수지 조성물을 이루는 각 성분에 대하여 구체적으로 살펴본다. Hereinafter, each component of the thermoplastic resin composition according to an embodiment will be described in detail.
(A) 열가소성 수지(A) thermoplastic resin
상기 열가소성 수지는 용융 압출이 가능한 수지가 사용될 수 있으며, 구체적으로는 용융점(Tm) 또는 결정화온도(Tc)가 230℃ 이하, 더욱 구체적으로는 180 내지 230℃ 인 수지가 사용될 수 있다. 　상기 범위의 용융점(Tm) 또는 결정화온도(Tc)를 가진 열가소성 수지가 사용될 경우 용융 압출 공정 중에 발생할 수 있는 천연섬유의 분해를 최소화할 수 있다.As the 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. When a thermoplastic resin having a melting point (Tm) or a crystallization temperature (Tc) in the above range is used, it is possible to minimize decomposition of natural fibers that may occur during the melt extrusion process.
상기 열가소성 수지의 구체적인 예로는, 폴리카보네이트 수지, 폴리유산 수지, 폴리올레핀 수지, 비닐계 공중합체 수지, 폴리에스테르 수지, 아크릴계 수지, 액정 고분자, 폴리페닐렌술파이드 수지, 폴리아세탈 수지, 폴리페닐렌옥사이드 수지, 폴리술폰 수지, 폴리에테르 술폰 수지, 폴리에테르케톤 수지, 폴리에테르이미드 수지 및 이들의 조합으로 이루어진 군에서 선택되는 것을 들 수 있다. Specific examples of the thermoplastic resin 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.
상기 폴리카보네이트 수지는 디페놀류와 포스겐, 할로겐 포르메이트, 탄산 에스테르 및 이들의 조합으로 이루어진 군에서 선택되는 화합물을 반응시켜 제조될　수 있다. 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.
상기 폴리카보네이트 수지는 중량평균 분자량이 5,000 내지 200,000 g/mol인 것을 사용할 수 있으며, 구체적으로는 낮은 온도에서 가공하기 위해 5,000 내지 10,000 g/mol인 것을 사용할 수 있다. 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.
상기 폴리카보네이트 수지는 2종 이상의 디페놀류로부터 제조된 공중합체의 혼합물일 수도 있다. 　또한 상기 폴리카보네이트 수지는 선형 폴리카보네이트 수지, 분지형(branched) 폴리카보네이트 수지, 폴리에스테르카보네이트 공중합체 수지 등을 사용할 수 있다.The polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols. In addition, the polycarbonate resin may be used a linear polycarbonate resin, branched (branched) polycarbonate resin, polyester carbonate copolymer resin and the like.
상기 선형 폴리카보네이트 수지로는 비스페놀-A계 폴리카보네이트 수지 등을 들 수 있다. 　상기 분지형 폴리카보네이트 수지로는 트리멜리틱 무수물, 트리멜리틱산 등과 같은 다관능성 방향족 화합물을 디페놀류 및 카보네이트와 반응시켜 제조한 것을 들 수 있다. 　상기 다관능성 방향족 화합물은 분지형 폴리카보네이트 수지 총량에 대하여 0.05 내지 2 몰%로 포함될 수 있다. 　상기 폴리에스테르카보네이트 공중합체 수지로는 이관능성 카르복실산을 디페놀류 및 카보네이트와 반응시켜 제조한 것을 들 수 있다. 　이때 상기 카보네이트로는 디페닐카보네이트 등과 같은 디아릴카보네이트, 에틸렌 카보네이트 등을 사용할 수 있다. Bisphenol-A type | system | group polycarbonate resin etc. are mentioned as said linear polycarbonate resin. Examples of 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. As 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.
상기 폴리유산 수지는 옥수수 전분을 분해하여 얻은 유산(lactic acid)을 단량체로 하여 에스테르 반응에 의해 제조되는 폴리에스테르계 수지로서, 상업적 구입이 용이하다.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.
상기 폴리유산 수지는 L-유산, D-유산, L,D-유산 및 이들의 조합으로 이루어진 군에서 선택되는 유산으로부터 유도된 반복단위를 포함할 수 있다. 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.
상기 폴리유산 수지는 폴리유산 단일 중합체(homopolymer), 폴리유산 공중합체(copolymer) 및 이들의 조합으로 이루어진 군에서 선택되는 것이 사용될 수 있다. The polylactic acid resin may be selected from the group consisting of polylactic acid homopolymers, polylactic acid copolymers, and combinations thereof.
상기 폴리유산 중합체는 상기 L-유산, D-유산 및 이들의 조합으로 이루어진 군에서 선택되는 유산을 개환 중합하여 제조되는 중합체인 것이 좋다.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.
상기 폴리올레핀 수지는 고밀도 폴리에틸렌(high density polyethylene, HDPE) 수지, 선형 저밀도 폴리에틸렌(linear low density polyethylene, LLDPE) 수지, 폴리프로필렌 수지, 에틸렌-프로필렌 공중합체 수지, 에틸렌-비닐알코올 공중합체 수지 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있으며, 이 중 구체적으로는 폴리프로필렌 수지를 사용할 수 있다. 　이때 상기 고밀도 폴리에틸렌 수지는 0.94 내지 0.965의 밀도 범위를 가지는 것을 의미하며, 상기 선형 저밀도 폴리에틸렌 수지는 0.91 내지 0.94의 밀도 범위를 가지는 것을 의미한다. 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. In this case, the high density polyethylene resin means that it has a density range of 0.94 to 0.965, and the linear low density polyethylene resin means that it has a density range of 0.91 to 0.94.
상기 비닐계 공중합체 수지는 비닐계 중합체 5 내지 95 중량%를 고무질 중합체 5 내지 95 중량%에 그라프트 중합시킨 공중합체이다. 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.
상기 비닐계 중합체는 방향족 비닐 단량체, 아크릴계 단량체 및 이들의 조합으로 이루어진 군에서 선택되는 제1 비닐계 단량체 50 내지 95 중량%; 및 불포화 니트릴 단량체, 아크릴계 단량체 및 이들의 조합으로 이루어진 군에서 선택되는 제2 비닐계 단량체 5 내지 50 중량%로 이루어진 공중합체를 사용할 수 있다. 　이때 상기 제1 비닐계 단량체 및 제2 비닐계 단량체는 서로 다른 것이 사용된다. 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. In this case, the first vinyl monomer and the second vinyl monomer are different from each other.
상기 방향족 비닐 단량체로는 스티렌, C1 내지 C10의 알킬 치환 스티렌, 할로겐 치환 스티렌 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. 　상기 알킬 치환 스티렌의 구체적인 예로는 o-에틸 스티렌, m-에틸 스티렌, p-에틸 스티렌, α-메틸　스티렌 등을 들 수 있다. 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. Specific examples of the alkyl-substituted styrene include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, α-methyl styrene and the like.
상기 아크릴계 단량체로는 (메타)아크릴산 알킬 에스테르, (메타)아크릴산 에스테르 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. 　이때 상기 알킬은 C1 내지 C10의 알킬을 의미한다. 　상기 (메타)아크릴산 알킬 에스테르의 구체적인 예로는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트 등을 들 수 있으며, 이 중 좋게는 메틸(메타)아크릴레이트가 사용될 수 있다. The acrylic monomer may be selected from the group consisting of (meth) acrylic acid alkyl esters, (meth) acrylic acid esters, and combinations thereof. In this case, 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.
상기 불포화 니트릴 단량체로는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof.
상기 고무질 중합체는 부타디엔 고무, 아크릴 고무, 에틸렌/프로필렌 고무, 스티렌/부타디엔 고무, 아크릴로니트릴/부타디엔 고무, 이소프렌 고무, 에틸렌-프로필렌-디엔의 삼원 공중합체(EPDM) 고무, 폴리오가노실록산/폴리알킬(메타)아크릴레이트 고무 복합체 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.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.
상기 고무 변성 비닐계 그라프트 공중합체를 제조하는 방법은 이 분야의 통상의 지식을 가진 자에게 이미 잘 알려져 있는 것으로서, 유화중합, 현탁중합, 용액중합 또는 괴상중합 중 어느 방법이나 사용할 수 있고, 구체적인 예로는 고무질 중합체의 존재 하에 전술한 방향족 비닐 단량체를 투입하여 중합 개시제를 사용하여 유화중합 또는 괴상중합시키는 것을 들 수 있다.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.
상기 폴리에스테르 수지는 방향족 폴리에스테르 수지로서, 테레프탈산 또는 테레프탈산 알킬 에스테르와 2 내지 10개의 탄소 원자를 갖는 글리콜 성분으로부터 용융 중합에 의하여 축중합된 수지를 사용할 수 있다. 　이때 상기 알킬은 C1 내지 C10의 알킬을 의미한다. 　As the 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. In this case, the alkyl means C1 to C10 alkyl.
이러한 방향족 폴리에스테르 수지의 구체적인 예로는, 폴리에틸렌 테레프탈레이트 수지, 폴리트리메틸렌 테레프탈레이트 수지, 폴리부틸렌 테레프탈레이트 수지, 폴리헥사메틸렌 테레프탈레이트 수지, 폴리시클로헥산 디메틸렌 테레프탈레이트 수지, 이들 수지에 일부 다른 단량체를 혼합하여 비결정성으로 개질한 수지 및 이들의 조합으로 이루어진 군에서 선택되는 수지를 사용할 수 있으며, 이들 중에서 더 구체적으로는 폴리에틸렌 테레프탈레이트 수지, 폴리트리메틸렌 테레프탈레이트 수지, 폴리부틸렌 테레프탈레이트 수지, 비결정성 폴리에틸렌 테레프탈레이트 수지 등을 사용할 수 있다.Specific examples of such 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.
전술한 종류의 열가소성 수지는 단독으로 또는 둘 이상을 혼합하여 사용할 수 있다. 　구체적으로 두 종류의 열가소성 수지를 혼합하여 사용하는 경우, 1:9 내지 9:1의 비율로 혼합하여 사용할 수 있다. The above-mentioned 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.
상기 열가소성 수지는 상기 열가소성 수지 조성물 총량에 대하여 55　내지 95　중량%로 포함될 수 있고, 구체적으로는 70　내지 85 중량%로 포함될 수 있다. 　열가소성 수지가 상기 함량 범위 내로 포함되는 경우 강성, 내열성, 가공성 등이 우수하다.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.
　
(B) 인계 난연제로 전처리된 천연섬유 분말(B) Natural fiber powder pretreated with phosphorus flame retardant
상기 천연섬유 분말은 상기 열가소성 수지에 보강제로 포함되는 것으로서, 아마(flax), 대마(hemp), 황마(jute), 양마(kenaf), 대나무, 모시풀(ramie), 쿠라우아(curaua), 목분, 호두껍질 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. 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.
상기 천연섬유 분말을 열가소성 수지에 혼합함으로써 환경 친화적이고 우수한 강성 및 내열성을 가진 열가소성 수지 조성물을 얻을 수 있다. By mixing the natural fiber powder in a thermoplastic resin, it is possible to obtain a thermoplastic resin composition which is environmentally friendly and has excellent rigidity and heat resistance.
상기 천연섬유 분말은 셀룰로오스(cellulose),　리그닌(lignin)　및 세미셀룰로오스(semicellulose)로　구성된다. 　이 중 상기 리그닌은 방향족 고리(aromatic ring)가 다량 포함되어 있고 주사슬이 서로 연결되어 있는 가교(cross-linking) 구조를 가짐에 따라, 발화시 탄화(char) 층을 형성하기 쉬우므로 난연성을 기대할 수 있다.The natural fiber powder is composed of cellulose, lignin, and semicellulose. Of these, 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.
상기 천연섬유 분말은 평균길이가 0.01　내지 100 mm 일 수 있으며, 구체적으로는 0.1　내지 10　mm 일 수 있다. 　천연섬유 분말의 평균길이가 상기 범위 내인 경우　인장강도, 굴곡강도, 굴곡탄성율 등의 기계적 강도의 향상과 우수한 가공성 및 외관 특성이 나타날 수 있다.The natural fiber powder may have an average length of 0.01 to 100mm, specifically 0.1 구체적 to 10 mm. When 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.
상기 천연섬유 분말은 평균직경이 0.001　내지 50 ㎛ 일 수 있으며, 구체적으로는 0.01　내지　5　㎛ 일 수 있다. 　천연섬유 분말의 평균직경이 상기 범위 내인 경우 가공성 및 표면 광택이 우수하다. The natural fiber powder may have an average diameter of 0.001 to 50µm, specifically 0.01 to 5 µm. When the average diameter of the natural fiber powder is in the above range is excellent in workability and surface gloss.
일 구현예에 따르면, 상기 천연섬유 분말은 인계 난연제로 전처리되어 사용될 수 있다. According to one embodiment, the natural fiber powder may be pretreated with a phosphorus-based flame retardant.
상기 전처리는 천연섬유 분말에 인계 난연제가 충분히 스며들도록, 인계 난연제, 구체적으로는 인계 난연제 용액에 천연섬유 분말을 함침하여 수행된다. 　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.
상기 인계 난연제는 액상인 것이 사용될 수 있다. 　전술한 천연섬유 분말은 많은 기공을 가진 구조로서, 전처리는 액상인 인계 난연제가 기공 속으로 스며들면서 수행되며, 이에 따라 난연 효율성을 증대시킬 수 있다. 　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.
또한 액상인 인계 난연제가 고상인 경우보다 천연섬유 분말에 고루 스며들어 섞일 수 있다. 　인계 난연제로 전처리함으로써 천연섬유 분말의 성분인 셀룰로오스와 인계 난연제의 화합물이 분자간 인력에 의해 결합하게 되는데, 액상인 인계 난연제의 경우 고상인 경우보다 상기 결합의 효율성이 우수하다. In addition, the liquid phosphorous flame retardant may be mixed with the natural fiber powder evenly when the solid phase. By pretreatment with 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.
상기 인계 난연제로는 포스페이트(phosphate) 화합물, 포스피네이트(phosphinate) 화합물, 포스포네이트(phosphonate) 화합물, 포스포나이트(phosphonite) 화합물, 포스파이트(phosphite) 화합물 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. 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.
상기 포스페이트 화합물의 구체적인 예로는, 트리페닐포스페이트, 트리크레실포스페이트(tricresyl phosphate), 크레실디페닐포스페이트, 트리크실릴포스페이트(trixylyl phosphate), 트리(2,4,6-트리메틸페닐)포스페이트, 트리(2,4-디터셔리부틸페닐)포스페이트, 트리(2,6-디터셔리부틸페닐)포스페이트, 레조시놀비스(디페닐포스페이트), 히드로퀴논비스(디페닐포스페이트), 비스페놀A-비스(디페닐포스페이트), 레조시놀비스(2,6-디터셔리부틸페닐포스페이트), 히드로퀴논비스(2,6-디메틸페닐포스페이트) 등을 들 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 　 Specific examples of the phosphate compound 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. 　
상기 포스피네이트 화합물의 구체적인 예로는, 알루미늄 디에틸포스피네이트(aluminum diethylphosphinate), 알루미늄 메틸에틸포스피네이트(aluminum methylethylphosphinate) 등을 들 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. Specific examples of the phosphinate compound include aluminum diethylphosphinate, aluminum methylethylphosphinate, and the like, and these may be used alone or in combination of two or more thereof.
상기 포스파이트 화합물의 구체적인 예로는, 트리스(2,4-t-부틸 페닐)포스파이트, 트리스(노닐페닐)포스파이트 등을 들 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. Specific examples of the phosphite compound 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.
상기 종류의 인계 난연제는 전처리시 천연섬유 분말의 구성 성분 중 셀룰로오스와 물리적으로 결합함에 따라 기공 속을 채우고 있다가 발화시 천연섬유 분말 및 열가소성 수지의 탄화(char) 형성을 촉진하게 되며, 그에 따라 난연 효율성이 증가될 수 있다. 　즉, 인계 난연제로 전처리된 천연섬유 분말을 사용할 경우 난연성의 시너지 효과를 기대할 수 있다.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.
이와 같이 일 구현예에 따르면, 리그닌을 정제하지 않은 천연섬유 분말을 인계 난연제로 전처리하여 난연 효율성을 증대시킬 수 있다. As such, according to one embodiment, the natural fiber powder without lignin purification may be pretreated with a phosphorus-based flame retardant to increase the flame retardant efficiency.
상기 전처리는 상기 천연섬유 분말 100 중량부에 대하여 상기 인계 난연제 5 내지 40 중량부, 구체적으로는 10 내지 35 중량부의 함량으로 천연섬유 분말 및 인계 난연제를 혼합함으로써 수행할 수 있다. 　상기 함량 비율로 혼합하는 경우 난연성이 우수하면서 다른 기본 물성을 저해하지 않는다.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. When mixed in the content ratio is excellent flame retardancy and does not inhibit other basic physical properties.
상기 인계 난연제로 전처리된 천연섬유 분말은　상기 열가소성 수지 조성물 총량에 대하여 5 내지 45 중량%로 포함될 수 있고, 구체적으로는 5　내지 25 중량%로 포함될 수 있다. 　인계 난연제로 전처리된 천연섬유 분말이 상기 범위 내로 포함되는 경우, 난연성 뿐만 아니라 강성, 내열성 및 가공성이 모두 우수하다. 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%. When 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.
　
(C) 난연제(C) flame retardant
일 구현예에 따른 열가소성 수지 조성물은 난연성을 극대화하기 위해 난연제를 더 포함할 수 있다.The thermoplastic resin composition according to one embodiment may further include a flame retardant to maximize flame retardancy.
상기 난연제는 특별히 한정되는 것은 아니며, 구체적으로는 인계 난연제, 질소 화합물계 난연제, 실리콘계 난연제, 무기계 난연제 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. 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.
상기 인계 난연제로는 유기 인계 화합물, 적색 인 등을 들 수 있다.As said phosphorus flame retardant, an organophosphorus compound, red phosphorus, etc. are mentioned.
상기 유기 인계 화합물로는 포스페이트(phosphate) 화합물, 포스피네이트(phosphinate) 화합물, 포스포네이트(phosphonate) 화합물, 포스포나이트(phosphonite) 화합물, 포스파이트(phosphite) 화합물, 포스파겐(phosphagen) 화합물 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. 　각 화합물의 구체적인 예는 위에서 언급한 바와 같다.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.
상기 질소 화합물계 난연제로는 지방족 아민 화합물, 방향족 아민 화합물, 함질소 복소환 화합물, 시안(cyan) 화합물, 지방족 아미드, 방향족 아미드, 요소, 티오(thio) 요소 등을 들 수 있다. Examples of the nitrogen compound-based flame retardant include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyan compounds, aliphatic amides, aromatic amides, urea and thio urea.
상기 지방족 아민 화합물로는 에틸 아민, 부틸 아민, 디에틸 아민, 에틸렌 디아민, 트리에틸렌 테트라민, 디아미노 사이클로헥산, 디아미노 사이클로옥탄, 구아닌, 디아미노 퓨린, 트리피리딘, 트리아진 화합물 등을 들 수 있다. Examples of the aliphatic amine compounds include ethyl amine, butyl amine, diethyl amine, ethylene diamine, triethylene tetramine, diamino cyclohexane, diamino cyclooctane, guanine, diamino purine, tripyridine, and triazine compounds. have.
상기 실리콘계 난연제로는 실리콘 수지 또는 실리콘 오일을 들 수 있다.The silicone flame retardant may be a silicone resin or silicone oil.
상기 실리콘 수지는 RSiO3/2, RSiO, RSiO1/2의 단위를 조합시킬 수 있는 삼차원 망상 구조를 가지는 수지 등을 들 수 있다. 　여기에서 R은 메틸기, 에틸기, 프로필기 등의 C1 내지 C10의 알킬기, 방향족기 또는 상기 치환기에 비닐기를 함유한 치환기를 나타낸다.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.
상기 실리콘 오일은 폴리 디메틸 실록산 및 폴리 디메틸 실록산의 측쇄 또는 말단의 적어도 1개의 메틸기가 수소, 알킬기, 사이클로헥실기, 페닐기, 벤질기, 에폭시기, 폴리에테르기, 카르복실기, 메르캅토기, 클로로알킬기, 알킬 알코올 에스테르기, 알코올기, 알릴기, 비닐기, 트리플루오로 메틸기 및 이들의 조합으로 이루어진 군에서 선택되는 것에 의해 변성되는 개질 폴리실록산 또는 이러한 혼합물이다.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.
상기 무기계 난연제로서는 산화규소(SiO2), 수산화마그네슘, 수산화알루미늄, 삼산화안티몬, 오산화안티몬, 안티몬, 탄산나트륨, 히드록시 주석산 아연, 주석산 아연, 메타주석산, 황산 아연, 산화 아연, 산화 제1 철, 산화 제2 철, 산화 제1 주석(SnO), 산화 제2 주석(SnO2), 붕산 아연, 붕산 칼슘, 붕산 암모늄, 옥타몰리브덴 산 암모늄, 텅스텐 산의 금속염, 텅스텐과 메탈로이드(metalloid)와의 복합 산화물, 지르코늄계 화합물, 구아니딘계 화합물, 흑연, 활석, 팽창성 흑연 등을 들 수 있으며, 이 중 좋게는 수산화알루미늄 및 활석이 사용될 수 있다. Examples of the inorganic flame retardant 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 Ferric oxide, ferrous tin oxide (SnO), ferric tin (SnO 2 ), zinc borate, calcium borate, ammonium borate, ammonium octamolybdate, metal salts of tungstic acid, complex oxides of tungsten and metalloid , Zirconium compounds, guanidine compounds, graphite, talc, expandable graphite, and the like, and among these, aluminum hydroxide and talc may be used.
상기 난연제는　상기 열가소성 수지 조성물 100 중량부에 대하여 1 내지 30 중량부로 포함될 수 있고, 구체적으로는 5　내지 20 중량부로 포함될 수 있다. 　난연제가 상기 범위 내로 포함되는 경우 난연성이 우수할 뿐만 아니라, 강성 및 내열성 모두 우수하다. 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.
　
(D) 충격보강제(D) impact modifier
일 구현예에 따른 열가소성 수지 조성물은 충격보강제를 더 포함할 수 있다.The thermoplastic resin composition according to one embodiment may further include an impact modifier.
상기 충격보강제는 코어-쉘 구조의 공중합체, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.The impact modifier may be selected from the group consisting of a core-shell copolymer, an olefin copolymer and a combination thereof.
상기 코어-쉘 구조의 공중합체는 고무의 코어 구조에 불포화 단량체가 그라프트되어 딱딱한 쉘을 형성함으로써 코어-쉘 구조를 갖는 것으로, 디엔계　단량체,　아크릴계　단량체,　실리콘계　단량체 및 이들의 조합으로 이루어진 군에서 선택되는 단량체를 중합한 고무질 중합체에, 아크릴계 단량체, 방향족 비닐 단량체, 불포화 니트릴 단량체, 이들 1종 이상의 단량체로부터 형성되는 중합체 및 이들의 조합으로 이루어진 군에서 선택되는 불포화 화합물이 그라프트된 공중합체이다.The core-shell copolymer has a core-shell structure by grafting an unsaturated monomer to a rubber core structure to form a hard shell. In the group consisting of diene monomers, acrylic monomers, silicone monomers, and combinations thereof 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.
상기 디엔계　단량체로는　C4 내지 C6의 부타디엔,　이소프렌　등을 들 수 있으며, 그　중　좋게는 부타디엔이 사용될 수 있다. 　상기 디엔계 단량체를 중합한 고무질 중합체의 구체적인 예로는 부타디엔 고무, 아크릴 고무, 스티렌/부타디엔 고무, 아크릴로니트릴/부타디엔 고무, 이소프렌 고무, 에틸렌-프로필렌-디엔의 삼원공중합체(EPDM) 등이 있다.Examples of the diene-based monomers 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).
상기 아크릴계　단량체로는　메틸(메타)아크릴레이트,　에틸(메타)아크릴레이트,　n-프로필(메타)아크릴레이트,　n-부틸(메타)아크릴레이트,　2-에틸헥실(메타)아크릴레이트,　헥실(메타)아크릴레이트,　2-에틸헥실(메타)아크릴레이트 등을 들 수 있다. 　이때, 에틸렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 1,3-부틸렌글리콜디(메타)아크릴레이트, 1,4-부틸렌글리콜디(메타)아크릴레이트, 알릴(메타)아크릴레이트, 트리알릴시아누레이트 등의 경화제를 사용할 수 있다.　Examples of the acrylic monomers 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. At this time, 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.
상기 실리콘계　단량체로는　헥사메틸시클로트리실록산,　옥타메틸시클로테트라실록산,　데카메틸시클로펜타실록산,　도데카메틸시클로헥사실록산,　트리메틸트리페닐시클로트리실록산,　테트라메틸테트라페닐시클로테트라실록산, 옥타페닐시클로테트라실록산 및 이들의 조합으로 이루어진 군에서 선택되는 시클로실록산 화합물을 사용할 수 있다. 　이때, 트리메톡시메틸실란, 트리에톡시페닐실란, 테트라메톡시실란, 테트라에톡시실란 등의 경화제를 사용할 수 있다.Examples of the silicone-based monomers include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decademethylmethylcyclopentasiloxane, decedocamethylcyclohexasiloxane, dectrimethyltriphenylcyclotrisiloxane, tet tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. And a cyclosiloxane compound selected from the group consisting of a combination thereof. At this time, curing agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane and tetraethoxysilane can be used.
상기 고무질 중합체의 고무 평균입경은 0.4 내지 1 ㎛ 인 것이 내충격성과 착색성 밸런스 유지 면에서 좋다. The rubber average particle diameter of the rubbery polymer is preferably 0.4 to 1 µm in terms of impact resistance and color balance maintenance.
상기 고무질 중합체의 함량은 상기 코어-쉘 구조의 공중합체 총량에 대하여 20 내지 80 중량%로 포함될 수 있으며, 상기 범위로 포함될 경우 충격 보강 효과 및 내열성 향상을 극대화할 수 있으며, 유동성도 현저히 개선된다.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. When 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.
상기 불포화 화합물 중 아크릴계 단량체로는 (메타)아크릴산 알킬 에스테르, (메타)아크릴산 에스테르 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. 　이때 상기 알킬은 C1 내지 C10의 알킬을 의미하는 것으로서, 상기 (메타)아크릴산 알킬 에스테르의 구체적인 예로는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트 등을 들 수 있으며, 이 중 좋게는 메틸(메타)아크릴레이트를 사용할 수 있다. 　Among the unsaturated compounds, an acrylic monomer may be selected from the group consisting of (meth) acrylic acid alkyl esters, (meth) acrylic acid esters, and combinations thereof. In this case, the alkyl means C1 to C10 alkyl, and 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.
상기 불포화 화합물 중 방향족 비닐 단량체로는 스티렌, C1 내지 C10의 알킬 치환 스티렌, 할로겐 치환 스티렌 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다. 　상기 알킬 치환 스티렌의 구체적인 예로는 o-에틸 스티렌, m-에틸 스티렌, p-에틸 스티렌, α-메틸 스티렌 등을 들 수 있다.Among the unsaturated compounds, 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. Specific examples of the alkyl substituted styrene include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, α-methyl styrene, and the like.
상기 불포화 화합물 중 불포화 니트릴 단량체로는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.Among the unsaturated compounds, unsaturated nitrile monomers may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof.
상기 불포화 화합물 중 이들 1종 이상의 단량체로부터 형성되는 중합체로는 폴리메틸메타크릴레이트 등을 들 수 있다. Polymethyl methacrylate etc. are mentioned as a polymer formed from these 1 or more types of monomers in the said unsaturated compound.
상기 코어-쉘 구조의 공중합체는 평균입자크기가 0.1 내지 0.5 ㎛　일 수 있으며, 상기 범위의 평균입자크기를 가지는 경우 폴리에스테르 매트릭스에 분산이 잘되어 외부에서 충격이 가해질 때, 그 충격 흡수가 용이하게 되어 충격보강 효과가 상승하게 된다. The core-shell copolymer may have an average particle size of 0.1 to 0.5 μm 경우, 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.
상기 올레핀계 공중합체는 올레핀계 단량체 및 아크릴계 단량체의 공중합체를 사용할 수 있다.The olefin copolymer may be a copolymer of an olefin monomer and an acrylic monomer.
상기 올레핀계 단량체로는 에틸렌, 프로필렌, 이소프로필렌, 부틸렌, 이소부틸렌 등을 들 수 있으며, 이들을 단독으로 또는 혼합하여 사용할 수 있다.Ethylene, propylene, isopropylene, butylene, isobutylene, etc. are mentioned as said olefin monomer, These can be used individually or in mixture.
상기 아크릴계 단량체로는 (메타)아크릴산 알킬 에스테르 또는 (메타)아크릴산 에스테르를 사용한다. 　이때 상기 알킬은 C1 내지 C10의 알킬을 의미하는 것으로서, 상기 (메타)아크릴산 알킬 에스테르의 구체적인 예로는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트 등을 들 수 있으며, 이 중 좋게는 메틸(메타)아크릴레이트를 사용할 수 있다. 　As the acrylic monomer, (meth) acrylic acid alkyl ester or (meth) acrylic acid ester is used. In this case, the alkyl means C1 to C10 alkyl, and 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.
상기 올레핀계 공중합체는 일반적인 올레핀 중합 촉매인 지글러-나타 촉매를 이용하여 제조할 수 있으며, 더욱 선택적인 구조를 만들기 위해서는 메탈로센계 촉매를 이용하여 제조할 수 있다. 　이 때 열가소성 수지와의 분산성을 향상시키기 위하여 무수말레인산 등과 같은 관능기를 올레핀계 공중합체에 그라프팅 반응시킬 수도 있다.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.
상기 충격보강제는 상기 열가소성 수지 조성물 100 중량부에 대하여　1 내지 20 중량부로 포함될 수 있으며, 구체적으로는 5　내지 15　중량부로 포함될 수 있다. 　충격보강제가 상기 범위 내로 포함되는 경우 충격 보강 효과 및 내열도의 상승을 극대화할 수 있으며, 유동성도 향상되어 사출 성형성이 개선될 수 있다. 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. When 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.
　
(E) 기타 첨가제(E) other additives
일 구현예에 따른 열가소성 수지 조성물은 각 용도에 따라 항균제, 열안정제, 산화방지제, 이형제, 광안정제, 무기물 첨가제, 계면활성제, 커플링제, 가소제, 혼화제, 착색제, 안정제, 활제, 정전기방지제, 조색제, 방염제, 내후제, 자외선 흡수제, 자외선 차단제, 난연제, 충전제, 핵 형성제, 접착 조제, 점착제 및 이들의 혼합물로 이루어진 군에서 선택되는 첨가제를　더　포함할 수 있다. 　Thermoplastic resin composition according to one embodiment 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.
상기 산화방지제로는 페놀형, 포스파이트(phosphite)형, 티오에테르형 또는 아민형 산화방지제를 사용할 수 있으며, 상기 이형제로는 불소 함유 중합체, 실리콘 오일, 스테아린산(stearic acid)의 금속염, 몬탄산(montanic acid)의 금속염, 몬탄산 에스테르 왁스 또는 폴리에틸렌 왁스를 사용할 수 있다. 　또한 상기 내후제로는 벤조페논형 또는 아민형 내후제를 사용할 수 있고, 상기 착색제로는 염료 또는 안료를 사용할 수 있다. 　또한 상기 자외선 차단제로는 산화티탄(TiO2)　또는 카본블랙을 사용할 수 있고, 상기 충전제로는 유리섬유, 탄소섬유, 실리카, 마이카, 알루미나, 점토, 탄산칼슘, 황산칼슘 또는 유리 비드를 사용할 수 있으며, 상기와 같은 충전제를 첨가할 경우 기계적 강도 및 내열성 등의 물성을 향상시킬 수 있다. 　또한 상기 핵 형성제로는 탈크 또는 클레이를 사용할 수 있다.　As 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. In addition, 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, and the filler may be glass fiber, carbon fiber, silica, mica, alumina, clay, calcium carbonate, calcium sulfate, or glass beads. When the filler is added as described above, physical properties such as mechanical strength and heat resistance may be improved. In addition, talc or clay may be used as the nucleating agent.
상기 첨가제는 상기 열가소성 수지 조성물 100 중량부에 대하여　0.1 내지 30 중량부로 포함될 수 있다. 　첨가제가 상기 범위 내로 포함되는 경우 각 용도에 따른 첨가제의 효과를 얻을 수 있으며 우수한 기계적 물성 및 향상된 표면의 외관을 얻을 수 있다.The additive may be included in 0.1 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin composition. When 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.
　
일 구현예에 따른 열가소성 수지 조성물은 공지의 방법으로 제조될 수 있다. 　예를 들면, 상술한 본 발명의 구성 성분과 첨가제를 혼합한 후에, 압출기 내에서 용융 압출하고 펠렛 형태로 제조할 수 있다. 　The thermoplastic resin composition according to one embodiment 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.
본 발명의 다른 일 구현예에 따르면, 전술한 열가소성 수지 조성물을 성형하여 제조한 성형품을 제공한다. 　상기 열가소성 수지 조성물은 강성, 내열성, 난연성　등이 중요시하게 요구되는 분야의 성형제품, 예를 들면, 자동차, 기계 부품, 전지전자 부품, 통신기기, 건축재, 사무기기, 잡화 등과 같은 성형품 재료에　유용하게 적용될 수 있다. According to another embodiment of the present invention, a molded article manufactured by molding the aforementioned thermoplastic resin composition is provided. The 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.
이하, 본 발명의 바람직한 실시예를 기재한다.　　다만, 하기의 실시예는 본 발명의 바람직한 일 실시예일뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다. Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.
[실시예] 　EXAMPLE
일 구현예에 따른 열가소성 수지 조성물의 제조에 사용되는 각 구성 성분은 다음과 같다. 　Each component used in the preparation of the thermoplastic resin composition according to one embodiment is as follows.
(A) 열가소성 수지(A) thermoplastic resin
(A-1) 폴리유산 수지(A-1) polylactic acid resin
미국　NatureWorks　LLC에서　제조된　4032D를　사용하였다.We used the US4032D manufactured by NatureWorks LLC in the United States.
(A-2) 폴리카보네이트 수지(A-2) polycarbonate resin
LG-Dow사의 CALIBRE 1080DVD　제품을 사용하였다.LG-Dow's CALIBER 1080DVD was used.
(B) 인계 난연제로 전처리된 천연섬유 분말(B) Natural fiber powder pretreated with phosphorus flame retardant
인계 난연제(Daihachi사의 CR-741 제품)로 전처리된 목분을 사용하였다. 　이때 전처리는 목분을 상기 목분 100 중량부에 대하여 인계 난연제 용액 20 중량부에 함침하여, 50℃ 오븐에서 5시간 건조시켜 수행하였다. 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 ℃ oven.
(B') 아무 처리도 되지 않은 목분을 사용하였다.(B ') Untreated wood flour was used.
(B'') 실란 커플링제(SILQUEST사의 A-187 SILANE)로 전처리된 목분을 사용하였다. 　이때 목분을 실란 커플링제 수용액에 1분 담궜다가 꺼낸 후 50℃ 오븐에서 5시간 건조시켰다.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.
(C) 난연제(C) flame retardant
Daihachi사의 CR-741 제품을 사용하였다.Daihachi CR-741 was used.
(D) 충격보강제(D) impact modifier
Mitsubishi Rayon사의 METABLEN C-223A을 사용하였다.Mitsubishi Rayon's METABLEN C-223A was used.
(E) 첨가제(E) additive
산화방지제로서 Ciba사의 Irganox 1076을 사용하였다.Ciba Irganox 1076 was used as an antioxidant.
　
실시예 1 내지 5 및 비교예 1 내지 5Examples 1-5 and Comparative Examples 1-5
상기에서 언급한 성분들을　하기 표 1에 나타낸 바와 같은 함량으로 각각 혼합하여 열가소성 수지　조성물을 제조하고, 통상의 이축 압출기에서 190 내지 220℃의 온도범위로 압출한 후, 압출물을 펠렛 형태로 제조하였다. The above-mentioned components were mixed in the amounts as shown in Table 1, respectively, to prepare 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. .
상기 실시예 1 내지 5 및 비교예 1 내지 5에 따라 제조된 시편의 각종 물성을 아래와 같은 방법으로 측정하였으며, 그 결과를 하기 표 1에 나타내었다.Various physical properties of the specimens prepared according to Examples 1 to 5 and Comparative Examples 1 to 5 were measured by the following method, and the results are shown in Table 1 below.
(1) 난연성: UL-94 V Vertical Burning Test에 준하여 측정하였다(2mm 두께 시편 기준).(1) Flame retardancy: measured according to the UL-94 V Vertical Burning Test (based on 2mm thick specimen).
(2) 굴곡탄성율: ASTM D790에 준하여 측정하였다. (2) Flexural modulus: Measured according to ASTM D790.
(3) 열변형온도(HDT):　ASTM　D648에　준하여　측정하였다(18.56 kgf/cm2　하중).(3) Heat Deflection Temperature (HDT): Measured according to ASTM D648 (18.56 kgf / cm 2 load).
(4) 가공성: 압출되어 나오는 스트랜드의 끊김은 없는지 육안으로 관찰함.(4) Processability: Observe visually whether there is any breakage of the extruded strand.
　
표 1
　 단위 실시예 비교예
1 2 3 4 5 1 2 3 4 5
(A) (A-1) 중량% - - 15 15 - - - - - 15
(A-2) 중량% 90 70 75 55 60 90 96 50 90 85
(B) 중량% 10 30 10 30 40 - 4 50 - -
(B') 중량% - - - - - 10 - - - -
(B'') 중량% - - - - - - - - 10 -
(C) 중량부* 7 7 15 15 - 7 7 7 7 15
(D) 중량부* 4 4 4 4 4 4 4 4 4 4
(E) 중량부* 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
난연성** - V-0 V-0 V-0 V-0 V-1 fail fail 압출불가 fail V-2
굴곡탄성율　 kgf/cm2 23000 25000 27000 28000 29000 25500 23000 26000 24000
열변형온도　 ℃ 120 125 105 103 108 127 130 125 107
가공성 - 양호 양호 양호 양호 양호 양호 양호 양호 양호
Table 1
unit EXAMPLE Comparative example
One 2 3 4 5 One 2 3 4 5
(A) (A-1) weight% - - 15 15 - - - - - 15
(A-2) weight% 90 70 75 55 60 90 96 50 90 85
(B) weight% 10 30 10 30 40 - 4 50 - -
(B ') weight% - - - - - 10 - - - -
(B '') weight% - - - - - - - - 10 -
(C) Parts by weight * 7 7 15 15 - 7 7 7 7 15
(D) Parts by weight * 4 4 4 4 4 4 4 4 4 4
(E) Parts by weight * 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Flame Retardant ** - V-0 V-0 V-0 V-0 V-1 fail fail Non-extrusion fail V-2
Flexural modulus kgf / cm 2 23000 25000 27000 28000 29000 25500 23000 26000 24000
Heat deflection temperature ℃ 120 125 105 103 108 127 130 125 107
Machinability - Good Good Good Good Good Good Good Good Good
* 중량부는 (A), 그리고　(B), (B') 또는 (B'')의 총량 100 중량부를 기준으로 나타낸 함량 단위이다.* Parts by weight are content units based on 100 parts by weight of (A) and 100 parts by weight of (B), (B ') or (B' ').
** 난연성: 난연성의 등급은 V-0 ＞ V-1 ＞ V-2 ＞ fail 와 같다.** Flame retardancy: The flame retardancy is the same as V-0> V-1> V-2> fail.
상기 표 1을 통하여, 일 구현예에 따라 열가소성 수지 및 인계 난연제로 전처리된 천연섬유 분말을 사용한 실시예 1 내지 5의 경우, 아무 처리도 되지 않은 천연섬유 분말을 사용한 비교예 1, 인계 난연제로 전처리된 천연섬유 분말을 일 구현예에 따른 범위를 벗어난 함량으로 사용한 비교예 2 및 3, 실란 커플링제로 전처리된 천연섬유 분말을 사용한 비교예 4, 그리고 인계 난연제로 전처리된 천연섬유 분말을 전혀 사용하지 않은 비교예 5의 경우와 비교하여 우수한 강성 및 내열성을 유지하면서 난연성이 현저히 증대되는 것을 확인할 수 있다. Through Table 1, in the case of Examples 1 to 5 using the natural fiber powder pre-treated with a thermoplastic resin and phosphorus-based flame retardant according to one embodiment, 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.
특히 인계 난연제로 전처리된 천연섬유 분말을 일 구현예에 따른 함량 범위를 벗어나 과량으로 사용한 비교예 3의 경우는 압출이 불가하여 어떤 물성도 얻을 수 없음을 확인할 수 있다.In particular, in the case of Comparative Example 3 using an excess of the natural fiber powder pretreated with a phosphorus-based flame retardant in excess of the content range according to one embodiment, it can be confirmed that no physical properties can be obtained because extrusion is impossible.
본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다.　　그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다.　　　The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (15)

  1. (A) 열가소성 수지 55　내지 95　중량%; 및(A) 55 to 95% by weight of the thermoplastic resin; And
    (B) 인계 난연제로 전처리된 천연섬유 분말 5 내지 45 중량%를 포함하는 열가소성 수지 조성물.(B) a thermoplastic resin composition comprising 5 to 45% by weight of the natural fiber powder pretreated with a phosphorus-based flame retardant.
  2. 제1항에 있어서,The method of claim 1,
    상기 열가소성 수지는 폴리카보네이트 수지, 폴리유산 수지, 폴리올레핀 수지, 비닐계 공중합체 수지, 폴리에스테르 수지, 아크릴계 수지, 액정 고분자, 폴리페닐렌술파이드 수지, 폴리아세탈 수지, 폴리페닐렌옥사이드 수지, 폴리술폰 수지, 폴리에테르 술폰 수지, 폴리에테르케톤 수지, 폴리에테르이미드 수지 및 이들의 조합으로 이루어진 군에서 선택되는 것인 열가소성 수지 조성물.The thermoplastic resin may be 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 , A polyether sulfone resin, a polyether ketone resin, a polyetherimide resin, and a combination thereof.
  3. 제1항에 있어서,The method of claim 1,
    상기 열가소성 수지는 용융점(Tm) 또는 결정화온도(Tc)가 230℃ 이하인 것인 열가소성 수지 조성물.The thermoplastic resin has a melting point (Tm) or crystallization temperature (Tc) is 230 ℃ or less.
  4. 제1항에 있어서,The method of claim 1,
    상기 천연섬유 분말은 아마(flax), 대마(hemp), 황마(jute), 양마(kenaf), 대나무, 모시풀(ramie), 쿠라우아(curaua), 목분, 호두껍질 및 이들의 조합으로 이루어진 군에서 선택되는 것인 열가소성 수지 조성물.The natural fiber powder in the group consisting of flax, hemp, jute, jute, kenaf, bamboo, ramie, curaua, wood flour, walnut shells and combinations thereof The thermoplastic resin composition is selected.
  5. 제1항에 있어서,The method of claim 1,
    상기 인계 난연제는 액상인 것인 열가소성 수지 조성물.The phosphorous flame retardant is a thermoplastic resin composition.
  6. 제1항에 있어서,The method of claim 1,
    상기 인계 난연제는 포스페이트(phosphate) 화합물, 포스피네이트(phosphinate) 화합물, 포스포네이트(phosphonate) 화합물, 포스포나이트(phosphonite) 화합물, 포스파이트(phosphite) 화합물 및 이들의 조합으로 이루어진 군에서 선택되는 것인 열가소성 수지 조성물. The phosphorus flame retardant is selected from the group consisting of phosphate compounds, phosphinate compounds, phosphonate compounds, phosphonite compounds, phosphite compounds, and combinations thereof The thermoplastic resin composition.
  7. 제1항에 있어서,The method of claim 1,
    상기 전처리는 상기 인계 난연제에 상기 천연섬유 분말을 함침하여 수행되는 것인 열가소성 수지 조성물. The pretreatment is carried out by impregnating the natural fiber powder in the phosphorus-based flame retardant.
  8. 제1항에 있어서,The method of claim 1,
    상기 전처리는 상기 천연섬유 분말 100 중량부에 대하여 상기 인계 난연제 5 내지 40 중량부로 수행되는 것인 열가소성 수지 조성물.The pretreatment is performed with 5 to 40 parts by weight of the phosphorus-based flame retardant based on 100 parts by weight of the natural fiber powder.
  9. 제1항에 있어서,The method of claim 1,
    상기 열가소성 수지 조성물은 상기 열가소성 수지 조성물 100 중량부에 대하여 (C) 난연제 1 내지 30 중량부를 더 포함하는 것인 열가소성 수지 조성물.The thermoplastic resin composition further comprises 1 to 30 parts by weight of (C) flame retardant based on 100 parts by weight of the thermoplastic resin composition.
  10. 제9항에 있어서,The method of claim 9,
    상기 난연제는 인계 난연제, 질소 화합물계 난연제, 실리콘계 난연제, 무기계 난연제 및 이들의 조합으로 이루어진 군에서 선택되는 것인 열가소성 수지 조성물.The flame retardant is a thermoplastic resin composition selected from the group consisting of phosphorus flame retardant, nitrogen compound flame retardant, silicone flame retardant, inorganic flame retardant and combinations thereof.
  11. 제1항에 있어서,The method of claim 1,
    상기 열가소성 수지 조성물은 상기 열가소성 수지 조성물 100 중량부에 대하여 (D) 충격보강제 1 내지 20 중량부를 더 포함하는 것인 열가소성 수지 조성물.The thermoplastic resin composition further comprises 1 to 20 parts by weight of the impact modifier (D) based on 100 parts by weight of the thermoplastic resin composition.
  12. 제11항에 있어서,The method of claim 11,
    상기 충격보강제는 코어-쉘 구조의 공중합체, 올레핀계 공중합체 및 이들의 조합으로 이루어진 군에서 선택되는 것인 열가소성 수지 조성물.The impact modifier is selected from the group consisting of a core-shell copolymer, an olefin copolymer and a combination thereof.
  13. 제12항에 있어서,The method of claim 12,
    상기 코어-쉘 구조의 공중합체는 디엔계　단량체,　아크릴계　단량체,　실리콘계　단량체 및 이들의 조합으로 이루어진 군에서 선택되는 단량체를 중합한 고무질 중합체에, 아크릴계 단량체, 방향족 비닐 단량체, 불포화 니트릴 단량체, 이들 1종 이상의 단량체로부터 형성되는 중합체 및 이들의 조합으로 이루어진 군에서 선택되는 불포화 화합물이 그라프트된 공중합체이고,The core-shell copolymer is a rubbery polymer obtained by polymerizing a monomer selected from the group consisting of diene-based monomers, acrylic-based monomers, silicone-based monomers, and combinations thereof, acrylic monomers, aromatic vinyl monomers, unsaturated nitrile monomers, and one of these. An unsaturated compound selected from the group consisting of polymers and combinations thereof formed from the above monomers is a grafted copolymer,
    상기 올레핀계 공중합체는 올레핀계 단량체 및 아크릴계 단량체의 공중합체인 것인 열가소성 수지 조성물.The olefin copolymer is a thermoplastic resin composition is a copolymer of an olefin monomer and an acrylic monomer.
  14. 제1항에 있어서,The method of claim 1,
    상기 열가소성 수지 조성물은 항균제, 열안정제, 산화방지제, 이형제, 광안정제, 무기물 첨가제, 계면활성제, 커플링제, 가소제, 혼화제, 착색제, 안정제, 활제, 정전기방지제, 조색제, 방염제, 내후제, 자외선 흡수제, 자외선 차단제, 난연제, 충전제, 핵 형성제, 접착 조제, 점착제 및 이들의 혼합물로 이루어진 군에서 선택되는 (E) 첨가제를 더 포함하는 것인 열가소성 수지 조성물.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, a admixture, a colorant, a stabilizer, a lubricant, an antistatic agent, a colorant, a flame retardant, a weather agent, a ultraviolet absorber, A thermoplastic resin composition further comprising (E) an additive selected from the group consisting of a sunscreen, a flame retardant, a filler, a nucleating agent, an adhesion aid, an adhesive, and a mixture thereof.
  15. 제1항 내지 제14항 중 어느 한 항의 열가소성 수지 조성물로부터 제조된 성형품.The molded article manufactured from the thermoplastic resin composition of any one of Claims 1-14.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015170803A1 (en) * 2014-05-07 2015-11-12 삼성에스디아이 주식회사 Polycarbonate resin composition and molded articles prepared therefrom
CN105419264A (en) * 2014-09-12 2016-03-23 韩华道达尔有限公司 Flame-retardant polylactic resin composition
CN108976471A (en) * 2018-06-27 2018-12-11 杭州本松新材料技术股份有限公司 Fire retardant compound system and halogen-free flame-retardant resin based composites comprising it

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101464250B1 (en) * 2011-12-20 2014-11-24 제일모직주식회사 Thermoplastic Resin Composition With Improved White Turbidity Phenomenon at Low Temperature
KR101400737B1 (en) * 2012-03-28 2014-05-29 (주)썬패치테크노 UV-curable pressure sensitive adhesive composition for repair and reinforcement of the facility
KR101575458B1 (en) 2014-03-07 2015-12-07 현대자동차주식회사 Polyolefin-natural fiber composites for extrusion molding
KR101583924B1 (en) * 2014-05-09 2016-01-08 현대자동차주식회사 Polypropxlene and polylactic acid composites and method of manufacturing the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003231816A (en) * 2002-02-12 2003-08-19 Asahi Kasei Corp Flame-retardant polymer composition molded form
KR20080025072A (en) * 2005-07-08 2008-03-19 도레이 가부시끼가이샤 Resin composition and molded article comprising the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003231816A (en) * 2002-02-12 2003-08-19 Asahi Kasei Corp Flame-retardant polymer composition molded form
KR20080025072A (en) * 2005-07-08 2008-03-19 도레이 가부시끼가이샤 Resin composition and molded article comprising the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RYSZARD KOZLOWSKI ET AL., FLAMMABILITY AND FIRE RESISTANCE OF COMPOSITES REINFORCED BY NATURAL FIBERS, April 2008 (2008-04-01), pages 446 - 450 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015170803A1 (en) * 2014-05-07 2015-11-12 삼성에스디아이 주식회사 Polycarbonate resin composition and molded articles prepared therefrom
CN105419264A (en) * 2014-09-12 2016-03-23 韩华道达尔有限公司 Flame-retardant polylactic resin composition
CN108976471A (en) * 2018-06-27 2018-12-11 杭州本松新材料技术股份有限公司 Fire retardant compound system and halogen-free flame-retardant resin based composites comprising it

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