Classifications

• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/42—Chemical after-treatment
• • 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
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

• thermoplastic resin composition It relates to a thermoplastic resin composition.
• Polycarbonate resins are excellent in heat resistance and transparency, and their range of application, such as electrical and electronic product exterior materials and automobile parts, is increasing day by day.
• polycarbonate resin is used in blend with a styrene-containing copolymer.
• the rubber-modified styrene-based copolymer resin is blended with a polycarbonate resin because of its good processability, excellent impact strength, and excellent appearance, and thus is widely used in electrical and electronic products.
• Korean Patent Publication Nos. 2007-0071446, 2009-0026359 and 2010-0022376 propose a method of improving chemical resistance by blending with other resin having chemical resistance.
• this method can slightly improve the chemical resistance, but the effect is weak and the impact characteristics are reduced.
• One embodiment of the present invention can provide a resin composition that is improved in low-temperature impact strength and does not reduce the heat resistance.
• thermoplastic resin In one embodiment of the present invention, a thermoplastic resin; Modified polycarbonates; And it may provide a thermoplastic resin composition comprising a diene copolymer.
• the modified polycarbonate may include a repeating structure of Formula 2 below.
• R 1 and R 2 are independently a substituted or unsubstituted C1 to C6 alkyl group, a and b are independently an integer of 0 to 4).
• the modified polycarbonate may include a repeating structure of Formula 1 and Formula 2 below.
• R 1 and R 2 are independently a substituted or unsubstituted C1 to C6 alkyl group, a and b are independently an integer of 0 to 4).
• R 1 and R 2 are independently a substituted or unsubstituted C1 to C6 alkyl group, a and b are independently an integer of 0 to 4).
• the thermoplastic resin may be a polycarbonate resin, a rubber modified vinyl copolymer resin, a polyester resin, a polyalkyl (meth) acrylate resin, a polystyrene resin, a polyolefin resin, or a combination thereof.
• the thermoplastic resin may be a polyester resin.
• the thermoplastic resin may be a polybutylene terephthalate resin.
• the thermoplastic resin composition includes 4 to 15 parts by weight of a diene copolymer with respect to 100 parts by weight of the thermoplastic resin and the modified polycarbonate, and 100 parts by weight of the thermoplastic resin and the modified polycarbonate are 30 to 60 parts by weight of the thermoplastic resin. %; And 40 to 70% by weight of modified polycarbonate.
• the diene copolymer may be present on the modified polycarbonate matrix.
• One embodiment of the present invention can provide a resin composition that is improved in low-temperature impact strength and does not reduce the heat resistance.
• chemical resistance, fluidity or flame retardancy can be achieved with this.
• (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.
• average particle diameter of the plate-shaped particles means “long diameter”
• long diameter means the longest length of a line connecting two points in a closed curve
• closed curve means a curve in which a point on the curve moves in one direction and returns to the starting point.
• thermoplastic resin a thermoplastic resin
• Modified polycarbonates a thermoplastic resin composition comprising a diene copolymer.
• the thermoplastic resin may be various resins described below, but for example, may be polybutylene terephthalate resin. In such a case, since the polybutylene terephthalate resin and the modified polycarbonate are included together, it is possible to mold a product having improved heat resistance with low temperature impact strength.
• the thermoplastic resin composition includes 4 to 15 parts by weight of a diene copolymer with respect to 100 parts by weight of the thermoplastic resin and the modified polycarbonate, and 100 parts by weight of the thermoplastic resin and the modified polycarbonate are 30 to 60% by weight of the thermoplastic resin. ; And 40 to 70% by weight of modified polycarbonate.
• the diene copolymer may be present on the modified polycarbonate matrix.
• the diene copolymer may be an impact modifier.
• the impact strength of the molded article may be effectively improved by being present on the polycarbonate matrix that is weak to impact.
• Any impact modifier that may be present on the polycarbonate among various impact modifiers may be used in one embodiment of the present invention.
• thermoplastic resin known as the thermoplastic resin can be used without limitation, and for example, polycarbonate resin, rubber modified vinyl graft copolymer resin, polyester resin, polyalkyl (meth) acrylate resin, polystyrene resin, polyolefin Resin or a combination thereof can be used.
• the thermoplastic resin may impart basic physical properties such as impact resistance, heat resistance, bending property, and tensile property.
• the polycarbonate resin may be prepared by reacting diphenols with phosgene, halogen formate, carbonate ester or a combination thereof.
• diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also called 'bisphenol-A'), 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro 4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2 , 2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether and the like.
• 2,2-bis (4-hydroxyphenyl) propane 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) Cyclohexane can be used, more preferably 2,2-bis (4-hydroxyphenyl) propane.
• the polycarbonate resin may use a weight average molecular weight of 10,000 to 200,000 g / mol, specifically may be used 15,000 to 80,000 g / mol, but is not limited thereto.
• 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 rubber-modified vinyl-based graft copolymer resin is a copolymer in which 5 to 95 wt% of the vinyl polymer is grafted to 5 to 95 wt% of the rubbery polymer.
• 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 or a combination thereof can be used.
• the vinyl polymer may include 50 to 95% by weight of the first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And 5 to 50% by weight of a second vinyl monomer of an unsaturated nitrile monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof.
• styrene As the aromatic vinyl monomer, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, or a combination thereof may be used.
• alkyl substituted styrene include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, ⁇ -methyl styrene, and the like.
• the thing of (meth) acrylic-acid alkylester, (meth) acrylic acid ester, or a combination thereof can be used.
• 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.
• (meth) acrylate etc. are mentioned as a specific example of the said (meth) acrylic acid ester.
• heterocyclic monomer maleic anhydride, alkyl or phenyl N-substituted maleimide or a combination thereof can be used.
• an acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof can be used as the unsaturated nitrile monomer.
• the rubber particle size of the rubber-modified vinyl graft copolymer may be 0.05 to 4 ⁇ m in order to improve impact resistance and surface properties of the molded product.
• the rubber particle size is 0.05 to 4 ⁇ m, the impact strength is excellent. Can be secured.
• the rubber modified vinyl graft copolymer may be used alone or in the form of a mixture of two or more thereof.
• the rubber-modified vinyl-based graft copolymer include graft copolymerization of styrene, acrylonitrile and optionally methyl (meth) acrylate in the form of a mixture of butadiene rubber, acrylic rubber or styrene / butadiene rubber. have.
• rubber-modified vinyl-based graft copolymers include those obtained by graft copolymerization of methyl (meth) acrylate on butadiene rubber, acrylic rubber or styrene / butadiene rubber.
• rubber-modified graft copolymers include acrylonitrile-butadiene-styrene graft copolymers.
• 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 resin examples include polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin, or some of these resins.
• a polyester resin modified to be amorphous by mixing other monomers may be used, and among these, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin and amorphous polyethylene terephthalate resin may be used. And more preferably polybutylene terephthalate resin and polyethylene terephthalate resin.
• the polybutylene terephthalate resin is a polymer polycondensed by direct esterification or transesterification of a 1,4-butanediol monomer and a terephthalic acid or dimethyl terephthalate monomer.
• the polybutylene terephthalate resin may be selected from polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), low molecular weight aliphatic polyester or aliphatic poly. It may be used in the form of a modified polybutylene terephthalate resin copolymerized with an amide or blended with an impact improving component.
• PTMG polytetramethylene glycol
• PEG polyethylene glycol
• PPG polypropylene glycol
• the polybutylene terephthalate resin may have an intrinsic viscosity [ ⁇ ] of 0.35 to 1.5 dl / g when measured at 25 ° C. of o-chlorophenol, and specifically 0.5 to 1.3 dl / g.
• the intrinsic viscosity of the polybutylene terephthalate resin is within the above range, the mechanical strength, the moldability, and the like are excellent.
• the polyalkyl (meth) acrylate resin can be obtained by polymerizing a raw material monomer containing an alkyl (meth) acrylate by a known polymerization method such as suspension polymerization, bulk polymerization, emulsion polymerization or the like.
• the alkyl (meth) acrylate has an alkyl group of C1 to C10, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (Meth) acrylate etc. are mentioned.
• the alkyl (meth) acrylate may be included in more than 50% by weight relative to the total amount of polyalkyl (meth) acrylate.
• the polyalkyl (meth) acrylate may have a weight average molecular weight in the range of 10,000 to 200,000 g / mol, specifically, may have a range of 15,000 to 150,000 g / mol.
• weight average molecular weight of polyalkyl (meth) acrylate is the said range, it is excellent in hydrolysis resistance, scratch resistance, workability, etc.
• polystyrene resin for example, rubber-modified polystyrene resin (HIPS) reinforced with impact strength may be used.
• HIPS rubber-modified polystyrene resin
• the polyolefin resin may be a polyethylene resin (PE), a polypropylene resin (PP), a resin in a copolymerized form thereof, or the like.
• the thermoplastic resin may be used in the form of an alloy mixed with two or more kinds, and examples thereof include polycarbonate, acrylonitrile-butadiene-styrene graft resin (ABS), and styrene-acrylonitrile copolymer resin (SAN). mixture; Or when using a mixture of polycarbonate, acrylate-styrene-acrylonitrile graft resin (ASA) and styrene-acrylonitrile copolymer resin (SAN).
• ABS acrylonitrile-butadiene-styrene graft resin
• SAN styrene-acrylonitrile copolymer resin
• the modified polycarbonate according to an embodiment of the present invention may include a repeating structure of Formula 2 below.
• R 1 and R 2 are independently a substituted or unsubstituted C1 to C6 alkyl group, a and b are independently an integer of 0 to 4).
• the modified polycarbonate according to one embodiment of the present invention may include a repeating structure of Formula 1 and Formula 2:
• R 1 and R 2 are independently a substituted or unsubstituted C1 to C6 alkyl group, a and b are independently an integer of 0 to 4).
• R 1 and R 2 are independently a substituted or unsubstituted C1 to C6 alkyl group, a and b are independently an integer of 0 to 4).
• the modified polycarbonate may be prepared by specifically transesterifying a diol represented by Chemical Formulas 1-1 and 2-1 with a diaryl carbonate.
• R 1 and R 2 are independently a substituted or unsubstituted C1 to C6 alkyl group, a and b are independently an integer of 0 to 4).
• R 1 and R 2 are independently a substituted or unsubstituted C1 to C6 alkyl ring, a and b independently represent an integer of 0 to 4.
• Examples of the formula 1-1 include 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2- Bis- (3,5-diisopropyl-4-hydroxyphenyl) -propane and the like, preferably 2,2-bis- (4-hydroxyphenyl) -propane, also called bisphenol-A.
• Examples of Formula 2-1 include 4,4'-biphenol, 2,2'-dimethyl 4,4'-biphenyldiol, 3,3-dimethyl 4,4-dihydroxy biphenyl, 2,2 ' , 6,6 ',-tetramethyl-4,4'-biphenol and the like. Among these, 4,4'-biphenol is preferable.
• the molar ratio of Formula 1-1 and Formula 2-1 may be 40 to 95 mol%: 5 to 60 mol%. Within this range, it is possible to obtain a balance of physical properties of impact strength, chemical resistance and fluidity. When the content of Formula 2-1 is 60% or more, crystallization occurs and polymerization may not be performed.
• diaryl carbonate examples include diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, Dicyclohexyl carbonate etc. are mentioned, It is not necessarily limited to this. These may be used alone or in combination of two or more, preferably diphenyl carbonate.
• the diol-based compounds of Formulas 1-1 and 2-1 may be used in a molar ratio of 0.6 to 1.0, preferably 0.7 to 0.9, with respect to the diaryl carbonate.
• 0.6 to 1.0 preferably 0.7 to 0.9
• the diol-based compounds of Formulas 1-1 and 2-1 may be used in a molar ratio of 0.6 to 1.0, preferably 0.7 to 0.9, with respect to the diaryl carbonate.
• it has particularly excellent heat resistance and impact resistance at room temperature.
• a low refractive index has excellent compatibility when blended with other resins.
• the transesterification reaction may proceed under reduced pressure at 150 to 300 °C, preferably 160 to 280 °C, more preferably 190 to 260 °C. It is preferable in the reaction rate and side reaction reduction in the above temperature range.
• the transesterification reaction is at least 10 minutes, preferably 15 minutes to 24 hours, under reduced pressure conditions of 100 torr or less, for example 75 torr or less, preferably 30 torr or less, more preferably 1 torr or less. More preferably, running 15 minutes to 12 hours is preferred in terms of reaction rate and side reaction reduction.
• the modified polycarbonate may be prepared by reacting at a reaction temperature of 160 to 260 ° C. for about 2 to 9 hours.
• the transesterification reaction can be carried out in the presence of an alkali metal and alkaline earth metal catalyst.
• alkali metal and alkaline earth metal catalysts include LiOH, NaOH, KOH, and the like, but are not necessarily limited thereto. These may be used alone or in combination of two or more thereof.
• the content of the catalyst can be determined by the amount of aromatic dihydroxy compound used. In one embodiment of the present invention can be used in the range of about 1 ⁇ 10 -8 to 1 ⁇ 10 -3 moles per mole of aromatic dihydroxy compound. In the above content range, by-products due to sufficient reactivity and side reactions may be minimized, thereby improving thermal stability and color stability.
• the modified polycarbonate has a molar ratio of Formula 1 (M1), and Formula 2 (M2) that meets the following conditions:
• the modified polycarbonate may constitute a base resin, thereby obtaining a balance of physical properties of impact strength, transparency, heat resistance, chemical resistance, flame retardancy, and processability.
• the diene copolymer used in the embodiment of the present invention may be a diene core-shell copolymer.
• the diene-based core-shell copolymer was polymerized with at least one selected from among diene rubbers having 4 to 6 carbon atoms, and then grafted at least one monomer selected from graftable vinyl monomers to rubber to form a core-shell structure.
• the rubber content may be 20 to 90% by weight.
• the vinyl monomer used in the preparation of the shell of the core-shell copolymer may be selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, acrylic ester monomers and maleimide monomers.
• aromatic vinyl monomer styrene, t-butyl styrene, alpha methyl styrene, p-methyl styrene, vinyl toluene, monochloro styrene, dichloro styrene, dibromostyrene, ethyl styrene, vinyl naphthalene, divinylbenzene, etc. may be used. It is preferable to use styrene or alphamethyl styrene.
• Acrylonitrile, methacrylonitrile, ethacrylonitrile and the like can be used as the vinyl cyanide monomer, and preferably acrylonitrile is used.
• acrylic ester monomer methyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl methacrylate, and the like can be used, and preferably methyl methacrylate or ethyl It is preferable to use acrylates.
• the maleimide monomers include maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-dichlorohexylmaleimide, N-phenylmaleimide and N-trimaleimide Etc. can be used, Preferably maleimide or N-methyl maleimide is used.
• the thermoplastic resin composition may include an antibacterial agent, a heat stabilizer, an antioxidant, a mold release agent, a light stabilizer, 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 sunscreen, It may further include an additive of a nucleating agent, an adhesion aid, an adhesive, or a combination thereof.
• the antioxidant may be a phenolic, phosphite or thioether type antioxidant
• the release agent is a fluorine-containing polymer, silicone oil, metal salt of stearic acid, metal salt of montanic acid, Montan acid ester waxes or polyethylene waxes can be used.
• a benzophenone type, a benzotriazole type or a phenyltriazine type weathering agent may be used as the weathering agent, a dye or a pigment may be used as the colorant, and titanium dioxide (TiO 2) or carbon black may be used as the sunscreen.
• talc or clay may be used as the nucleating agent.
• the additive may be suitably included within a range that does not impair the physical properties of the thermoplastic resin composition, specifically, may be included in 40 parts by weight or less based on 100 parts by weight of the thermoplastic resin composition, more specifically 0.1 to 30% by weight. It can be included as a wealth.
• thermoplastic resin composition can be manufactured by the well-known method of manufacturing a resin composition.
• the components and other additives according to one embodiment may be mixed simultaneously, then melt extruded in an extruder and prepared in pellet form.
• a molded article manufactured by molding the aforementioned thermoplastic resin composition is provided. That is, a molded article can be manufactured by various processes, such as injection molding, blow molding, extrusion molding, and thermoforming, using the said thermoplastic resin composition.
• one embodiment of the present invention can provide a resin composition which is improved at low temperature impact strength and at the same time does not reduce the heat resistance, and with this, chemical resistance, fluidity or flame retardancy can be achieved.
• thermoplastic resin composition was prepared as shown in Table 1 below.
• SC-1080 of Cheil Industries whose weight average molecular weight was 28,000 g / mol, was used.
• DHK 011 manufactured by Shinkong which has an intrinsic viscosity [ ⁇ ] of 1.2 dl / g, was used.
• the temperature range of 240 to 270 °C in a conventional twin screw extruder After extruding, the extrudate was prepared in pellet form.
• thermoplastic resin compositions of Examples 1 to 3 have improved gloss (gloss) in the appearance of the injection, and improved heat resistance along with low temperature impact strength.

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