WO2016089172A1 - Polycarbonate composition and article comprising same - Google Patents

Polycarbonate composition and article comprising same Download PDF

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Publication number
WO2016089172A1
WO2016089172A1 PCT/KR2015/013247 KR2015013247W WO2016089172A1 WO 2016089172 A1 WO2016089172 A1 WO 2016089172A1 KR 2015013247 W KR2015013247 W KR 2015013247W WO 2016089172 A1 WO2016089172 A1 WO 2016089172A1
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WIPO (PCT)
Prior art keywords
polycarbonate
weight
formula
repeating unit
polycarbonate composition
Prior art date
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PCT/KR2015/013247
Other languages
French (fr)
Korean (ko)
Inventor
정윤선
이무석
이률
안성태
조익환
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020150171781A external-priority patent/KR101809649B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201580002739.9A priority Critical patent/CN105899608B/en
Priority to US15/026,905 priority patent/US9580597B2/en
Publication of WO2016089172A1 publication Critical patent/WO2016089172A1/en

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Classifications

    • 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
    • C08G64/20—General preparatory processes
    • C08G64/38—General preparatory processes using other monomers
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a polycarbonate composition having excellent mechanical properties and appearance and to an article comprising the same.
  • Polycarbonate resin is a resin prepared by the polycondensation of aromatic diul such as bisphenol A and a carbonate precursor such as phosgene, and has excellent mechanical and thermal properties. In particular, it has high impact resistance at room temperature and excellent dimensional stability.
  • aromatic diul such as bisphenol A
  • carbonate precursor such as phosgene
  • Polycarbonate resin compositions which have high processability in combination with ABS (acrylonitrile-butadiene-styrene copolymer) in addition to polycarbonate resins, and are commonly used as PC / ABS resins or PC / ABS Al. It's called loy.
  • the present inventors have made diligent efforts to solve the problem of appearance defects caused by including the inorganic layer agent in the PC resin, and as described below, a copolycarbonate including two or more different repeating units in addition to the inorganic layer agent is described.
  • the present invention was completed by confirming that the problem of appearance defects could be solved while maintaining the effect of improving the mechanical properties according to the addition of the inorganic layer agent.
  • the present invention is to provide a polycarbonate composition excellent in mechanical properties and appearance.
  • the present invention also provides an article comprising the polycarbonate composition.
  • Aromatic polycarbonate-based first repeating unit And an aromatic polycarbonate-based second repeating unit having one or more siloxane bonds, and
  • the one repeating unit is represented by the following formula (1),
  • the second repeating unit includes a repeating unit represented by the following Formula 2 and a repeating unit represented by the following Formula 3,
  • Ri to R4 are each independently hydrogen, Cwo alkyl, d- 10 alkoxy, or halogen,
  • Z is unsubstituted or substituted phenyl or CHO alkylene, unsubstituted or substituted with Cwo alkyl, C 3 to - 15, and cycloalkylene, 0, S, SO, S0 2, or CO,
  • Each 3 ⁇ 4 is independently hydrogen; Unsubstituted or oxiranyl group, substituted with oxiranyl-10 alkoxy, or C 6 - 20 aryl substituted with a d- 15 alkyl; halogen; CHQ alkoxy; Allyl; d-o haloalkyl; 20 is an aryl, - or C 6
  • n is an integer from 10 to 200
  • 3 ⁇ 4 are each independently C wo alkylene
  • the polycarbonate composition comprises 1 to 13 parts by weight of polycarbonate, 1 part by weight of layer reinforcing agent, 1 to 6 parts by weight of copoly-carbonate, and 0.5 to 4 parts by weight of inorganic layering agent.
  • the polycarbonate composition according to the present invention includes a polycarbonate and a layer reinforcing agent, and includes an inorganic layer agent for improving its mechanical properties. In addition, in order to solve the problem of appearance defect occurring while including the inorganic layer agent And copolycarbonates described above.
  • Copolycarbonate according to the present invention is to introduce a specific siloxane compound into the polycarbonate backbone, it is possible to solve the problem of poor appearance while maintaining the effect of improving the mechanical properties according to the addition of the inorganic filler, improve the mechanical properties and appearance at the same time It is effective to let.
  • the present invention will be described in more detail.
  • the polycarbonate used by this invention is distinguished from the copolycarbonate mentioned later in that the polysiloxane structure is not introduce
  • the polycarbonate composition according to the present invention in addition to the polycarbonate, in order to improve impact resistance, heat resistance and moldability, further includes an impact modifier.
  • an impact modifier used in the present invention, a methyl methacrylate butadiene-styrene copolymer, a styrene-acrylonitrile copolymer, an acrylonitrile-butadiene-styrene series, or a mixture thereof can be used.
  • MBS resin SAN resin
  • ABS resin respectively.
  • the polycarbonate preferably comprises 5 to 13 parts by weight, more preferably 8 to 11 parts by weight. It is excellent in the improvement effect, such as layer resistance, heat resistance, and moldability, in the said range.
  • the polycarbonate is prepared by reacting an aromatic diol compound and a carbonate precursor, and preferably includes a repeating unit represented by Formula 4 below:
  • R'i to R'4 are each independently hydrogen, d- 10 alkyl, alkoxy, or halogen,
  • Z ' is a C 3 alkylene substituted with CHO, unsubstituted or CHO-alkyl substituted by unsubstituted or phenyl-15 cycloalkylene, 0, S, SO, S0 2, or CO.
  • the polycarbonate preferably has a weight average molecular weight (g / mol) of 1,000 to 100,000, more preferably 15,000 to 35, 000. More preferably, the weight average molecular weight is 20,000 or more , More than 21,000, More than 22,000, More than 23,000, More than 24,000 :
  • R'i to R ' 4 are each independently hydrogen, methyl, chloro, bromo.
  • Z ' is straight-chain or branched 10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethanol 1,1-diyl, propane 2, 2-diyl butane-2 , 2-diyl, 1-phenylethane ⁇ 1,1-diyl, or diphenylmethylene ⁇
  • the repeating unit represented by Chemical Formula 4 is bis (4-hydroxyphenyl) methane, bis (4'hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ) Sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis (4 ⁇ hydride) Hydroxyphenyl) butane, 1,1-bis (4 ⁇ hydroxyphenyl) cyclonucleic acid, 2,2-bis (4—hydroxy-3, 5-dibromophenyl) propane, 2,2-bis (4- Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2bisbis (4-hydroxy-3-chlorophenyl) propane, 2 , 2-bis (4-hydroxy-3-methylphenyl) propane
  • the term “derived from an aromatic diol compound” means that a hydroxyl group of an aromatic diol compound reacts with a carbonate precursor to form a repeating unit represented by the formula (4).
  • a repeating unit represented by the formula (4) is represented by the following Formula 4-1:
  • Examples of the carbonate precursor include dimethyl carbonate, diethyl carbonate dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate and bis At least one selected from the group consisting of (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate can be used.
  • triphosgene or phosgene can be used.
  • the copolycarbonate used by this invention means the polymer in which the polysiloxane structure was introduce
  • the copolycarbonate has an effect of suppressing appearance defects caused by the addition of the inorganic filler.
  • the copolycarbonate Based on 1 part by weight of the impact modifier, the copolycarbonate comprises 1 to 6 parts by weight, more preferably 2 to 5 parts by weight. It is excellent in the effect which suppresses external appearance quantity in the said range.
  • the main chain of the polycarbonate is formed by reacting an aromatic di compound with a carbonate precursor, and specifically means a repeating unit represented by Chemical Formula 1.
  • 3 ⁇ 4 to 3 ⁇ 4 are each independently hydrogen, methyl, chloro, or bromo.
  • Z is straight or branched chain c 10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane 1, 1-diyl, propane-2, 2-diyl, butane— 2, 2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene.
  • Z is cyclonucleic acid -1, 1 ⁇ diyl, 0, S, SO, S0 2 , or CO.
  • the repeating unit represented by Chemical Formula 1 is bis (4-hydroxyphenyl) methane, bis (4'hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4'hydroxyphenyl) ) Sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2, 2-bis (4 ⁇ hydride) Hydroxyphenyl) butane, 1, 1-bis (4-hydroxyphenyl) cyclonucleic acid, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4- Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2 , 2-bis (4-hydroxy ⁇ 3-methylphenyl) propane, 2,2'bis (4-hydroxy-3, 5-d
  • the term “derived from an aromatic diol compound” means that the hydroxy group and the carbonate precursor of the aromatic diol compound react to form a repeating unit represented by the formula (1).
  • the repeating unit represented by Formula 1 is It is represented by Formula 1-1:
  • Examples of the carbonate precursor include dimethyl carbonate, diethyl carbonate dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate and bis
  • One or more selected from the group consisting of (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate can be used.
  • triphosgene or phosgene can be used.
  • the polysiloxane structure means a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3.
  • 3 ⁇ 4 are each independently C 2 - 4 alkylene and is, most preferably, propane-1,3-diyl-10 alkylene, more preferably C 2. Also preferably, ⁇ is hydrogen or d- 6 alkoxy, more preferably hydrogen or d- 4 alkoxy, most preferably hydrogen or methoxy. Also preferably, 3 ⁇ 4 is independently hydrogen, methyl, ethyl, propyl,
  • 3 ⁇ 4 is each independently Cwo alkyl, more preferably d- 6 alkyl, more preferably d- 3 alkyl, most preferably methyl.
  • n is 10 or more, 15 or more, 20 or more, 25 or more,
  • 3 ⁇ 4 are each independently a C 2 - to 10 alkylene, more preferably C 2 - 6 alkylene and most preferably isobutylene.
  • Y 2 is hydrogen.
  • 3 ⁇ 4 is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl,.
  • 3 ⁇ 4 is each independently d- 10 alkyl, more preferably d- 6 alkyl, more preferably d- 3 alkyl, and most preferably methyl.
  • m is 40 or more, 45 or more, 50 or more, 55 or more, 56 or more, 57 or more, or 58 or more, 80 or less, 75 or less, 70 or less, 65 or less, 64 or less, 63 or less, or It is an integer of 62 or less.
  • the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 are each derived from a siloxane compound represented by Formula 2-1 and a siloxane compound represented by Formula 3-1.
  • Y 2 , R 6 and m are the same as defined above.
  • the term “derived from the siloxane compound” means that the hydroxyl group and the carbonate precursor of each siloxane compound react to form a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3 .
  • the carbonate precursors that can be used to form the repeating units of Formulas 2 and 3 are the same as those described above for the carbonate precursors that can be used to form the repeating units of Formula 1.
  • the method for producing the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 3-1 is as follows.
  • X 2 , Y 2 , Re and m are as defined above. It is preferable that the reaction of Banung 1 and Banung 2 is performed under a metal catalyst. It is preferable to use a Pt catalyst as the metal catalyst, an Ashby catalyst, a Karlstedt catalyst, Lamoreaux Catalyst, Speier Catalyst, PtCl 2 (C0D),
  • At least one selected from the group consisting of PtCl 2 (benzonitrile) 2 , and H 2 PtBr 6 can be used.
  • the metal catalyst is 0.001 parts by weight, 0.005 parts by weight, or 0.01 parts by weight or more, 1 part by weight, 0.1 parts by weight, or 0.05 parts by weight or less based on 100 parts by weight of the compound represented by Chemical Formula 7 or 9.
  • the reaction temperature is preferably so to locrc.
  • the reaction time is preferably 1 hour to 5 hours.
  • the compound may be prepared by reacting organodisiloxane and organocyclosiloxane under an acid catalyst, and n and m may be controlled by adjusting the content of the reaction material.
  • the reaction is preferably 50 to 70 ° C.
  • the reaction time is preferably 1 hour to 6 hours.
  • the organodisiloxane one or more selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, nuxamethyldisiloxane and nuxaphenyldisiloxane can be used.
  • an organocyclotetrasiloxane can be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like.
  • the organodisiloxane may be 0.1 part by weight or more, or 2 parts by weight or more, 10 parts by weight or less, or 8 parts by weight or less, based on 100 parts by weight of the organocyclosiloxane.
  • the acid catalyst one or more selected from the group consisting of H 2 S04, HC10 4 , AICI3, SbCl 5 , SnCl 4, and acidic clay may be used.
  • the acid catalyst is 0.1 parts by weight or more, based on 100 parts by weight of the organosaclosiloxane, 0.5 It is more than 1 weight part or 1 weight part or more, 10 weight part or less, 5 weight part or less, or 3 weight part or less can be used.
  • the weight ratio between the repeating units may be 1:99 to 99: 1.
  • it is 3: 97-97: 3, 5: 95-95: 5, 10: 90-90: 10, or 15: 85-85: 15, More preferably, it is 20: 80-80: 20.
  • the weight ratio of the repeating unit is based on the weight ratio of the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 2-1.
  • the repeating unit represented by Formula 2 is . , Represented by the following Chemical Formula 2-2:
  • 3 ⁇ 4 and n are as defined above.
  • 3 ⁇ 4 is methyl.
  • the repeating unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-2:
  • a copoly in Chemical Formula 3 ′ 2, 3 ⁇ 4 and m are as defined above. Preferably, 3 ⁇ 4 is methyl.
  • a copoly in the copolycarbonate (A), a copoly includes both a repeating unit represented by Formula 1-1, a repeating unit represented by Formula 2 ′ 2 and a repeating unit represented by Formula 3 ′ 2 Provide carbonate.
  • the weight ratio of the weight of the repeating unit represented by the formula (1) and the total weight of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) is 1 : 0.04-0.07 is preferable.
  • the present invention also provides a process for preparing copolycarbonate (A), comprising the step of polymerizing an aromatic diol compound, a carbonate precursor and at least one siloxane compound.
  • the aromatic diol compound, carbonate precursor and one or more siloxane compounds are as described above.
  • the at least one siloxane compound is at least 1 weight 3 ⁇ 4), at least 1 weight 1, at least 1.2 weight%, at least 1.3 weight%, 1.4 to 100% by weight of the aromatic diol compound, the carbonate precursor and the at least one siloxane compound.
  • the aromatic diol compound is 40% by weight or more, 50% by weight or more, or 55% by weight, 80% by weight or less, 70% by weight, based on 100% by weight of the aromatic diol compound, the carbonate precursor and one or more siloxane compounds in total. Or less than or equal to 65% by weight.
  • the carbonate precursor is 10% by weight, 20% by weight, or 30% by weight, 60% by weight, 50.% by weight or less, based on 100% by weight of the total aromatic di-compound, carbonate precursor and one or more siloxane compounds. Can be used in 40% by weight or less.
  • an interfacial polymerization method may be used as the polymerization method. In this case, the polymerization reaction is possible at atmospheric pressure and low silver, and the molecular weight is easily controlled.
  • the interfacial polymerization is preferably carried out in the presence of an acid binder and an organic solvent.
  • the interfacial polymerization may include, for example, adding a coupling agent after prepolymerization (pre-polymer i zat ion) and then polymerizing again, in which case a high molecular weight copolycarbonate (A) is obtained.
  • a coupling agent after prepolymerization (pre-polymer i zat ion) and then polymerizing again, in which case a high molecular weight copolycarbonate (A) is obtained.
  • A high molecular weight copolycarbonate
  • the materials used for the interfacial polymerization are not particularly limited as long as they are materials that can be used for the polymerization of polycarbonate, and the amount of the materials used may be adjusted as necessary.
  • the acid binder for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound of pyridine round may be used.
  • the organic solvent is not particularly limited as long as it is a solvent usually used for polymerization of polycarbonate, and for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene may be used.
  • the interfacial polymerization may be performed in order to promote reaction, such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, tertiary , amine compound, quaternary ammonium compound, quaternary phosphonium compound, and the like.
  • Reaction accelerators may be further used.
  • the reaction temperature of the interfacial polymerization is preferably 0 to 4 (rc, The time is preferably 10 minutes to 5 hours. Moreover, it is preferable to maintain pH in 9 or more or 11 or more in interfacial polymerization reaction.
  • the interfacial polymerization may be performed by further including a molecular weight regulator. The molecular weight modifier may be added before the start of polymerization, during the start of the polymerization, or after the start of the polymerization.
  • Mono-alkylphenol may be used as the molecular weight modifier, and the mono-alkylphenol is, for example, p-tert-butylphenol, P-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nuxadecylphenol, octadecyl It is at least one selected from the group consisting of phenol, eicosylphenol, docosylphenol and triacontylphenol, preferably p-ter.t-butylphenol, in which case the molecular weight control effect is large.
  • the molecular weight modifier may be, for example, 0.01 parts by weight or more, 0,1 parts by weight, or 1 part by weight or more, 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of aromatic diol compound. It is possible to obtain a desired molecular weight within this range.
  • the copolycarbonate preferably has an increased average molecular weight (g / mol) of 1,000 to 100, 000, more preferably 15,000 to 35,000. More preferably, the weight average molecular weight is 20,000 or more, 21,000 or more, 22,000 or more, 23,000 or more, 24,000 or more, 25,000 or more, 26,000 or more, 27,000 or more, or 28,000 or more. In addition, the said weight average molecular weight is 34,000 or less, 33,000 or less, or 32,000 or less. Inorganic layer agent
  • the inorganic layer filler used in the present invention is used to improve the physical properties of the polycarbonate.
  • inorganic fillers when inorganic fillers are included, physical properties are reinforced. There is a problem in that appearance defects occur, such as a f low mark during processing such as molding.
  • the inorganic filler Based on 1 part by weight of the impact modifier, the inorganic filler comprises 0.5 to 4 parts by weight, more preferably 0.5 to 3 parts by weight, most preferably 0.5 to 2 parts by weight. It is excellent in the physical property improvement effect in the said range.
  • the inorganic layer agent talc, wol l astoni te, mica, or a mixture thereof may be used.
  • the polycarbonate resin composition in the present invention includes the polycarbonate, the layer reinforcement agent, the copolycarbonate, and the inorganic layer filler described above.
  • the polycarbonate resin composition if necessary, group consisting of flame retardant 1, antioxidant, heat stabilizer, light stabilizer, plasticizer, antistatic agent, nucleating agent, lubricant, laminar enhancer, fluorescent brightener, ultraviolet absorber, pigment and dye It may further comprise any one or more additives selected from.
  • a phosphorus-based flame retardant may be used as the flame retardant.
  • the phosphorus-based flame retardant is not particularly limited as long as it is commonly used in the art, for example, bisphenol-A bis (diphenyl phosphate) (Bi sphenol-A bi s (diphenyl phosphate)) may be used.
  • the flame retardant may include 0.5 to 4 parts by weight, it is excellent in the flame retardancy improving effect in the above range.
  • the present invention also provides an article comprising the polycarbonate composition.
  • the article is an injection molded article.
  • the polycarbonate composition according to the present invention includes a polycarbonate and a layer reinforcing agent, includes an inorganic filler for improving its mechanical properties, and solves the problem of appearance defects occurring while including the inorganic filler by including copolycarbonate. Can be.
  • the polycarbonate composition according to the present invention and the additives are mixed as necessary using a mixer, and then extruded with an extruder to produce pellets, the pellets are dried and then injected into an injection molding machine. It may include a step.
  • the polycarbonate composition according to the present invention includes a polycarbonate and a layer reinforcing agent, includes an inorganic layering agent for improving its mechanical properties, and addresses problems of appearance defects occurring while including an inorganic layering agent.
  • a polycarbonate includes a polycarbonate and a layer reinforcing agent, includes an inorganic layering agent for improving its mechanical properties, and addresses problems of appearance defects occurring while including an inorganic layering agent.
  • IZ0D impact strength (kg. Cm / cm): measured in accordance with the specimen 1/8 '' according to ASTM D256.
  • Flame retardancy was evaluated based on UL 94V. Specifically, five 1.0 mm thick flame retardant specimens required for the flame retardant test application were prepared and evaluated as follows.
  • the flexural strength and the IZ0D laminar strength were significantly higher than those of the comparative example, and it was confirmed that the appearance was remarkably excellent. Therefore, when the inorganic resin and copolycarbonate are simultaneously included in the PC resin as in the present invention, it was confirmed that the appearance defects can be suppressed at the same time while improving the mechanical properties.

Abstract

A polycarbonate composition according to the present invention comprises a polycarbonate and an impact modifier, and further comprises an inorganic filler for improving mechanical properties thereof. The polycarbonate composition can solve the problem of appearance defects, caused by the inclusion of the inorganic filler, by comprising a co-polycarbonate.

Description

【명세서】  【Specification】
【발명의 명칭】  [Name of invention]
폴리카보네이트 조성물 및 이를 포함하는 물품  Polycarbonate Compositions and Articles Comprising the Same
【관련 출원 (들)과의 상호 인용】  [Cross Citation with Related Application (s)]
본 출원은 2014년 12월 4일자 한국 특허 출원 게 10-2014-0173005호 및 2015년 12월 3일자 한국 특허 출원 제 10-2015-0171781호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.  This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0173005 dated December 4, 2014 and Korean Patent Application No. 10-2015-0171781 dated December 3, 2015. All content disclosed in the literature is included as part of this specification.
【기술분야】  Technical Field
본 발명은 기계적 물성 및 외관이 우수한 폴리카보네이트 조성물 및 이를 포함하는 물품에 관한 것이다.  The present invention relates to a polycarbonate composition having excellent mechanical properties and appearance and to an article comprising the same.
【배경기술】  Background Art
폴리카보네이트 수지는 비스페놀 A와 같은 방향족 디을과 포스겐과 같은 카보네이트 전구체가 축중합하여 제조되는 수지로서, 우수한 기계적 물성 및 열적 물성을 가지고 있다. 특히 상온에서 높은 내충격성을 가지고 있으며 , 치수 안정성이 우수하다. 현재까지 폴리카보네이트 수지에 다양한 종류의 층진제를 보강하여 우수한 물성을 구현하는 연구가 진행되고 있다. 최근에는， 폴리카보네이트 수지 외에 ABS (아크릴로니트릴ᅳ부타디엔- 스티렌계 공증합체)와 흔합하여 가공성을 높인 폴리카보네이트 수지 조성물에 대한 연구가 활발히 진행되고 있으며， 이를 통상 PC/ABS 수지 또는 PC/ABS Al loy라고 한다. PC/ABS 수지의 경우 기계적 물성을 보다 강화하기 위하여 무기 충전제， 예를 들어 탈크 (tal c)가 첨가되고 있는데, 이를 통하여 기계적 물성의 향상이 가능하나 사출 성형시 흐름 자국 ( f low mark)가 생기는 단점이 있다. 흐름 자국과 같은 외관 불량이 생기면 후처리 과정으로 도장 등의 추가 공정이 필요하여 제조 단가가 높아지는 문제가 있다. 한편， 폴리카보네이트 수지는 최근 보다 다양한 분야에 적용하기 위해 2종 이상의 서로 다른 구조의 방향족 디올 화합물을 공중합하여 구조가 다른 단위체를 폴리카보네이트의 주쇄에 도입하여 원하는 물성을 얻고자 하는 연구가 많이 시도되고 있다. 이에 본 발명자들은, PC 수지에 무기 층전제를 포함하면서 발생하는 외관 불량의 문제점을 해결하기 위하여 예의 노력한 결과， 후술할 바와 같이 무기 층전제 외에 2종 이상의 서로 다른 반복단위를 포함하는 코폴리카보네이트를 함께 포함할 경우， 무기 층전제 첨가에 따른 기계적 물성 향상의 효과는 유지하면서도 외관 블량의 문제를 해결할 수 있음을 확인하여 본 발명을 완성하였다. Polycarbonate resin is a resin prepared by the polycondensation of aromatic diul such as bisphenol A and a carbonate precursor such as phosgene, and has excellent mechanical and thermal properties. In particular, it has high impact resistance at room temperature and excellent dimensional stability. Until now, research has been conducted to reinforce various kinds of layering agents in polycarbonate resins to realize excellent physical properties. In recent years, research has been actively conducted on polycarbonate resin compositions which have high processability in combination with ABS (acrylonitrile-butadiene-styrene copolymer) in addition to polycarbonate resins, and are commonly used as PC / ABS resins or PC / ABS Al. It's called loy. In the case of PC / ABS resins, inorganic fillers such as talc are added to reinforce the mechanical properties, but mechanical properties can be improved through this, but f low marks are generated during injection molding. There are disadvantages. If appearance defects such as flow marks occur, there is a problem that an additional process such as painting is required as a post-treatment process, thereby increasing the manufacturing cost. On the other hand, polycarbonate resin has recently copolymerized two or more kinds of aromatic diol compounds of different structures in order to apply to various fields Many studies have been conducted to obtain desired physical properties by introducing monomers having different structures into the main chain of polycarbonate. Accordingly, the present inventors have made diligent efforts to solve the problem of appearance defects caused by including the inorganic layer agent in the PC resin, and as described below, a copolycarbonate including two or more different repeating units in addition to the inorganic layer agent is described. When included together, the present invention was completed by confirming that the problem of appearance defects could be solved while maintaining the effect of improving the mechanical properties according to the addition of the inorganic layer agent.
【발명의 내용】 ,  【Contents of the Invention】
【해결하려는 과제】  [Problem to solve]
본 발명은 기계적 물성 및 외관이 우수한 폴리카보네이트 조성물을 제공하기 위한 것이다.  The present invention is to provide a polycarbonate composition excellent in mechanical properties and appearance.
또한， 본 발명은 상기 폴리카보네이트 조성물을 포함하는 물품을 제공하기 위한 것이다.  The present invention also provides an article comprising the polycarbonate composition.
【과제의 해결 수단】  [Measures of problem]
상기 과제를 해결하기 위하여， 본 발명은  In order to solve the above problems, the present invention
폴리카보네이트，  Polycarbonate,
충격 보강제，  Impact modifier ，
방향족 폴리카보네이트계 제 1 반복 단위; 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는 코폴리카보네이트， 및  Aromatic polycarbonate-based first repeating unit; And an aromatic polycarbonate-based second repeating unit having one or more siloxane bonds, and
무기 충전제를 포함하고，  Including inorganic fillers ，
상기 게 1 반복 단위는 하기 화학식 1로 표시되고，  The one repeating unit is represented by the following formula (1),
상기 제 2 반복 단위는 하기 화학식 2로 표시되는 반복 단위 및 하기 화학식 3으로 표시되는 반복 단위를 포함하는，  The second repeating unit includes a repeating unit represented by the following Formula 2 and a repeating unit represented by the following Formula 3,
폴리카보네이트 조성물을 제공하기 위한 것이다.  To provide a polycarbonate composition.
[화학식 1]
Figure imgf000004_0001
상기 화학식 l에서， [Formula 1]
Figure imgf000004_0001
In Chemical Formula l,
Ri 내지 R4는 각각 독립적으로 수소， Cwo 알킬， d— 10 알콕시， 또는 할로겐이고， Ri to R4 are each independently hydrogen, Cwo alkyl, d- 10 alkoxy, or halogen,
Z는 비치환되거나 또는 페닐로 치환된 CHO 알킬렌， 비치환되거나 또는 Cwo 알킬로 치환된 C3-15 사이클로알킬렌， 0 , S , SO , S02 , 또는 CO이고， Z is unsubstituted or substituted phenyl or CHO alkylene, unsubstituted or substituted with Cwo alkyl, C 3 to - 15, and cycloalkylene, 0, S, SO, S0 2, or CO,
Figure imgf000004_0002
Figure imgf000004_0002
상기 화학식 2에서,  In Chemical Formula 2,
)^은 각각 독립적으로 d- o 알킬렌이고，  ) ^ Are each independently d-o alkylene,
¾는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 -10 알콕시， 또는 C6-20 아릴로 치환된 d-15 알킬; 할로겐; CHQ 알콕시 ; 알릴; d- o 할로알킬; 또는 C6-20 아릴이고， Each ¾ is independently hydrogen; Unsubstituted or oxiranyl group, substituted with oxiranyl-10 alkoxy, or C 6 - 20 aryl substituted with a d- 15 alkyl; halogen; CHQ alkoxy; Allyl; d-o haloalkyl; 20 is an aryl, - or C 6
n은 10 내지 200의 정수이고,  n is an integer from 10 to 200,
Figure imgf000004_0003
Figure imgf000004_0003
상기 화학식 3에서，  In Chemical Formula 3,
¾은 각각 독립적으로 Cwo 알킬렌이고, ¾ are each independently C wo alkylene,
^은 각각 독립적으로 수소， d-6 알킬, 할로겐， 히드록시, d 알콕시 , 또는 C6-20 아릴이고, ¾는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 d-10 알콕시， 또는 C6-20 아릴로 치환된 d-15 알킬; 할로겐; d-10 알콕시 ; 알릴; d-io 할로알킬; 또는 C6— 20 아릴이고， ^ Is hydrogen, d- 6 alkyl, halogen, hydroxy, d-alkoxy, or C 6 each independently - A 20 aryl, Each ¾ is independently hydrogen; Unsubstituted or oxiranyl group, a d- 10 alkoxy substituted by oxiranyl group, or a C 6 - 15 alkyl substituted with a d- 20 aryl; halogen; d- 10 alkoxy; Allyl; d-io haloalkyl; Or C 6 — 20 aryl,
m은 10 내지 200의 정수이다. 바람직하게는， 상기 폴리카보네이트 조성물은， 1 내지 13 중량부의 폴리카보네이트， 1 중량부의 층격 보강제， 1 내지 6 중량부의 코폴리—카보네이트, 및 0.5 내지 4 중량부의 무기 층전제를 포함한다. 본 발명에 따른 폴리카보네이트 조성물은， 폴리카보네이트 및 층격 보강제를 포함하고， 이의 기계적 물성을 향상시키기 위한 무기 층전제를 포함한다ᅳ 또한， 무기 층전제를 포함하면서 발생하는 외관 블량의 문제를 해결하기 위하여 , 상술한 코폴리카보네이트를 포함한다. 본 발명에 따른 코폴리카보네이트는 특정 실록산 화합물을 폴리카보네이트 주쇄에 도입한 것으로， 무기 충전제의 첨가에 따른 기계적 물성 향상 효과는 유지하면서도 외관 불량의 문제를 해소할 수 있어， 기계적 물성과 외관을 동시에 향상시키는 효과가 있다. 이하에서， 본 발명을 보다 상세히 설명한다. 폴리카보네이트 및 층격 보강제  m is an integer of 10-200. Preferably, the polycarbonate composition comprises 1 to 13 parts by weight of polycarbonate, 1 part by weight of layer reinforcing agent, 1 to 6 parts by weight of copoly-carbonate, and 0.5 to 4 parts by weight of inorganic layering agent. The polycarbonate composition according to the present invention includes a polycarbonate and a layer reinforcing agent, and includes an inorganic layer agent for improving its mechanical properties. In addition, in order to solve the problem of appearance defect occurring while including the inorganic layer agent And copolycarbonates described above. Copolycarbonate according to the present invention is to introduce a specific siloxane compound into the polycarbonate backbone, it is possible to solve the problem of poor appearance while maintaining the effect of improving the mechanical properties according to the addition of the inorganic filler, improve the mechanical properties and appearance at the same time It is effective to let. Hereinafter, the present invention will be described in more detail. Polycarbonate and Lamellar Reinforcement
본 발명에서 사용하는 폴리카보네이트는， 플리카보네이트의 주쇄에 폴리실록산 구조가 도입되어 있지 않다는 점에서, 후술할 코폴리카보네이트와 구분된다. 본 발명에 따른 폴리카보네이트 조성물은， 상기 폴리카보네이트 외에 내충격성， 내열성 및 성형성 등의 개선을 위하여， 충격 보강제를 추가로 포함한다. 본 발명에서 사용할 수 있는 충격 보강제로는， 메틸메타크릴레이트ᅳ 부타디엔-스티렌계 공중합체， 스티렌 -아크릴로니트릴계 공중합체 , 아크릴로니트릴-부타디엔 -스티렌계 , 또는 이의 흔합물을 사용할 수 있다. 상기 순서대로 당업계에 각각 MBS 수지， SAN 수지， ABS 수지로 알려져 있다. 보다 바람직하게는， 상기 충격 보강제로 MBS 수지 및 SAN 수지의 흔합물을 사용할 수 있으며， 이의 중량비는 1:10 내지 10:1， 보다 바람직하게는 1:5 내지 5:1， 가장 바람직하게는 1:3 내지 3:1로 사용할 수 있다. 상기 충격 보강제 1 중량부를 기준으로, 상기 폴리카보네이트는 바람직하게는 5 내지 13 중량부， 보다 바람직하게는 8 내지 11 중량부를 포함한다. 상기 범위에서 내층격성， 내열성 및 성형성 등의 개선 효과가 우수하다. 상기 폴리카보네이트는 방향족 디올 화합물 및 카보네이트 전구체가 반웅하여 제조되는 것으로, 바람직하게는 하기 화학식 4로 표시되는 반복 단위를 포함한다: The polycarbonate used by this invention is distinguished from the copolycarbonate mentioned later in that the polysiloxane structure is not introduce | transduced into the main chain of a polycarbonate. The polycarbonate composition according to the present invention, in addition to the polycarbonate, in order to improve impact resistance, heat resistance and moldability, further includes an impact modifier. As the impact modifier used in the present invention, a methyl methacrylate butadiene-styrene copolymer, a styrene-acrylonitrile copolymer, an acrylonitrile-butadiene-styrene series, or a mixture thereof can be used. In the above order, known in the art as MBS resin, SAN resin, ABS resin, respectively. More preferably, a mixture of MBS resin and SAN resin may be used as the impact modifier, and the weight ratio thereof may be 1:10 to 10: 1, more preferably 1: 5 to 5: 1, most preferably 1 : 3 to 3: 1 can be used. Based on 1 part by weight of the impact modifier, the polycarbonate preferably comprises 5 to 13 parts by weight, more preferably 8 to 11 parts by weight. It is excellent in the improvement effect, such as layer resistance, heat resistance, and moldability, in the said range. The polycarbonate is prepared by reacting an aromatic diol compound and a carbonate precursor, and preferably includes a repeating unit represented by Formula 4 below:
[화학식 4]  [Formula 4]
Figure imgf000006_0001
상기 화학식 4에서，
Figure imgf000006_0001
In Chemical Formula 4,
R'i 내지 R'4는 각각 독립적으로 수소， d-10 알킬， 알콕시， 또는 할로겐이고， R'i to R'4 are each independently hydrogen, d- 10 alkyl, alkoxy, or halogen,
Z'는 비치환되거나 또는 페닐로 치환된 CHO 알킬렌， 비치환되거나 또는 CHO 알킬로 치환된 C3-15 사이클로알킬렌, 0, S, SO, S02, 또는 CO이다. 또한， 상기 폴리카보네이트는， 바람직하게는 중량 평균 분자량 (g/mol)이 1,000 내지 100 ,000이고, 보다 바람직하게는 15,000 내지 35, 000이다. 보다 바람직하게는, 상기 중량 평균 분자량은 20,000 이상， 21,000 이상， 22,000 이상， 23,000 이상， 24,000 이상 : Z 'is a C 3 alkylene substituted with CHO, unsubstituted or CHO-alkyl substituted by unsubstituted or phenyl-15 cycloalkylene, 0, S, SO, S0 2, or CO. Further, the polycarbonate preferably has a weight average molecular weight (g / mol) of 1,000 to 100,000, more preferably 15,000 to 35, 000. More preferably, the weight average molecular weight is 20,000 or more ， More than 21,000, More than 22,000, More than 23,000, More than 24,000 :
26,000 이상， 27,000 이상， 또는 28,000 이상이다. 또한， 26,000 or more, 27,000 or more, or 28,000 or more. Also,
분자량은 34,000 이하， 33,000 이하, 또는 32,000 이하이다. 바람직하게는， R'i 내지 R'4는 각각 독립적으로 수소， 메틸， 클로로， 브로모이다. 또한 바람직하게는， Z'는 비치환되거나 또는 페닐로 치환된 직쇄 또는 분지쇄의 10 알킬렌이며, 보다 바람직하게는 메틸렌， 에탄ᅳ 1,1-디일， 프로판ᅳ2， 2-디일 부탄 -2， 2-디일， 1-페닐에탄ᅳ1，1-디일， 또는 디페닐메틸렌이다ᅳ 또한 바람직하게는， z'는 사이클로핵산ᅳ1，1-디일， 0， S,The molecular weight is 34,000 or less, 33,000 or less, or 32,000 or less. Preferably, R'i to R ' 4 are each independently hydrogen, methyl, chloro, bromo. Also preferably, Z 'is straight-chain or branched 10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethanol 1,1-diyl, propane 2, 2-diyl butane-2 , 2-diyl, 1-phenylethane ᅳ 1,1-diyl, or diphenylmethylene ᅳ Also, z 'is cyclonucleic acid ᅳ 1,1-diyl, 0, S,
SO, S02, 또는 CO이다. 바람직하게는， 상기 화학식 4로 표시되는 반복단위는 비스 (4- 히드록시페닐)메탄， 비스 (4ᅳ히드록시페닐)에테르， 비스 (4- 히드록시페닐)설폰， 비스 (4-히드록시페닐)설폭사이드， 비스 (4- 히드록시페닐)설파이드， 비스 (4-히드록시페닐)케톤， 1，1-비스(4- 히드록시페닐)에탄， 비스페놀 A, 2,2-비스 (4ᅳ히드록시페닐)부탄， 1,1- 비스 (4ᅳ히드록시페닐)시클로핵산， 2 , 2-비스 (4—히드록시 -3， 5- 디브로모페닐)프로판， 2，2-비스 (4-히드록시 -3，5-디클로로페닐)프로판， 2,2- 비스 (4-히드록시 -3-브로모페닐)프로판， 2,2ᅳ비스 (4-히드록시 -3- 클로로페닐)프로판， 2,2—비스 (4-히드록시 -3-메틸페닐)프로판， 2，2-비스 (4- 히드록시 -3， 5-디메틸페닐)프로판， 1， 1-비스 (4-히드록시페닐) -1-페닐에탄， 비스 (4-히드록시페닐)디페닐메탄, 및 &，0 -비스[3-( 0- 히드록시페닐)프로필]폴리디메틸실록산으로 이루어진 군으로부터 선택되는 어느 하나 이상의 방향족 디올 화합물로부터 유래할 수 있다. 상기 '방향족 디올 화합물로부터 유래한다'의 의미는， 방향족 디올 화합물의 하이드록시기와 카보네이트 전구체가 반웅하여 상기 화학식 4로 표시되는 반복단위를 형성하는 것을 의미한다. 예컨대, 방향족 디올 화합물인 비스페놀 A와 카보네이트 전구체인 트리포스겐이 중합된 경우, 상기 화학식 4로 표시되는 반복단위는 하기 화학식 4-1로 표시된다: SO, S0 2 , or CO. Preferably, the repeating unit represented by Chemical Formula 4 is bis (4-hydroxyphenyl) methane, bis (4'hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ) Sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis (4 ᅳ hydride) Hydroxyphenyl) butane, 1,1-bis (4 ᅳ hydroxyphenyl) cyclonucleic acid, 2,2-bis (4—hydroxy-3, 5-dibromophenyl) propane, 2,2-bis (4- Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2bisbis (4-hydroxy-3-chlorophenyl) propane, 2 , 2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 1, 1-bis (4-hydroxyphenyl) -1 -Phenylethane, bis (4-hydroxyphenyl) diphenylmethane, and & 0 -bis [3- (0-hydroxyphenyl) propyl] polydimethylsiloxane can be derived from any one or more aromatic diol compounds selected from the group consisting of. The term “derived from an aromatic diol compound” means that a hydroxyl group of an aromatic diol compound reacts with a carbonate precursor to form a repeating unit represented by the formula (4). For example, when an aromatic diol compound bisphenol A and a carbonate precursor triphosgene are polymerized, the repeating unit represented by Formula 4 is represented by the following Formula 4-1:
4-1]  4-1]
Figure imgf000008_0001
Figure imgf000008_0001
상기 카보네이트 전구체로는， 디메틸 카보네이트， 디에틸 카보네이트 디부틸 카보네이트， 디시클로핵실 카보네이트, 디페닐 카보네이트， 디토릴 카보네이트, 비스 (클로로페닐) 카보네이트， 디 -m-크레실 카보네이트， 디나프틸 카보네이트， 비스 (디페닐) 카보네이트， 포스겐， 트리포스겐， 디포스겐， 브로모포스겐 및 비스할로포르메이트로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 바람직하게는， 트리포스겐 또는 포스겐을 사용할 수 있다. 코폴리카보네이트 Examples of the carbonate precursor include dimethyl carbonate, diethyl carbonate dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate and bis At least one selected from the group consisting of (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate can be used. Preferably, triphosgene or phosgene can be used. Copolycarbonate
본 발명에서 사용하는 코폴리카보네이트는, 폴리카보네이트의 주쇄에 폴리실록산 구조가 도입된 고분자를 의미한다. 상기 코폴리카보네이트는， 무기 충전제의 첨가에 따라 발생하는 외관 불량을 억제하는 효과가 있다. 상기 충격 보강제 1 중량부를 기준으로, 상기 코폴리카보네이트는 1 내지 6 중량부， 보다 바람직하게는 2 내지 5 중량부를 포함한다. 상기 범위에서 외관 블량을 억제하는 효과가 우수하다. 상기 폴리카보네이트의 주쇄는, 방향족 디을 화합물과 카보네이트 전구체가 반응하여 형성되며， 구체적으로 상기 화학식 1로 표시되는 반복단위를 의미한다. 상기 화학식 1에서， 바람직하게는， ¾ 내지 ¾는 각각 독립적으로 수소， 메틸， 클로로， 또는 브로모이다. 또한 바람직하게는ᅳ Z는 비치환되거나 또는 페닐로 치환된 직쇄 또는 분지쇄의 c 10 알킬렌이며， 보다 바람직하게는 메틸렌， 에탄ᅳ 1 , 1-디일, 프로판 -2， 2-디일， 부탄— 2， 2-디일， 1-페닐에탄 -1，1-디일, 또는 디페닐메틸렌이다. 또한 바람직하게는， Z는 사이클로핵산 -1，1ᅳ디일， 0， S, SO, S02 , 또는 CO이다. 바람직하게는, 상기 화학식 1로 표시되는 반복단위는 비스 (4- 히드록시페닐)메탄， 비스 (4ᅳ히드록시페닐)에테르， 비스 (4- 히드록시페닐)설폰， 비스 (4ᅳ히드록시페닐)설폭사이드， 비스 (4- 히드록시페닐)설파이드， 비스 (4-히드록시페닐)케톤， 1，1-비스 (4- 히드록시페닐)에탄， 비스페놀 A , 2 , 2-비스 (4ᅳ히드록시페닐)부탄， 1 , 1- 비스 (4-히드록시페닐)시클로핵산， 2，2-비스 (4-히드록시 -3 , 5- 디브로모페닐)프로판， 2，2-비스 (4-히드록시 -3 , 5-디클로로페닐)프로판, 2 , 2- 비스 (4-히드록시 -3-브로모페닐 )프로판， 2 , 2-비스 (4-히드록시 -3- 클로로페닐)프로판， 2 , 2-비스 (4-히드록시ᅳ 3-메틸페닐)프로판， 2，2ᅳ비스 (4- 히드록시 -3 , 5-디메틸페닐)프로판， 1，1-비스(4-히드록시페닐)ᅳ1ᅳ페닐에탄， 비스 (4-히드록시페닐)디페닐메탄， 및 α， ωᅳ비스 [3-( 0 - 히드록시페닐)프로필]폴리디메틸실록산으로 이루어진 군으로부터 선택되는 어느 하나 이상의 방향족 디올 화합물로부터 유래할 수 있다. 상기 '방향족 디을 화합물로부터 유래한다'의 의미는， 방향족 디올 화합물의 하이드록시기와 카보네이트 전구체가 반웅하여 상기 화학식 1로 표시되는 반복단위를 형성하는 것을 의미한다. 예컨대， 방향족 디을 화합물인 비스페놀 Α와 카보네이트 전구체인 트리포스겐이 중합된 경우， 상기 화학식 1로 표시되는 반복단위는 하기 화학식 1-1로 표시된다: The copolycarbonate used by this invention means the polymer in which the polysiloxane structure was introduce | transduced into the main chain of polycarbonate. The copolycarbonate has an effect of suppressing appearance defects caused by the addition of the inorganic filler. Based on 1 part by weight of the impact modifier, the copolycarbonate comprises 1 to 6 parts by weight, more preferably 2 to 5 parts by weight. It is excellent in the effect which suppresses external appearance quantity in the said range. The main chain of the polycarbonate is formed by reacting an aromatic di compound with a carbonate precursor, and specifically means a repeating unit represented by Chemical Formula 1. In Chemical Formula 1, preferably, ¾ to ¾ are each independently hydrogen, methyl, chloro, or bromo. Also preferably, Z is straight or branched chain c 10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane 1, 1-diyl, propane-2, 2-diyl, butane— 2, 2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, Z is cyclonucleic acid -1, 1 ᅳ diyl, 0, S, SO, S0 2 , or CO. Preferably, the repeating unit represented by Chemical Formula 1 is bis (4-hydroxyphenyl) methane, bis (4'hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4'hydroxyphenyl) ) Sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2, 2-bis (4 ᅳ hydride) Hydroxyphenyl) butane, 1, 1-bis (4-hydroxyphenyl) cyclonucleic acid, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4- Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2 , 2-bis (4-hydroxy ᅳ 3-methylphenyl) propane, 2,2'bis (4-hydroxy-3, 5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ᅳ 1 ᅳ phenylethane, bis (4-hydroxyphenyl) diphenylmethane, and α, ω It may be derived from any one or more aromatic diol compounds selected from the group consisting of C: bis [3- (0-hydroxyphenyl) propyl] polydimethylsiloxane. The term “derived from an aromatic diol compound” means that the hydroxy group and the carbonate precursor of the aromatic diol compound react to form a repeating unit represented by the formula (1). For example, when the bisphenol A, which is an aromatic di compound, and triphosphene, which is a carbonate precursor, are polymerized, the repeating unit represented by Formula 1 is It is represented by Formula 1-1:
1-1]  1-1]
Figure imgf000010_0001
Figure imgf000010_0001
상기 카보네이트 전구체로는， 디메틸 카보네이트， 디에틸 카보네이트 디부틸 카보네이트, 디시클로핵실 카보네이트, 디페닐 카보네이트， 디토릴 카보네이트， 비스 (클로로페닐) 카보네이트， 디 -m-크레실 카보네이트， 디나프틸 카보네이트, 비스 (디페닐) 카보네이트， 포스겐， 트리포스겐, 디포스겐， 브로모포스겐 및 비스할로포르메이트로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 바람직하게는， 트리포스겐 또는 포스겐을 사용할 수 있다. 상기 폴리실록산 구조는， 상기 화학식 2로 표시되는 반복 단위 및 상기 화학식 3으로 표시되는 반복 단위를 의미한다 . 상기 화학식 2에서， 바람직하게는， ¾는 각각 독립적으로 C2-10 알킬렌이고， 보다 바람직하게는 C2-4 알킬렌이고, 가장 바람직하게는 프로판 -1 ,3-디일이다. 또한 바람직하게는， ^는 수소, 또는 d-6 알콕시이고， 보다 바람직하게는 수소 , 또는 d-4 알콕시이고, 가장 바람직하게는 수소， 또는 메톡시이다. 또한 바람직하게는， ¾는 각각 독립적으로 수소， 메틸， 에틸, 프로필，Examples of the carbonate precursor include dimethyl carbonate, diethyl carbonate dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate and bis One or more selected from the group consisting of (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate can be used. Preferably, triphosgene or phosgene can be used. The polysiloxane structure means a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3. In the above formula (2), preferably, ¾ are each independently C 2 - 4 alkylene and is, most preferably, propane-1,3-diyl-10 alkylene, more preferably C 2. Also preferably, ^ is hydrogen or d- 6 alkoxy, more preferably hydrogen or d- 4 alkoxy, most preferably hydrogen or methoxy. Also preferably, ¾ is independently hydrogen, methyl, ethyl, propyl,
3-페닐프로필， 2-페닐프로필, 3ᅳ (옥시라닐메록시)프로필， 플루오로， 클로로， 브로모， 아이오도， 메톡시， 에록시, 프로폭시， 알릴， 2 , 2 , 2- 트리플루오로에틸, 3，3，3-트리플루오로프로필, 페닐， 또는 나프틸이다. 또한 바람직하게는， ¾는 각각 독립적으로 Cwo 알킬이고， 보다 바람직하게는 d-6 알킬이고 , 보다 바람직하게는 d-3 알킬이고， 가장 바람직하게는 메틸이다. 또한 바람직하게는， 상기 n은 10 이상, 15 이상, 20 이상， 25 이상，3-phenylpropyl, 2-phenylpropyl, 3 '(oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2, 2, 2-trifluoro Roethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. Also preferably, ¾ is each independently Cwo alkyl, more preferably d- 6 alkyl, more preferably d- 3 alkyl, most preferably methyl. Also preferably, n is 10 or more, 15 or more, 20 or more, 25 or more,
30 이상, 31 이상， 또는 32 이상이고， 75 이하， 70 이하， 65 이하， 60 이하， 55 이하， 50 이하， 45 이하, 40 이하, 39 이하， 38 이하， 또는 37 이하의 정수이다. 상기 화학식 3에서， 바람직하게는, ¾는 각각 독립적으로 C2-10 알킬렌이고, 보다 바람직하게는 C2-6 알킬렌이고， 가장 바람직하게는 이소부틸렌이다. 또한 바람직하게는, Y2는 수소이다. 또한 바람직하게는， ¾는 각각 독립적으로 수소， 메틸， 에틸， 프로필， 3-페닐프로필， 2-페닐프로필， . 3- (옥시라닐메톡시 )프로필， 플루오로， 클로로， 브로모, 아이오도， 메톡시， 에톡시, 프로폭시， 알릴， 2，2，2- 트리폴루오로에틸， 3，3，3-트리플루오로프로필, 페닐， 또는 나프틸이다. 또한 바람직하게는， ¾는 각각 독립적으로 d-10 알킬이고， 보다 바람직하게는 d-6 알킬이고， 보다 바람직하게는 d-3 알킬이고， 가장 바람직하게는 메틸이다. 또한 바람직하게는， 상기 m은 40 이상， 45 이상， 50 이상， 55 이상， 56 이상， 57 이상， 또는 58 이상이고， 80 이하， 75 이하， 70 이하, 65 이하, 64 이하， 63 이하， 또는 62 이하의 정수이다. 상기 화학식 2로 표시되는 반복 단위 및 상기 화학식 3으로 표시되는 반복 단위는 각각 하기 화학식 2-1로 표시되는 실록산 화합물 및 하기 화학식 3-1로 표시되는 실록산 화합물로부터 유래한다.
Figure imgf000012_0001
It is an integer of 30 or more, 31 or more, or 32 or more, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, 50 or less, 45 or less, 40 or less, 39 or less, 38 or less, or 37 or less. In Formula 3, preferably, ¾ are each independently a C 2 - to 10 alkylene, more preferably C 2 - 6 alkylene and most preferably isobutylene. Also preferably, Y 2 is hydrogen. Also preferably, ¾ is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl,. 3- (Oxiranylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2,2- trifluoroethyl, 3,3,3- Trifluoropropyl, phenyl, or naphthyl. Also preferably, ¾ is each independently d- 10 alkyl, more preferably d- 6 alkyl, more preferably d- 3 alkyl, and most preferably methyl. Also preferably, m is 40 or more, 45 or more, 50 or more, 55 or more, 56 or more, 57 or more, or 58 or more, 80 or less, 75 or less, 70 or less, 65 or less, 64 or less, 63 or less, or It is an integer of 62 or less. The repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 are each derived from a siloxane compound represented by Formula 2-1 and a siloxane compound represented by Formula 3-1.
Figure imgf000012_0001
상기 화학식 2-1에서， ， Yi , R5 및 n의 정의는 앞서 정의한 바와 같다. In Formula 2-1,?, Yi, R 5 and n are as defined above.
[화학식 3-1]  [Formula 3-1]
Figure imgf000012_0002
상기 화학식 3-1에서， ¾， Y2 , R6 및 m의 정의는 앞서 정의한 바와 같다. 상기 '실록산 화합물로부터 유래한다'의 의미는， 상기 각각의 실록산 화합물의 하이드록시기와 카보네이트 전구체가 반웅하여 상기 각각의 화학식 2로 표시되는 반복 단위 및 화학식 3으로 표시되는 반복 단위를 형성하는 것을 의미한다. 또한， 상기 화학식 2 및 3의 반복 단위의 형성에 사용할 수 있는 카보네이트 전구체는， 앞서 설명한 화학식 1의 반복 단위의 형성에 사용할 수 있는 카보네이트 전구체에서 설명한 바와 같다. 상기 화학식 2-1로 표시되는 실록산 화합물 및 상기 화학식 3-1로 표시되는 실록산 화합물의 제조 방법은 각각 하기 반웅식 1 및 2와 같다.
Figure imgf000012_0002
In Formula 3-1, ¾, Y 2 , R 6 and m are the same as defined above. The term “derived from the siloxane compound” means that the hydroxyl group and the carbonate precursor of each siloxane compound react to form a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3 . In addition, the carbonate precursors that can be used to form the repeating units of Formulas 2 and 3 are the same as those described above for the carbonate precursors that can be used to form the repeating units of Formula 1. The method for producing the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 3-1 is as follows.
[반응식 1] Scheme 1
Figure imgf000013_0001
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000013_0002
2-1 상기 반웅식 1에서，  2-1 in the above formula 1,
Χι'는 C2-10 알케닐이고, Χι 'is C 2 - 10 alkenyl, and Al,
Xi, Yi, R5 및 n의 정의는 앞서 정의한 바와 같고 The definitions of Xi, Yi, R 5 and n are as defined above
Figure imgf000013_0003
Figure imgf000013_0003
3-1  3-1
상기 반응식 2에서,  In Scheme 2,
Χ2'는 C2— 10 알케닐이고， Χ 2 'is C 2 — 10 alkenyl,
X2, Y2, Re 및 m의 정의는 앞서 정의한 바와 같다. 상기 반웅식 1 및 반웅식 2의 반응은， 금속 촉매 하에 수행하는 것이 바람직하다. 상기 금속 촉매로는 Pt 촉매를 사용하는 것이 바람직하며， Pt 촉매로 애쉬바이 (Ashby)촉매， 칼스테드 (Karstedt)촉매， 라모레오 (Lamoreaux)촉매 , 스파이어 (Speier)촉매， PtCl2(C0D) ,The definitions of X 2 , Y 2 , Re and m are as defined above. It is preferable that the reaction of Banung 1 and Banung 2 is performed under a metal catalyst. It is preferable to use a Pt catalyst as the metal catalyst, an Ashby catalyst, a Karlstedt catalyst, Lamoreaux Catalyst, Speier Catalyst, PtCl 2 (C0D),
PtCl2(벤조니트릴 )2， 및 H2PtBr6로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 상기 금속 촉매는 상기 화학식 7 또는 9로 표시되는 화합물 100 중량부를 기준으로 0.001 중량부 이상， 0.005 중량부 이상， 또는 0.01 중량부 이상이고， 1 중량부 이하， 0.1 중량부 이하， 또는 0.05 중량부 이하로 사용할 수 있다. 또한， 상기 반웅 온도는 so 내지 locrc가 바람직하다. 또한， 상기 반웅 시간은 1시간 내지 5시간이 바람직하다. 또한， 상기 화학식 7 또는 9로 표시되는 . 화합물은 오르가노디실록산과 오르가노시클로실록산을 산 촉매 하에서 반웅시켜 제조할 수 있으며， 상기 반웅 물질의 함량을 조절하여 n 및 m을 조절할 수 있다. 상기 반웅 은도는 50 내지 70°C가 바람직하다. 또한， 상기 반응 시간은 1시간 내지 6시간이 바람직하다. 상기 오르가노디실록산으로， 테트라메틸디실록산， 테트라페닐디실록산， 핵사메틸디실록산 및 핵사페닐디실록산으로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 또한, 상기 오르가노시클로실록산은 일례로 오르가노시클로테트라실록산을 사용할 수 있으며， 이의 일례로 옥타메틸시클로테트라실록산 및 옥타페닐시클로테트라실록산 등을 들 수 있다. 상기 오르가노디실록산은， 상기 오르가노시클로실록산 100 중량부를 기준으로 0.1 중량부 이상, 또는 2 중량부 이상이고, 10 중량부 이하, 또는 8 중량부 이하로 사용할 수 있다. 상기 산 촉매로는 H2S04, HC104, AICI3 , SbCl5, SnCl4 및 산성 백토로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 또한， 상기 산 촉매는 오르가노사클로실록산 100 중량부를 기준으로 0.1 중량부 이상， 0.5 중량부 이상， 또는 1 증량부 이상이고， 10 증량부 이하， 5 중량부 이하, 또는 3 중량부 이하로 사용할 수 있다. 특히， 상기 화학식 2로 표시되는 반복 단위와 상기 화학식 3으로 표시되는 반복 단위의 함량을 조절하여, 코폴리카보네이트 (A)의 물성을 조절할 수 있다. 상기 반복단위 간의 중량비는 1:99 내지 99:1가 될 수 있다. 바람직하게는 3:97 내지 97:3, 5:95 내지 95:5， 10： 90 내지 90:10， 또는 15:85 내지 85:15이고, 보다 바람직하게는 20:80 내지 80:20이다. 상기 반복 단위의 중량비는 실특산 화합물， 예컨대 상기 화학식 2-1로 표시되는 실록산 화합물 및 상기 화학식 3-1로 표시되는 실록산 화합물의 중량비에 대웅된다. 바람직하게는， 상기 화학식 2로 표시되는 반복 단위는.， 하기 화학식 2— 2로 표시된다: At least one selected from the group consisting of PtCl 2 (benzonitrile) 2 , and H 2 PtBr 6 can be used. The metal catalyst is 0.001 parts by weight, 0.005 parts by weight, or 0.01 parts by weight or more, 1 part by weight, 0.1 parts by weight, or 0.05 parts by weight or less based on 100 parts by weight of the compound represented by Chemical Formula 7 or 9. Can be used as In addition, the reaction temperature is preferably so to locrc. In addition, the reaction time is preferably 1 hour to 5 hours. In addition, represented by the formula (7) or (9). The compound may be prepared by reacting organodisiloxane and organocyclosiloxane under an acid catalyst, and n and m may be controlled by adjusting the content of the reaction material. The reaction is preferably 50 to 70 ° C. In addition, the reaction time is preferably 1 hour to 6 hours. As the organodisiloxane, one or more selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, nuxamethyldisiloxane and nuxaphenyldisiloxane can be used. As the organocyclosiloxane, an organocyclotetrasiloxane can be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. The organodisiloxane may be 0.1 part by weight or more, or 2 parts by weight or more, 10 parts by weight or less, or 8 parts by weight or less, based on 100 parts by weight of the organocyclosiloxane. As the acid catalyst, one or more selected from the group consisting of H 2 S04, HC10 4 , AICI3, SbCl 5 , SnCl 4, and acidic clay may be used. In addition, the acid catalyst is 0.1 parts by weight or more, based on 100 parts by weight of the organosaclosiloxane, 0.5 It is more than 1 weight part or 1 weight part or more, 10 weight part or less, 5 weight part or less, or 3 weight part or less can be used. In particular, by adjusting the content of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3), it is possible to control the physical properties of the copolycarbonate (A). The weight ratio between the repeating units may be 1:99 to 99: 1. Preferably it is 3: 97-97: 3, 5: 95-95: 5, 10: 90-90: 10, or 15: 85-85: 15, More preferably, it is 20: 80-80: 20. The weight ratio of the repeating unit is based on the weight ratio of the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 2-1. Preferably, the repeating unit represented by Formula 2 is . , Represented by the following Chemical Formula 2-2:
[화학식 2-2]  [Formula 2-2]
Figure imgf000015_0001
상기 화학식 2-2에서， ¾ 및 n은 앞서 정의한 바와 같다. 바람직하게는， ¾은 메틸이다. 또한 바람직하게는, 화학식 3으로 표시되는 반복 단위는, 하기 화학식 3-2로 표시된다 :
Figure imgf000015_0001
In Formula 2-2, ¾ and n are as defined above. Preferably, ¾ is methyl. Also preferably, the repeating unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-2:
[화학식 3-2]  [Formula 3-2]
Figure imgf000015_0002
상기 화학식 3ᅳ 2에서， ¾ 및 m은 앞서 정의한 바와 같다. 바람직하게는， ¾는 메틸이다. 또한， 상기 코폴리카보네이트 (A)에 있어， 상기 화학식 1-1로 표시되는 반복 단위， 상기 화학식 2ᅳ 2로 표시되는 반복 단위 및 상기 화학식 3ᅳ2로 표시되는 반복 단위를 모두 포함하는 코폴리카보네이트를 제공한다. 또한, 상기 화학식 1로 표시되는 반복 단위의 중량과， 상기 화학식 2로 표시되는 반복 단위 및 상기 화학식 3으로 표시되는 반복 단위의 총 중량의 중량비 (화학식 1 : (화학식 2 + 화학식 3) )는 1 : 0.04-0.07이 바람직하다. 또한， 본 발명은 상술한 코폴리카보네이트 (A)의 제조 방법으로서， 방향족 디올 화합물， 카보네이트 전구체 및 하나 이상의 실록산 화합물을 중합하는 단계를 포함하는 코폴리카보네이트 (A)의 제조 방법을 제공한다. 상기 방향족 디올 화합물， 카보네이트 전구체 및 하나 이상의 실록산 화합물은 앞서 설명한 바와 같다. 상기 증합시， 상기 하나 이상의 실록산 화합물은， 방향족 디올 화합물， 카보네이트 전구체 및 하나 이상의 실록산 화합물 총합 100 중량 %에 1 중량 ¾) 이상， 1. 1 중량 이상， 1.2 중량 % 이상， 1.3 중량 % 이상， 1.4 증량 % 이상, 또는 1.5 증량 % 이상이고 3 중량 % 이하， 2.9 증량 ¾> 이하， 2.8 중량 % 이하， 2.7 증량 % 이하， 2.6 중량 % 이하， 2.5 중량 % 이하, 2.4 중량 % 이하， 2.3 중량 % 이하， 2.2 중량 % 이하， 2. 1 중량 % 이하, 또는 2 중량 % 이하를 사용할 수 있다. 또한， 상기 방향족 디올 화합물은， 방향족 디을 화합물， 카보네이트 전구체 및 하나 이상의 실록산 화합물 총합 100 중량 %에 대해 40 증량 % 이상， 50 중량 % 이상, 또는 55 중량 이상이고， 80 중량 ¾> 이하， 70 증량 % 이하， 또는 65 중량 % 이하로 사용할 수 있다. 또한, 상기 카보네이트 전구체는， 방향족 디을 화합물， 카보네이트 전구체 및 하나 이상의 실록산 화합물 총합 100 중량%에 대해 10 중량 % 이상， 20 중량 % 이상， 또는 30 중량 %이고， 60 중량 % 이하， 50. 증량 % 이하， 또는 40 증량 % 이하로 사용할 수 있다. 또한， 상기 중합 방법으로는， 일례로 계면중합 방법을 사용할 수 있으며， 이 경우 상압과 낮은 은도에서 중합 반응이 가능하며 분자량 조절이 용이한 효과가 있다. 상기 계면중합은 산결합제 및 유기용매의 존재 하에 수행하는 것이 바람직하다. 또한, 상기 계면중합은 ,일례로 선중합 (pre-polymer i zat ion) 후 커플링제를 투입한 다음， 다시 중합시키는 단계를 포함할 수 있고， 이 경우 고분자량의 코폴리카보네이트 (A)를 얻을 수 있다. 상기 계면중합에 사용되는 물질들은 폴리카보네이트의 중합에 사용될 수 있는 물질이면 특별히 제한되지 않으며， 그 사용량도 필요에 따라 조절할 수 있다. 상기 산결합제로는 일례로 수산화나트륨, 수산화칼륨 등의 알칼리금속 수산화물 또는 피리딘 둥의 아민 화합물을 사용할 수 있다. 상기 유기 용매로는 통상 폴리카보네이트의 중합에 사용되는 용매이면 특별히 제한되지 않으며， 일례로 메틸렌클로라이드， 클로로벤젠 등의 할로겐화 탄화수소를 사용할 수 있다. 또한， 상기 계면중합은 반웅 촉진을 위해 트리에틸아민, 테트라 -n- 부틸암모늄브로마이드， 테트라 -n-부틸포스포늄브로마이드 등의 3차, 아민 화합물, 4차 암모늄 화합물， 4차 포스포늄 화합물 등과 같은 반응 촉진제를 추가로 사용할 수 있다. 상기 계면중합의 반웅 온도는 0 내지 4(rc인 것이 바람직하며， 반웅 시간은 10분 내지 5시간이 바람직하다. 또한， 계면중합 반웅 중， pH는 9이상 또는 11이상으로 유지하는 것이 바람직하다. 또한， 상기 계면중합은 분자량 조절제를 더 포함하여 수행할 수 있다. 상기 분자량 조절제는 중합개시 전， 중합개시 중 또는 중합개시 후에 투입할 수 있다. 상기 분자량 조절제로 모노 -알킬페놀을 사용할 수 있으며， 상기 모노 -알킬페놀은 일례로 p-tert-부틸페놀， P-쿠밀페놀， 데실페놀， 도데실페놀， 테트라데실페놀， 핵사데실페놀， 옥타데실페놀， 에이코실페놀， 도코실페놀 및 트리아콘틸페놀로 이루어진 군으로부터 선택된 1종 이상이고, 바람직하게는 p-ter.t-부틸페놀이며， 이 경우 분자량 조절 효과가 크다. 상기 분자량 조절제는 일례로 방향족 디을 화합물 100 중량부를 기준으로 0.01 중량부 이상， 0,1 중량부 이상， 또는 1 중량부 이상이고， 10 중량부 이하， 6 증량부 이하， 또는 5 중량부 이하로 포함되고, 이 범위 내에서 원하는 분자량을 얻을 수 있다. 상기 코폴리카보네이트는, 바람직하게는 증량 평균 분자량 (g/mol)이 1,000 내지 100， 000이고， 보다 바람직하게는 15,000 내지 35,000 이다. 보다 바람직하게는， 상기 중량 평균 분자량은 20,000 이상， 21,000 이상， 22,000 이상， 23,000 이상， 24,000 이상， 25,000 이상， 26,000 이상， 27,000 이상, 또는 28,000 이상이다. 또한， 상기 중량 평균 분자량은 34,000 이하， 33,000 이하, 또는 32,000 이하이다. 무기 층전제
Figure imgf000015_0002
In Chemical Formula 3 ′ 2, ¾ and m are as defined above. Preferably, ¾ is methyl. In addition, in the copolycarbonate (A), a copoly includes both a repeating unit represented by Formula 1-1, a repeating unit represented by Formula 2 ′ 2 and a repeating unit represented by Formula 3 ′ 2 Provide carbonate. In addition, the weight ratio of the weight of the repeating unit represented by the formula (1) and the total weight of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) (Formula 1: (Formula 2 + Formula 3)) is 1 : 0.04-0.07 is preferable. The present invention also provides a process for preparing copolycarbonate (A), comprising the step of polymerizing an aromatic diol compound, a carbonate precursor and at least one siloxane compound. The aromatic diol compound, carbonate precursor and one or more siloxane compounds are as described above. At the time of the polymerization, the at least one siloxane compound is at least 1 weight ¾), at least 1 weight 1, at least 1.2 weight%, at least 1.3 weight%, 1.4 to 100% by weight of the aromatic diol compound, the carbonate precursor and the at least one siloxane compound. Or more, or 1.5 or more, or more than 1.5% by weight, 3% by weight or less, 2.9% by weight ¾>, 2.8% by weight or less, 2.7% by weight or less, 2.6% by weight, 2.5% by weight, 2.4% by weight or less, 2.3% by weight or less , 2.2 wt% or less, 2. 1 wt% or less, or 2 wt% or less may be used. In addition, the aromatic diol compound is 40% by weight or more, 50% by weight or more, or 55% by weight, 80% by weight or less, 70% by weight, based on 100% by weight of the aromatic diol compound, the carbonate precursor and one or more siloxane compounds in total. Or less than or equal to 65% by weight. Also, The carbonate precursor is 10% by weight, 20% by weight, or 30% by weight, 60% by weight, 50.% by weight or less, based on 100% by weight of the total aromatic di-compound, carbonate precursor and one or more siloxane compounds. Can be used in 40% by weight or less. In addition, as the polymerization method, for example, an interfacial polymerization method may be used. In this case, the polymerization reaction is possible at atmospheric pressure and low silver, and the molecular weight is easily controlled. The interfacial polymerization is preferably carried out in the presence of an acid binder and an organic solvent. In addition, the interfacial polymerization may include, for example, adding a coupling agent after prepolymerization (pre-polymer i zat ion) and then polymerizing again, in which case a high molecular weight copolycarbonate (A) is obtained. Can be. The materials used for the interfacial polymerization are not particularly limited as long as they are materials that can be used for the polymerization of polycarbonate, and the amount of the materials used may be adjusted as necessary. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound of pyridine round may be used. The organic solvent is not particularly limited as long as it is a solvent usually used for polymerization of polycarbonate, and for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene may be used. In addition, the interfacial polymerization may be performed in order to promote reaction, such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, tertiary , amine compound, quaternary ammonium compound, quaternary phosphonium compound, and the like. Reaction accelerators may be further used. The reaction temperature of the interfacial polymerization is preferably 0 to 4 (rc, The time is preferably 10 minutes to 5 hours. Moreover, it is preferable to maintain pH in 9 or more or 11 or more in interfacial polymerization reaction. In addition, the interfacial polymerization may be performed by further including a molecular weight regulator. The molecular weight modifier may be added before the start of polymerization, during the start of the polymerization, or after the start of the polymerization. Mono-alkylphenol may be used as the molecular weight modifier, and the mono-alkylphenol is, for example, p-tert-butylphenol, P-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nuxadecylphenol, octadecyl It is at least one selected from the group consisting of phenol, eicosylphenol, docosylphenol and triacontylphenol, preferably p-ter.t-butylphenol, in which case the molecular weight control effect is large. The molecular weight modifier may be, for example, 0.01 parts by weight or more, 0,1 parts by weight, or 1 part by weight or more, 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of aromatic diol compound. It is possible to obtain a desired molecular weight within this range. The copolycarbonate preferably has an increased average molecular weight (g / mol) of 1,000 to 100, 000, more preferably 15,000 to 35,000. More preferably, the weight average molecular weight is 20,000 or more, 21,000 or more, 22,000 or more, 23,000 or more, 24,000 or more, 25,000 or more, 26,000 or more, 27,000 or more, or 28,000 or more. In addition, the said weight average molecular weight is 34,000 or less, 33,000 or less, or 32,000 or less. Inorganic layer agent
본 발명에서 사용되는 무기 층전제는， 폴리카보네이트의 물성을 향상시키기 위하여 사용된다. 일반적으로， 무기 충전제가 포함될 경우 물성이 보강되나， 사출 성형과 같은 가공시 흐름 자국 ( f low mark)이 생기는 등 외관 불량이 발생하는 문제가 있다. 그러나ᅳ 본 발명에서는 상술한 바와 같이 코폴리카보네이트를 포함함으로서， 이러한 외관 불량의 생성을 억제할 수 있다. 상기 충격 보강제 1 중량부를 기준으로, 상기 무기 충전제는 0.5 내지 4 중량부， 보다 바람직하게는 0.5 내지 3 중량부， 가장 바람직하게는 0.5 내지 2 중량부를 포함한다. 상기 범위에서 물성 향상 효과가 우수하다. 상기 무기 층전제로는， 탈크 ( talc) , 웰라스토나이트 (wol l astoni te) , 마이카 (mi ca) , 또는 이의 흔합물을 사용할 수 있다. 폴리카보네이트조성물 The inorganic layer filler used in the present invention is used to improve the physical properties of the polycarbonate. Generally, when inorganic fillers are included, physical properties are reinforced. There is a problem in that appearance defects occur, such as a f low mark during processing such as molding. However, in the present invention, as described above, by including the copolycarbonate, it is possible to suppress the generation of such appearance defects. Based on 1 part by weight of the impact modifier, the inorganic filler comprises 0.5 to 4 parts by weight, more preferably 0.5 to 3 parts by weight, most preferably 0.5 to 2 parts by weight. It is excellent in the physical property improvement effect in the said range. As the inorganic layer agent, talc, wol l astoni te, mica, or a mixture thereof may be used. Polycarbonate Composition
본 발명에 폴리카보네이트 수지 조성물은, 상술한 폴리카보네이트， 층격 보강제， 코폴리카보네이트， 및 무기 층전제를 포함한다. 또한， 상기 폴리카보네이트 수지 조성물은， 필요에 따라 난연거 1 , 산화방지제， 열안정제, 광안정화제， 가소제, 대전방지제， 핵제， 활제， 층격보강제， 형광증백제， 자외선흡수제， 안료 및 염료로 이루어진 군으로부터 선택된 어느 하나 이상의 첨가제를 추가로 포함할 수 있다. 특히， 상기 난연제로는 인계 난연제를 사용할 수 있다. 상기 인계 난연제는 당업계에서 통상적으로 사용되는 것이면 특별히 제한되지 않으며， 일례로 비스페놀 -A 비스 (디페닐 포스페이트) (Bi sphenol-A bi s(diphenyl phosphate) )를 사용할 수 있다. 상기 층격 보강제 1 중량부를 기준으로， 상기 난연제는 0.5 내지 4 중량부로 포함할 수 있으며， 상기 범위에서 난연성 향상 효과가 우수하다. 또한， 본 발명은 상기 폴리카보네이트 조성물을 포함하는 물품을 제공한다. 바람직하게는， 상기 물품은 사출 성형품이다. 상술한 바와 같이 본 발명에 따른 폴리카보네이트 조성물은， 폴리카보네이트 및 층격 보강제를 포함하고， 이의 기계적 물성을 향상시키기 위한 무기 충전제를 포함하고， 무기 충전제를 포함하면서 발생하는 외관 불량의 문제를 코폴리카보네이트를 포함함으로써 해결할 수 있다. 상기 물품의 제조 방법은， 본 발명에 따른 폴리카보네이트 조성물과 필요에 따라 첨가제를 믹서를 이용하여 흔합한 후, 이를 압출기로 압출성형하여 펠릿으로 제조하고， 상기 펠릿을 건조시킨 다음 사출성형기로 사출하는 단계를 포함할 수 있다. The polycarbonate resin composition in the present invention includes the polycarbonate, the layer reinforcement agent, the copolycarbonate, and the inorganic layer filler described above. In addition, the polycarbonate resin composition, if necessary, group consisting of flame retardant 1, antioxidant, heat stabilizer, light stabilizer, plasticizer, antistatic agent, nucleating agent, lubricant, laminar enhancer, fluorescent brightener, ultraviolet absorber, pigment and dye It may further comprise any one or more additives selected from. In particular, a phosphorus-based flame retardant may be used as the flame retardant. The phosphorus-based flame retardant is not particularly limited as long as it is commonly used in the art, for example, bisphenol-A bis (diphenyl phosphate) (Bi sphenol-A bi s (diphenyl phosphate)) may be used. Based on 1 part by weight of the layered reinforcing agent, the flame retardant may include 0.5 to 4 parts by weight, it is excellent in the flame retardancy improving effect in the above range. The present invention also provides an article comprising the polycarbonate composition. Preferably, the article is an injection molded article. As mentioned above The polycarbonate composition according to the present invention includes a polycarbonate and a layer reinforcing agent, includes an inorganic filler for improving its mechanical properties, and solves the problem of appearance defects occurring while including the inorganic filler by including copolycarbonate. Can be. In the method for producing the article, the polycarbonate composition according to the present invention and the additives are mixed as necessary using a mixer, and then extruded with an extruder to produce pellets, the pellets are dried and then injected into an injection molding machine. It may include a step.
【발명의 효과】  【Effects of the Invention】
상술한 바와 같이 본 발명에 따른 폴리카보네이트 조성물은， 폴리카보네이트 및 층격 보강제를 포함하고， 이의 기계적 물성을 향상시키기 위한 무기 층전제를 포함하고， 무기 층전제를 포함하면서 발생하는 외관 블량의 문제를 코폴리카보네이트를 포함함으로써 해결할 수 있다는 특징이 있다.  As described above, the polycarbonate composition according to the present invention includes a polycarbonate and a layer reinforcing agent, includes an inorganic layering agent for improving its mechanical properties, and addresses problems of appearance defects occurring while including an inorganic layering agent. There is a feature that can be solved by including a polycarbonate.
【발명을 실시하기 위한 구체적인 내용】  [Specific contents to carry out invention]
이하， 발명의 이해를 돕기 위하여 바람직한 실시예들이 제시된다. 그러나 하기의 실시예들은 본 발명을 예시하기 위한 것일 뿐, 본 발명을 이들만으로 한정하는 것은 아니다.  Hereinafter, preferred embodiments are presented to help understand the invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.
Figure imgf000020_0001
Figure imgf000020_0001
옥타메틸시클로테트라실록산 47.60 g( 160 讓 ol ) , 테트라메틸디실록산 2.40 g( 17.8 画 ol )을 혼합한 후, 상기 혼합물을 옥타메틸시클로테트라실록산 100 증량부 대비 산성백토 (DC-A3) 1 중량부와 함께 3L 플라스크에 넣고 60°C로 4시간 동안 반응시켰다. 반웅 종료 후， 에틸아세테이트로 희석하고 셀라이트를 사용하여 빠르게 필터링하였다. 이렇게 수득된 말단 미변성 폴리오르가노실록산의 반복단위 (n)는 47.60 g of octamethylcyclotetrasiloxane (160 μl) and 2.40 g (17.8 μl) of tetramethyldisiloxane were mixed, and then the mixture was mixed with 100 parts by weight of octamethylcyclotetrasiloxane (DC-A3), 1 weight It was put in a 3L flask with a portion and reacted at 60 ° C for 4 hours. After completion of reaction, the mixture was diluted with ethyl acetate and filtered quickly using Celite. The repeating unit (n) of the terminal unmodified polyorganosiloxane thus obtained is
확인한 결과 34이었다. 상기 수득된 말단 미변성 폴리오르가노실록산에 2-알릴페놀 4.81 g(35.9 瞧 ol)과 칼스테드 백금 촉매 (Karstedt's plat in簡 cata-lyst) 0.01 g(50 ρρη 을 투입하여 90°C에서 3시간 동안 반옹시켰다. 반응 종료 후, 미반응 실록산은 120°C. 1 torr의 조건으로 이베이퍼레이션하여 제거하였다. 이렇게 수득한 말단 변성 폴리오르가노실록산을 AP-PDMS(n=34)로 명명하였다. AP-PDMS는 연황색 오일이며， Varian 50( iz을 이용하여 NMR을 통해 반복단위 (n)는 34임을 확인하였으며， 더 이상의 정제는 필요하지 않았다. -PDMS(m=58) As a result, it was 34. To the terminal unmodified polyorganosiloxane, 4.81 g (35.9 瞧 ol) of 2-allylphenol and 0.01 g (50 ρρη) of Karlstedt's plat in cata-lyst were added to the terminal unmodified polyorganosiloxane at 90 ° C for 3 hours. After the reaction was completed, unreacted siloxane was removed by evaporation at 120 ° C. 1 torr.The terminally modified polyorganosiloxane thus obtained was named AP-PDMS (n = 34). AP-PDMS is a pale yellow oil, and the Varian 50 (iz using NMR confirmed that the repeat unit (n) was 34. No further purification was required. -PDMS (m = 58).
Figure imgf000021_0001
Figure imgf000021_0001
옥타메틸시클로테트라실록산 47.60 g(160 mmol), 테트라메틸디실록산 47.60 g (160 mmol) octamethylcyclotetrasiloxane, tetramethyldisiloxane
1.5 g(ll mmol)을 흔합한 후， 상기 혼합물을 옥타메틸시클로테트라실록산 100 중량부 대비 산성백토 (DC-A3) 1 중량부와 함께 3L 폴라스크에 넣고 60°C로 4시간 동안 반웅시켰다. 반웅 종료 후, 에틸아세테이트로 희석하고 셀라이트를 사용하여 빠르게 필터링하였다. 이렇게 수득된 말단 미변성 폴리오르가노실록산의 반복단위 (m)는 NMR로 확인한 결과 58이었다. 상기 수득된 말단 미변성 폴리오르가노실록산에 3-메틸부트 -3-에닐 4ᅳ하이드록시벤조에이트 (3-methylbut-3-enyl 4-hydroxybenzoate) 6.13 g(29.7 mmol)과 칼스테드 백금 촉매 (Karstedt ' s platinum catalyst) 0.01 g(50 ppm)을 투입하여 90°C에서 3시간 동안 반웅시켰다. 반응 종료 후， 미반웅 실록산은 120°C, 1 torr의 조건으로 이베이퍼레이션하여 제거하였다. 이렇게 수득한 말단 변성 폴리오르가노실록산을 MBHB-PDMS(m=58)로 명명하였다. MBHB-PDMS는 연황색 오일이며, Varian 500MHz을 이용하여 ¾ 丽 R을 통해 반복단위 (m)는 58임을 확인하였으며， 더 이상의 정제는 필요하지 않았다. 제조예 3: Si-PC After mixing 1.5 g (ll mmol), the mixture was placed in a 3L polar flask with 1 part by weight of acidic clay (DC-A3) to 100 parts by weight of octamethylcyclotetrasiloxane and reacted at 60 ° C. for 4 hours. After completion of reaction, the mixture was diluted with ethyl acetate and filtered quickly using Celite. The repeating unit (m) of the terminal unmodified polyorganosiloxane thus obtained was found to be 58 by NMR. 6.13 g (29.7 mmol) of 3-methylbut-3-enyl 4-hydroxybenzoate and Karlstedt platinum catalyst (Karstedt) were obtained in the terminal unmodified polyorganosiloxane obtained above. 0.01 g (50 ppm) of platinum catalyst was reacted at 90 ° C. for 3 hours. After completion of the reaction, Mibanung siloxane was removed by evaporation under conditions of 120 ° C. and 1 torr. The terminal modified polyorganosiloxane thus obtained was named MBHB-PDMS (m = 58). MBHB-PDMS is light yellow oil, ¾ using Varian 500 MHz Through R, it was confirmed that the repeating unit (m) was 58, and no further purification was necessary. Preparation Example 3 Si-PC
중합 반응기에 물 1784 g, NaOH 385 g 및 BPA bisphenol A) 232 g을 넣고， N2 분위기 하에 흔합하여 녹였다. 여기에 PTBP(para-tert butyl phenol) 4.3 g과 제조예 1에서 제조한 AP-PDMS(n=34) 5.91 g 및 제조예 2에서 제조한 MBHB-PDMS(m=58) 0.66 g의 흔합액 (증량비 90: 10)을 MCGnethylene chloride)로 용해하여 넣어주었다. 그 다음 TPG(tr iphosgene) 128 g을 MC에 녹여 pH를 11 이상으로 유지시켜 주면서 1시간 동안 투입하여 반웅시킨 다음 10분 뒤에 TEA(triethylaniine) 46 g을 넣어 커플랑 (coupl ing) 반웅을 시켰다. 총 반웅시간 1시간 20분이 지난 다음 pH를 4로 낮추어 TEA를 제거하였고， 증류수로 3회 세척하여 생성된 중합체의 pH를 6~7 중성으로 맞추었다. 이렇게 얻은 증합체를 메탄을과 핵산 흔합용액에서 재침전시켜 수득한 다음， 이를 120°C에서 건조하여 최종 코폴리카보네이트 (Mw = 31 ,500)를 얻었으며 , 이를 Si-PC로 명명하였다. 제조예 4: PC 1784 g of water, 385 g of NaOH, and 232 g of BPA bisphenol A) were added to the polymerization reactor, and the mixture was dissolved under N 2 atmosphere. A mixed solution of 4.3 g of PTBP (para-tert butyl phenol), 5.91 g of AP-PDMS prepared in Preparation Example 1 (n = 34) and 0.66 g of MBHB-PDMS prepared in Preparation Example 2 (m = 58) ( The increase ratio 90:10 was dissolved in MCGnethylene chloride). Then, 128 g of TPG (tr iphosgene) was dissolved in MC, and the pH was maintained at 11 or more. The reaction was added for 1 hour, and after 10 minutes, 46 g of TEA (triethylaniine) was added to react with a couple. After 1 hour 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and the resultant polymer was washed three times with distilled water to adjust the pH of the produced polymer to 6-7 neutral. The thus-obtained polymer was obtained by reprecipitation of methane in a nucleic acid mixture solution and then dried at 120 ° C. to obtain a final copolycarbonate (Mw = 31,500), which was named Si-PC. Preparation Example 4 PC
중합 반응기에 물 1784 g, NaOH 385 g 및 BPA(bisphenol A) 232 g을 넣고， N2 분위기 하에 흔합하여 녹였다. 여기에 PTBP(para-tert butyl phenol) 4.7 g을 MCGnethylene chloride)로 용해하여 넣어주었다. 그 다음 TPG(tr iphosgene) 128 g을 MC에 녹여 pH를 11 이상으로 유지시켜 주면서 1시간 동안 투입하여 반웅시킨 다음 10분 뒤에 TEA(triethylamine) 46 g을 넣어 커플링 (coupling) 반응을 시켰다. 총 반웅시간 1시간 20분이 지난 다음 pH를 4로 낮추어 TEA를 제거하였고， 증류수로 3회 세척하여 생성된 중합체의 PH를 6~7 중성으로 맞추었다. 이렇게 얻은 중합체를 메탄올과 핵산 흔합용액에서 재침전시켜 수득한 다음， 이를 120°C에서 건조하여 최종 폴리카보네이트 (Mw = 29,000)를 얻었으며， 이를 PC로 명명하였다. 실시예 및 비교예 상기 제조예 3에서 제조한 Si-PC, 상기 제조예 4에서 제조한 PC, 층격 보강제， 인계 난연제 (BDP) , 탈크， 및 기타 첨가제 ( Irganox 1076 0.1 wt , Irgafos 0.2 ^%)를 하기 표 1과 같은 중량비로 흔합하여 폴리카보네이트 수지 조성물을 제조하였다. 1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and the mixture was dissolved under N 2 atmosphere. Here, 4.7 g of PTBP (para-tert butyl phenol) was dissolved in MCGnethylene chloride). Then, 128 g of TPG (tr iphosgene) was dissolved in MC, and the pH was maintained at 11 or more. The reaction was added for 1 hour, and then, after 10 minutes, 46 g of TEA (triethylamine) was added for a coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and washed three times with distilled water to adjust the pH of the produced polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a methanol and nucleic acid mixture solution, which was then dried at 120 ° C. to obtain a final polycarbonate (Mw = 29,000), which was named PC. Examples and Comparative Examples Si-PC prepared in Preparation Example 3, PC prepared in Preparation Example 4, layer reinforcing agent, phosphorus flame retardant (BDP), talc, and other additives (Irganox 1076 0.1 wt, Irgafos 0.2 ^%) are shown in Table 1 below. It was mixed in the same weight ratio to prepare a polycarbonate resin composition.
【표 1】  Table 1
Figure imgf000023_0001
실험예
Figure imgf000023_0001
Experimental Example
상기 실시예 및 비교예의 폴리카보네이트 수지 조성물을， 벤트 부착 The polycarbonate resin composition of the said Example and the comparative example, with a vent
Φ30画 이축압출기를 사용하여， 펠릿화한 후， JSW (주) N— 20C 사출성형기를 사용하여 실린더 은도 3(xrc , 금형 온도 8(rc로 사출성형하여 시편을 제조하였다. 이의 물성을 하기와 같이 측정하였다. After pelletizing using a Φ30 画 twin screw extruder, a specimen was prepared by injection molding a cylinder silver degree 3 (xrc, mold temperature 8 (rc) using a JSW Co., Ltd. N—20C injection molding machine. Measured together.
1) 굴곡 강도 (kg/cm2) : ASTM D638에 의거하여， 시편 1/8"로 측정하였다. 1) Flexural strength (kg / cm 2 ): measured in specimens 1/8 "according to ASTM D638.
2) IZ0D 충격강도 (kg. cm/cm) : ASTM D256에 의거하여， 시편 1/8' '로 측정하였다.  2) IZ0D impact strength (kg. Cm / cm): measured in accordance with the specimen 1/8 '' according to ASTM D256.
3) 난연성: UL 94V에 의거하여 난연성을 평가하였다. 구체적으로， 난연 test 적용에 필요한 1.0 mm 두께의 난연 시편을 5개 준비하고， 하기에 따라 평가하였다.  3) Flame retardancy: Flame retardancy was evaluated based on UL 94V. Specifically, five 1.0 mm thick flame retardant specimens required for the flame retardant test application were prepared and evaluated as follows.
먼저， 20 mm 높이의 불꽃을 10초간 시편에 접염 후， 시편의 연소 시간 (t l)을 측정하고， 연소 양상을 기록하였다. 이어, 1차 접염 후 연소가 종료되면, 다시 10초간 접염 후 시편의 연소 시간 (t2) 및 불똥이 맺힌 시간 (glowing t ime , t3)을 측정하고， 연소 양상을 기톡하였다. 5개 시편에 대해 동일하게 적용한 다음， 하기 표 2의 기준으로 평가하였다. 【표 2] First, after the flame of 20 mm height was immersed in the specimen for 10 seconds, the burning time (tl) of the specimen was measured, and the burning pattern was recorded. Subsequently, when combustion was terminated after the first contact, the burning time (t2) and burning time (glowing time, t3) of the specimen after contacting for 10 seconds were measured again, and the combustion pattern was described. The same applies to the five specimens, and then evaluated based on the criteria in Table 2. [Table 2]
Figure imgf000024_0001
Figure imgf000024_0001
4) 백색도 (외관 평가， 황변 지수) : Di sk 시편 (1.5 薩)을 사출하여 색차계를 이용하여 L 값을 측정하였고， 추가로 육안을 사용하여 외관을 확인하였다. 상기 결과를 표 3에 나타내었다. 4) Whiteness (appearance evaluation, yellowing index): Di sk specimen (1.5 薩) was injected and the L value was measured using a colorimeter, and visually confirmed by visual observation. The results are shown in Table 3.
【표 3】 Table 3
Figure imgf000024_0002
상기 표 3에 나타난 바와 같이, 실시예의 경우 굴곡강도 및 IZ0D 층격강도가 비교예 대비 현저히 높았으며， 외관도 현저히 우수함을 확인할 수 있었다. 따라서, 본 발명과 같이 PC 수지에서 무기 층전제와 코폴리카보네이트를 동시에 포함할 경우， 기계적 물성을 향상시키면서 동시에 외관 불량을 억제할 수 있음을 확인할 수 있었다.
Figure imgf000024_0002
As shown in Table 3, in the case of the embodiment, the flexural strength and the IZ0D laminar strength were significantly higher than those of the comparative example, and it was confirmed that the appearance was remarkably excellent. Therefore, when the inorganic resin and copolycarbonate are simultaneously included in the PC resin as in the present invention, it was confirmed that the appearance defects can be suppressed at the same time while improving the mechanical properties.

Claims

【특허청구범위】 【청구항 1】 폴리카보네이트, 층격 보강제 , 방향족 폴리카보네이트계 게 1 반복 단위; 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는 코폴리카보네이트， 및 무기 충전제를 포함하고， 상기 게 1 반복 단위는 하기 화학식 1로 표시되고， 상기 제 2 반복 단위는 하기 화학식 2로 표시되는 반복 단위 및 하기 화학식 3으로 표시되는 반복 단위를 포함하는, 폴리카보네이트 조성물: Claims Claim 1 Polycarbonate, lamellar reinforcing agent, aromatic polycarbonate-based crab 1 repeating unit; And a copolycarbonate comprising an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, and an inorganic filler, wherein the first repeating unit is represented by the following Formula 1, and the second repeating unit is represented by the following formula A polycarbonate composition comprising a repeating unit represented by 2 and a repeating unit represented by Formula 3 below:
[화학식 1]  [Formula 1]
Figure imgf000025_0001
상기 화학식 1에서，
Figure imgf000025_0001
In Chemical Formula 1,
Rl 내지 ¾는 각각 독립적으로 수소， d-H) 알킬 , 알콕시 , 또는 할로겐이고，  R1 to ¾ are each independently hydrogen, d-H) alkyl, alkoxy, or halogen,
Z는 비치환되거나 또는 페닐로 치환된 d- ) 알킬렌， 비치환되거나 또는 Cwo 알킬로 치환된 C3-15 사이클로알킬렌, 0， S , SO , S02 , 또는 CO이고, And 15 cycloalkylene, 0, S, SO, S0 2, or CO, - Z is unsubstituted or substituted phenyl or a d-) alkylene, unsubstituted or substituted with Cwo a C 3 alkyl substituted with
Figure imgf000025_0002
Figure imgf000025_0002
상기 화학식 2에서,  In Chemical Formula 2,
¾은 각각 독립적으로 알킬렌이고， ¾는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 d-10 알콕시, 또는 C6-20 아릴로 치환된 d-15 알킬; 할로겐; d-10 알콕시; 알릴; d-10 할로알킬; 또는 c6—20 아릴이고, ¾ are each independently alkylene, Each ¾ is independently hydrogen; Unsubstituted or oxiranyl group, a d- 10 alkoxy substituted by oxiranyl group, or a C 6 - 15 alkyl substituted with a d- 20 aryl; halogen; d- 10 alkoxy; Allyl; d- 10 haloalkyl; Or c 6 — 20 aryl,
n은 10 내지 200의 정수이고，  n is an integer of 10 to 200,
[화학식 3]  [Formula 3]
Figure imgf000026_0001
상기 화학식 3에서，
Figure imgf000026_0001
In Chemical Formula 3,
¾은 각각 독립적으로 알킬렌이고,  ¾ are each independently alkylene,
Yr 각각 독립적으로 수소， d-6 알킬， 할로겐, 히드록시， d-6 알콕시， 또는 C6-20 아릴이고， Yr each independently hydrogen, d- 6 alkyl, halogen, hydroxy, d- 6 alkoxy, or C 6 - 20 aryl, and,
¾는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐, 옥시라닐로 치환된 Cwo 알콕시, 또는 C6-20 아릴로 치환된 d-15 알킬; 할로겐; CHO 알콕시 ; 알릴; 10 할로알킬; 또는 C6-20 아릴이고， Each ¾ is independently hydrogen; Unsubstituted or oxiranyl group, substituted with oxiranyl Cwo alkyl, or C 6 - 20 aryl substituted with a d- 15 alkyl; halogen; CHO alkoxy; Allyl; 10 haloalkyl; 20 is an aryl, - or C 6
m은 10 내지 200의 정수이다.  m is an integer of 10-200.
【청구항 2】 [Claim 2]
제 1항에 있어서，  The method of claim 1,
1 내지 13 중량부의 폴리카보네이트,  1 to 13 parts by weight of polycarbonate,
1 중량부의 충격 보강제, ' 1 part by weight of impact modifier, '
1 내지 6 중량부의 코폴리카보네이트, 및  1 to 6 parts by weight of copolycarbonate, and
0.5 내지 4 중량부의 무기 충전제를 포함하는 것을 특징으로 하는， 폴리카보네이트 조성물.  A polycarbonate composition, comprising 0.5 to 4 parts by weight of inorganic filler.
【청구항 3】 [Claim 3]
제 1항에 있어서，  The method of claim 1,
상기 폴리카보네이트는 하기 화학식 4로 표시되는 반복단위ᅵ 포함하는 것을 특징으로 하는， 폴리카보네이트 The polycarbonate is characterized in that it comprises a repeating unit ᅵ represented by the formula (4) Polycarbonate
4]  4]
Figure imgf000027_0001
상기 화학식 4에서，
Figure imgf000027_0001
In Chemical Formula 4,
R'i 내지 R'4는 각각 독립적으로 수소， CHO 알킬， d- ) 알콕시， 또는 할로겐이고,  R'i to R'4 are each independently hydrogen, CHO alkyl, d-) alkoxy, or halogen,
Z'는'비치환되거나 또는 페닐로 치환된 d-10 알킬렌， 비치환되거나 또는 CHQ 알킬로 치환된 C3-15 사이클로알킬렌， 0， S, SO, S02, 또는 CO이다. 【청구항 4】 And Z '' is unsubstituted or substituted with d- 10 alkylene, unsubstituted or CHQ alkyl substituted by phenyl C 3 - 15 cycloalkylene, 0, S, SO, S0 2, or CO. [Claim 4]
제 1항에 있어서,  The method of claim 1,
상기 층격 보강제는， 메틸메타크릴레이트-부타디엔-스티렌계 공중합체, 스티렌ᅳ아크릴로니트릴계 공중합체， 아크릴로니트릴-부타디엔- 스티렌계, 또는 이의 혼합물인 것을 특징으로 하는，  The layered reinforcing agent is a methyl methacrylate-butadiene-styrene-based copolymer, styrene-acrylonitrile-based copolymer, acrylonitrile-butadiene-styrene-based, or a mixture thereof,
폴리카보네이트 조성물.  Polycarbonate composition.
【청구항 5] [Claim 5]
제 1항에 있어서，  The method of claim 1,
상기 폴리카보네이트를 5 내지 13 중량부로 포함하는 것을 특징으로 하는,  Characterized in that it comprises 5 to 13 parts by weight of the polycarbonate,
폴리카보네이트 조성물.  Polycarbonate composition.
【청구항 6】 [Claim 6]
제 1항에 있어서，  The method of claim 1,
상기 폴리카보네이트의 중량평균분자량은 1,000 내지 100,000인 것을 특징으로 하는，  The weight average molecular weight of the polycarbonate is characterized in that 1,000 to 100,000,
폴리카보네이트 조성물. Polycarbonate composition.
【청구항 7】 [Claim 7]
제 1항에 있어서，  The method of claim 1,
상기 코폴리카보네이트의 중량평균분자량은 1,000 내지 100, 000인 것을 특징으로 하는，  The weight average molecular weight of the copolycarbonate is characterized in that 1,000 to 100, 000,
폴리카보네이트 조성물.  Polycarbonate composition.
【청구항 8】 [Claim 8]
제 1항에 있어서，  The method of claim 1,
상기 플리카보네이트 조성물은 0.5 내지 4 중량부의 난연제를 추가로 포함하는 것을 특징으로 하는，  The polycarbonate composition further comprises 0.5 to 4 parts by weight of a flame retardant,
폴리카보네이트 조성물.  Polycarbonate composition.
【청구항 9】 [Claim 9]
제 8항에 있어서，  The method of claim 8,
상기 난연제는 인계 난연제인 것을 특징으로 하는，  The flame retardant is characterized in that the phosphorus-based flame retardant,
폴리카보네이트 조성물.  Polycarbonate composition.
【청구항 10】 [Claim 10]
제 9항에 있어서，  The method of claim 9,
상기 인계 난연제는 비스페놀 -A 비스 (디페닐 포스페이트) (Bisphenol- A bis(diphenyl phosphate))인 것을 특징으로 하는，  The phosphorus-based flame retardant is bisphenol-A bis (diphenyl phosphate) (Bisphenol-A bis (diphenyl phosphate)), characterized in that
폴리카보네이트 조성물. 【청구항 11】  Polycarbonate composition. [Claim 11]
제 1항에 있어서，  The method of claim 1,
상기 무기 충전제는 탈크 (talc), 웰라스토나이트 (wollastonite), 마이카 (mica), 또는 이의 흔합물인 것을 특징으로 하는，  The inorganic filler is characterized in that talc, wollastonite, mica, or a combination thereof.
폴리카보네이트 조성물. 【청구항 12] Polycarbonate composition. [Claim 12]
제 1항 내지 제 11항 중 어느 한 항의 폴리카보네이트 조성물로 제조되는， 물품.  An article made from the polycarbonate composition of claim 1.
PCT/KR2015/013247 2014-12-04 2015-12-04 Polycarbonate composition and article comprising same WO2016089172A1 (en)

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