WO2016089135A2 - Composition de résine de copolycarbonate et article la comprenant - Google Patents

Composition de résine de copolycarbonate et article la comprenant Download PDF

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WO2016089135A2
WO2016089135A2 PCT/KR2015/013157 KR2015013157W WO2016089135A2 WO 2016089135 A2 WO2016089135 A2 WO 2016089135A2 KR 2015013157 W KR2015013157 W KR 2015013157W WO 2016089135 A2 WO2016089135 A2 WO 2016089135A2
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WIPO (PCT)
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formula
resin composition
repeating unit
copolycarbonate resin
group
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PCT/KR2015/013157
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English (en)
Korean (ko)
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WO2016089135A3 (fr
Inventor
황영영
반형민
박정준
홍무호
전병규
고운
이기재
손영욱
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주식회사 엘지화학
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Priority claimed from KR1020150170782A external-priority patent/KR101803960B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP15864965.7A priority Critical patent/EP3159367B1/fr
Priority to PL15864965T priority patent/PL3159367T3/pl
Priority to JP2017503823A priority patent/JP6649356B2/ja
Priority to US15/500,242 priority patent/US10196516B2/en
Priority to CN201580039083.8A priority patent/CN106661219B/zh
Publication of WO2016089135A2 publication Critical patent/WO2016089135A2/fr
Publication of WO2016089135A3 publication Critical patent/WO2016089135A3/fr

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  • Copolycarbonate resin composition and article comprising the same
  • the present invention relates to a copolycarbonate resin composition and an article comprising the same. More specifically, the present invention relates to a copolycarbonate resin composition having improved mechanical properties such as chemical resistance and impact resistance while maintaining the fluidity of the resin, and an article including the same.
  • Polycarbonate resins are prepared by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and excellent impact strength. It has numerical stability, heat resistance and transparency, and is applied to a wide range of fields such as exterior materials for automobiles, automobile parts, building materials, and optical parts. Recently, in order to apply such polycarbonate resins to a wider variety of fields, a study for obtaining desired physical properties by copolymerizing aromatic diol compounds having different structures and introducing units having different structures into the main chain of polycarbonates has been made. Many attempts have been made. In particular, research into introducing a polysiloxane structure into the backbone of polycarbonate is being conducted, but most of the technologies have high production costs, resulting in low economic efficiency.
  • the present invention is to provide a copolycarbonate resin composition with improved mechanical properties such as chemical resistance and impact resistance while maintaining the fluidity of the resin.
  • the present invention also provides an article comprising the copolycarbonate resin composition.
  • a copolycarbonate resin comprising an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond; And a polysiloxane polymer containing a hydrocarbon-based functional group of 2 carbon atoms.
  • an article including the copolycarbonate resin composition is also provided.
  • a copolycarbonate resin comprising an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond; And a copolycarbonate resin composition comprising a polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms may be provided.
  • the inventors of the present invention can improve the impact strength, particularly impact strength at low temperatures, with fluidity by the copolycarbonate resin containing a specific repeating unit, using a copolycarbonate resin composition described above, hydrocarbon-based functional group
  • the chemical stability is improved by the polysiloxane polymer containing, and the chemical resistance is secured.
  • the copolycarbonate resin composition is a general copolycarbonate resin obtained by condensation polymerization of an aromatic diol such as bisphenol A and a carbonate precursor such as phosgene or a copolycarbonate resin obtained by copolymerizing aromatic diol compounds having different structures.
  • the aromatic polycarbonate-based first repeating unit is formed by reacting an aromatic diol compound and a carbonate precursor. It may be represented by the following formula (1):
  • Chemical Formula 1 i to R4 are each independently hydrogen, C wo alkyl, d- 10 alkoxy, or halogen,
  • Z is unsubstituted or substituted with d- 10 alkylene, unsubstituted or substituted by phenyl, or 10 alkyl C 3 - 15 cycloalkylene, 0, S, SO, S0 2, or CO.
  • Z is straight or branched Cwo 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 Formula 1 is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Sulfoxide, bis (4-hydroxyphenyl) sulphi bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2bisbis (4-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
  • the meaning of 'derived from the aromatic diol compound' means that the hydroxyl group and the carbonate precursor of the aromatic diol compound react with the formula (1). It means forming a repeating unit to be displayed.
  • a unit is represented by the following Formula 1-1.
  • carbonate precursor examples include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, and dinaphthyl carbonate, Bis (diphenyl) carbonate phosgene. At least one selected from the group consisting of triphosgene, diphosgene, bromophosgene, and bishaloformate may be used, and preferably triphosgene or phosgene may be used.
  • the aromatic polycarbonate-based 2 ′′ repeating unit having one or more siloxane bonds may include one or more or two or more repeating units selected from the group consisting of repeating units represented by the following Formulas 2 to 4. :
  • ⁇ are each independently 10 alkylene
  • Each R 5 is independently hydrogen; Alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted d- 10 alkoxy, or C 6 -2o aryl; halogen; d- 10 alkoxy; Allyl .; Ci-io haloalkyl; 20 is an aryl, - or C 6
  • nl is an integer from 10 to 200
  • Each X 2 is independently d- ⁇ alkylene
  • ⁇ are each independently hydrogen, d- 6 alkyl, halogen, hydroxy, d- 6 alkoxy or C 6 - 20 aryl, and,.
  • Each R 6 is independently hydrogen; Unsubstituted or oxiranyl, the CHO-alkoxy substituted by oxiranyl group, or C 6 - 20 aryl substituted with a d- 15 alkyl; halogen; Alkoxy; Allyl; d- 10 haloalkyl; 20 is an aryl, - or C 6
  • n2 is an integer of 10 to 200
  • 3 ⁇ 4 are each independently Cwo alkylene
  • Each Y 2 is independently Cwo alkoxy
  • Each R 7 is independently hydrogen; Alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted d- 10 alkoxy, or C 6 — 20 aryl; halogen; CHO alkoxy; Allyl; Cwo haloalkyl; 20 is an aryl, - or C 6
  • n3 is an integer of 10-200.
  • 3 ⁇ 4 are each independently C 2 - 4 alkylene and is, most preferably, propane-1,3-diyl-10 alkylene, more preferably C 2.
  • 3 ⁇ 4 is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl. 2-phenylpropyl, 3— (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo. Methoxy, ethoxy, propoxy, allyl. 2, 2, 2-trifluoroethyl, 3, 3, 3 'trifluoropropyl, phenyl, or naphthyl.
  • 3 ⁇ 4 is each independently Cl - 10 alkyl, ⁇ more preferably d- 6 alkyl, more preferably d- 3 alkyl, and most preferably methyl.
  • ⁇ is i) an integer from 30 to 60, or ii) 20 or more. An integer of 25 or more, 30 or more, 40 or less, or 35 or less, or iii) 50 or more, or 55 or more, 70 or less, 65 or less, or 60 or less.
  • Chemical Formula 2 is represented by the following Chemical Formula 2-1:
  • 3 ⁇ 4 are each independently a C 2 - to 10 alkylene, more preferably C 2 - 6 alkylene and most preferably isobutylene.
  • ⁇ is hydrogen.
  • 3 ⁇ 4 is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2'phenalpropyl, 3 '(oxyranylme) propyl, fluoro, chloro, bromo, iodo, medo Toxy, Epoxy, Propoxy, Allyl . , 2, 2, 2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl.
  • 3 ⁇ 4 is each independently d-! Q alkyl, more preferably d-6 alkyl, more preferably d- 3 alkyl, and most preferably methyl.
  • n2 is i) an integer from 30 to 60, or ii) 20 or more, 25 or more, or 30 or more and 40 or less. Or iii) 50 or less, or 55 or more, 70 or less, 65 or less, or 60 or less.
  • Chemical Formula 3 is represented by the following Chemical Formula 3-1: [Formula 3-1]
  • C 2 _ 4 alkylene most preferably, propane-1, 3-diyl eu: - preferably in the general formula (4), it is, 3 ⁇ 4 are each independently C 2 10 alkylene,.
  • Y 2 is alkoxy. More preferably it is Cw alkoxy, most preferably methoxy.
  • each R 7 is independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, polouro, chloro, bromo, iodo, Methoxy, ethoxy, propoxy, allyl.
  • R 7 is each independently d-) alkyl, more preferably Is C- 6 alkyl, more preferably d- 3 alkyl, most preferably methyl.
  • n3 is i) an integer from 30 to 60, ii) 20 or more, 25 or more, or 30 or more, 40 or less, or 35 or less, or iii) 50 or more, or 55 or more It is an integer of 70 or less, 65 or less, or 60 or less.
  • Chemical Formula 4 is represented by Chemical Formula 4-1: [Formula 4-1]
  • the formula (2) From the group consisting of repeating units represented by four. One or more selected units, or two or more types may be included, and specifically, two or more types thereof may be included. In the case of including two or more of the repeating units represented by Formulas 2 to 4, it was confirmed that the improvement of the room temperature impact strength, the low temperature impact strength, and the fluidity properties were remarkably increased. Is due to the complementary effect of "A 2 or more types of repeating unit” means in this invention. It means that the structure includes two or more repeating units having different structures, or two or more repeating units having the same structure but different numbers of repeating units (nl, n2, n3) of silicon oxide in the structure of Formulas 2 to 4.
  • repeating unit represented by Formula 2 means in the present invention, 1) .
  • the 2 repeat at least one unit: 1) a repeating unit represented by the formula (2) first species and the repeating unit one compound represented by formula (3), 2), recurring unit to be displayed one of a repeating unit 1 species, and the formula (4) represented by the formula (2) Species, or 3) represented by the formula
  • the weight ratio between the two 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.
  • Repetitive units represented by Formulas 2 to 4 are each represented by the following Formula 2 '
  • siloxane compound represented by 2 the siloxane compound represented by following formula (3-2), and the siloxane compound represented by following formula (4-2).
  • X 2 , Y 1; R 6 and n 2 are the same as defined in Formula 3,
  • Y 2 , R 7 and n 3 are the same as defined in Formula 4 above.
  • the meaning of 'derived from the siloxane compound' means that the hydroxy group and the carbonate precursor of each of the siloxane compounds react to form a repeating unit represented by each of Chemical Formulas 2 to 4 above.
  • the carbonate precursors that can be used to form the repeating units of Formulas 2 to 4 are the same as those described above for the carbonate precursors that can be used to form the repeating units of Formula 1.
  • the compounds represented by Chemical Formulas 2-2, 3-2, and 4-2 may be prepared by the methods of the following Schemes 1 to 3, respectively.
  • 'It is C 2 - 10 alkenyl, and Al,, R 5, and nl are as defined above in formula (1).
  • ⁇ 2 ′ is C 2 10 alkenyl, 3 ⁇ 4, Y 1; As defined in R 6 and Formula 2,
  • R 7 and n 3 are the same as defined in Formula 3 above. It is preferable to perform the reactions of the reaction schemes 1 to 3 under a metal catalyst.
  • a metal catalyst Pt catalyst is preferably used.
  • an ashby catalyst, a Karlstedt catalyst, and a lamo are used. At least one selected from the group consisting of a Lamoreaux catalyst, a Speyer catalyst, PtCl 2 (C0D), PtC l 2 (benzonitrile) 2 , and PtBr 6 can be used.
  • the metal catalyst is 0.001 parts by weight or more, 0.005 parts by weight or more, or 0.01 parts by weight or more based on 100 parts by weight of the compound represented by Formula 11, 13, or 15, 1 part by weight or less, 0.1 part by weight or less, or It can be used at 0.05 parts by weight or less.
  • the reaction temperature is preferably so to ioo ° c.
  • the reaction time is preferably 1 hour to 5 hours.
  • the compound represented by Formula 6, 8 or 10 can be prepared by reacting the organodisiloxane and organocyclosiloxane under an acid catalyst, it is possible to control the content of the reactant to control nl, n2 and ⁇ 3 .
  • the reaction temperature 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 may be used.
  • an organocyclotetrasiloxane can be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like.
  • the acid catalyst is H 2 SO 4 , HCIO 4 , AICI 3, SbCl 5 . At least one selected from the group consisting of SnCl 4 and acidic clay may be used.
  • the acid catalyst may be used in an amount of 0.1 parts by weight, 0.5 parts by weight, or 1 part by weight, 10 parts by weight, 5 parts by weight, or 3 parts by weight or less based on 100 parts by weight of organocyclosiloxane. have.
  • the weight ratio of the repeating unit is a siloxane compound used for the polymerization of the copolycarbonate, for example the formula 1- It is based on the increase ratio of the siloxane compound represented by 2, 2-2, and 3-2.
  • the copolycarbonate resin composition may include a copolycarbonate resin including an aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond.
  • the aromatic polycarbonate-based first repeating unit and the at least one siloxane bond the aromatic polycarbonate-based first repeating unit and the at least one siloxane bond
  • the molar ratio of the aromatic polycarbonate-based second repeating unit may be 1: 0.0001 to 1: 0.01, or 1: 0.0005 to 1: 0.008, or 1: 0.001 to 1: 0.006, and the weight ratio is 1: 0.001 to 1: 1, Or 1: 0.005 to 1: 0.1, or 1: 0.01 to 1: 0.03.
  • the copolycarbonate resin including the aromatic polycarbonate-based first repeating unit and the aromatic polycarbonate-based second repeating unit having one or more siloxane bonds may include 0.001 to 10 weight 3 ⁇ 4 of the second repeating unit.
  • the first over-reduced second repeat unit content the first is an improvement in room temperature impact strength, low temperature impact strength and fluidity properties according to the second repeat unit it can be difficult to fully implement i.
  • the second repeating unit content is When excessively increased, the flowability and moldability may decrease while the molecular weight of the copolycarbonate resin is excessively increased.
  • the weight average molecular weight of the copolycarbonate resin including the aromatic polycarbonate-based crab 1 repeating unit and the aromatic polycarbonate-based 2 repeating unit having at least one siloxane bond is 1,000 to 100,000 g / mol, or 5,000 to 50,000 g / mol day Can be. In the weight average molecular weight range it can be improved ductility (ductility), and YI of the copolyester carbonate resin. It said copolycarbonate resin is at least one member selected from the group consisting of compounds represented by the formula 2-2 to 4-2,. Or it may be prepared in a manufacturing method comprising the step of polymerizing a composition comprising two or more compounds, an aromatic diol compound and a carbonate precursor.
  • the polymerization method may, using the interfacial polymerization method as an example, a case is possible polymerization at normal pressure and low temperature, and has an effect which facilitates the molecular weight control.
  • 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, after the pre-polymerization, the coupling body is introduced, and then polymerized again. In this case, a high molecular weight copolycarbonate may be obtained.
  • the material used for the interfacial polymerization is not particularly limited as long as it is a material that can be used for the polymerization of the copolycarbonate, the amount of use may be adjusted as necessary.
  • the acid binder examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or pyridine. Amine compounds, such as these, can be used.
  • the organic solvent is not particularly limited as long as it is a solvent usually used for polymerization of copolycarbonate. For example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used. Also.
  • the interfacial polymerization may be carried out by reaction agents such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds. Can be used additionally.
  • the reaction temperature of the interfacial polymerization is preferably 0 to 40 ° C, the reaction time is preferably 10 minutes to 5 hours.
  • the interfacial polymerization may be performed by further including a molecular weight regulator.
  • the molecular weight regulator may be added before the start of polymerization, during the start of polymerization, or after the start of polymerization.
  • Mono-alkylphenols may be used as the molecular weight regulator, and the mono-alkylphenols are, for example, p-tert-butylphenol, P-cumylphenol, decylphenol.
  • Dodecylphenol At least one member selected from the group consisting of tetradecylphenol, nuxadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol.
  • it is p-tert- butylphenol, In this case, a molecular weight control effect is large.
  • the molecular weight modifier is, for example, 0.01 part by weight, 0, 1 part by weight, or 1 part by weight or more based on 100 parts by weight of an aromatic diol compound. It is contained in 10 weight part or less, 6 weight part or less, or 5 weight part or less, and can obtain desired molecular weight within this range.
  • the polymerization At least one selected from the group consisting of compounds represented by Formulas 2-2 to 4-2, or at least two compounds and aromatic
  • the compound may form a repeating unit represented by Chemical Formulas 1 to 4 above. More specifically, the general formula (2) _2 to 4-2 at least one member selected from the group consisting of compounds represented by the following.
  • the copolycarbonate resin according to the present invention is a copolycarbonate comprising 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. Resin may be included.
  • the copolycarbonate resin composition has 2 or more carbon atoms, or 2 to
  • polysiloxane polymers containing 2 to 100, or 2 to 50, hydrocarbon-based functional groups may form a crosslinked structure through a hydrocarbon-based or more hydrocarbon-based functional group to absorb external shocks, and may be chemically stable to maximize chemical resistance.
  • the hydrocarbon-based functional group may include an aliphatic hydrocarbon functional group, at least one selected from the group consisting of alicyclic hydrocarbon and aromatic hydrocarbon functional groups functional groups.
  • the aliphatic hydrocarbon functional group, alicyclic hydrocarbon functional group or aromatic hydrocarbon functional group may each be a halogen group, an alkyl group, an alkenyl group, Alkoxy group, an aryl group, an arylalkyl group, and an aryl alkenyl group. It may be substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group, a carbazolyl group, a fluorenyl group, a nitrile group and an acetylene group.
  • the alicyclic hydrocarbon functional group may include a monocyclic or polycyclic cycloalkyl group having 3 or more carbon atoms, or 3 to 50 carbon atoms, and the aromatic hydrocarbon functional group may include 6 or more minor atoms, or 6 to 50 monocyclic or polycyclic aryl groups. Can be.
  • the monocyclic means that a single ring is included in the functional group
  • polycyclic means that two or more ring is contained in the functional group.
  • the aliphatic hydrocarbon functional group may include a linear or branched alkyl group or a vinyl functional group.
  • the linear or branched alkyl group having 2 or more carbon atoms is an alkyl group except for a methyl group having 1 carbon atom.
  • the functional group derived from the vinyl group means a functional group in which a part of the hydrogen atoms included in the vinyl group is substituted with another atomic group.
  • the vinyl-based functional group may be represented by the following formula (11). [Formula 11]
  • R 10 are each independently hydrogen, a straight chain having 1 to 20 carbon atoms or Alkyl group branched-chain, "cycloalkyl group having 6 to 20 carbon atoms of the aryl group, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, having 3 to 20 carbon atoms in a ketone group or an ester group.
  • An aryl group of 20, an alkenyl group of 2 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, a ketone group or an ester group may each be a halogen group, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, It may be substituted or unsubstituted with one or more substituents selected from the group consisting of an arylalkyl group, an arylalkenyl group, a heterocyclic group, a carbazolyl group, a fluorenyl group, a nitrile group and an acetylene group.
  • the aryl group can be monocyclic or polycyclic in organic radicals derived from aromatic hydrocarbons by one hydrogen removal.
  • the cycloalkyl group is not particularly limited, but may be monocyclic or polycyclic.
  • the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms may include 0.001 to 10 mol%, or 0.01 to 1 mol%, or 0.05 to 0.5 mol% of C 2 or more hydrocarbon-based functional groups. The carbon number is less than 0.001 mol% relative to the polysiloxane polymer containing the hydrocarbon group having at least 2 carbon atoms .
  • Impact resistance, chemical resistance, and fluidity improvement effect by two or more hydrocarbon-based functional groups may be difficult to be sufficiently realized, and the C 2 or more hydrocarbon-based functional group is 10 mol3 ⁇ 4 to the polysiloxane polymer containing the C 2 or more hydrocarbon-based functional group. If exceeded, the highly reactive hydrocarbon group having 2 or more carbon atoms is excessively high, and thus the compatibility with the polymer resin may be degraded, thereby reducing the mechanical and chemical properties.
  • the polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms may include a polysiloxane repeating unit and a polydimethylsiloxane repeating unit including a hydrocarbon-based functional group having 2 or more carbon atoms.
  • the polysiloxane repeating unit including the hydrocarbon group having 2 or more carbon atoms may include a repeating unit represented by the following Formula 12.
  • At least one of Rn to R 12 is a hydrocarbon-based functional group having at least 2 carbon atoms, and the rest are methyl groups.
  • Ru is a hydrocarbon group having 2 or more carbon atoms, and R 12 may be a methyl group.
  • the polydimethylsiloxane repeating unit may include? Repeating unit represented by the following formula (13). . '
  • the molar ratio of the polysiloxane repeating units including the C 2 hydrocarbon-based functional group to the repeating polydimethylsiloxane units is 0.00001 0.1, or 0.0005 to 0.001. 0.01, or 0.0007 to 0.0.
  • the polysiloxane polymer containing the hydrocarbon-based functional group having 2 or more carbon atoms may further include the hydrocarbon-based functional group having 2 or more carbon atoms bonded to the terminal of the polysiloxane polymer.
  • the terminal of the polysiloxane polymer means both ends of the polysiloxane main chain of the polysiloxane polymer containing the hydrocarbon group having 2 or more carbon atoms, and the hydrocarbon group having 2 or more carbon atoms has both or both ends of the polysiloxane main chain.
  • the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms has a carbon- 2 or more hydrocarbon-based functional group bonded to a main chain including a polysiloxane repeating unit and a polydimethylsiloxane repeating unit including a hydrocarbon-based functional group and 2 or more carbon atoms.
  • the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms may include a compound represented by the following Chemical Formula 14.
  • m is an integer of 10-20
  • n is an integer of 6,000-11.500, and is a C2 or more hydrocarbon-type functional group.
  • the content of the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms is 0.01 to 10% by weight, or 0.01 to 5% by weight, or 0.5 to 4% by weight based on the total weight of the copolycarbonate resin composition. Weight percent.
  • the content of the polysiloxane polymer containing the hydrocarbon-based functional group of 2 or more carbon atoms is too small, the 2 or more carbon atoms Chemical resistance and impact resistance improvement effect by the polysiloxane polymer containing a hydrocarbon-based functional group may be difficult to implement.
  • the content of the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms is too large, the mechanical or chemical properties of the copolycarbonate resin composition may be lowered.
  • the weight average molecular weight of the polysiloxane polymer containing a hydrocarbon-based functional group of 2 or more carbon atoms is 100, 000 to 1, 000, 000 g / mol, or 300, 000 to 900.000 g / mol, or 500, 000 to 850, 000 g / mol.
  • the example of the method of measuring the said weight average molecular weight is not specifically limited, For example, the weight average molecular weight of polystyrene conversion measured by the GPC method can be used.
  • the copolycarbonate resin composition may include a copolycarbonate resin comprising an aromatic polycarbonate-based U repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane linkage; And a polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms.
  • a copolycarbonate resin comprising an aromatic polycarbonate-based U repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane linkage
  • a polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms may be added to the copolycarbonate resin by adding a polysiloxane polymer and mixing using a mixer.
  • the copolycarbonate resin composition of the final article may further include various known additives, resins, and the like.
  • the additives include antioxidants, heat stabilizers, light stabilizers, plasticizers, antistatic agents, and nucleating agents.
  • the copolycarbonate resin composition may have a low temperature impact strength of 700 J / m or more measured at -30 ° C based on ASTM D256 (l / 8 inch, Notched Izod).
  • the copolycarbonate resin composition may have a low silver impact strength measured at -40 ° C based on ASTM D256 (l / 4 inch, Notched Izod) more than 200 J / m.
  • the copolycarbonate resin composition may be less than 10 gl 10m in melt index measured according to ASTM D1238 (300 ° C, 1.2kg conditions).
  • an article including the copolycarbonate resin composition of the above embodiment may be provided.
  • the article is an injection molded article.
  • the article is at least one selected from the group consisting of antioxidants, thermal stabilizers, photostabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent brighteners, ultraviolet absorbers, pigments and dyes. It can be included as.
  • Examples of the method for producing the article are not limited to, but for example, the step of drying the copolycarbonate resin composition according to the present invention, for example, pellet form copolycarbonate resin composition and then injection into an injection molding machine can do.
  • Information on the copolycarbonate resin composition includes the above-described content with respect to the embodiment.
  • Copolycarbonate resin composition and the article containing the same improved mechanical properties can be provided.
  • SF39Q0C manufactured by KCC: vinyl group content: 0.07 mol% was added to the copolycarbonate resin prepared in Preparation Example 3 in a content of 1 wt%, and mixed with a mixer.
  • a copolycarbonate resin composition was prepared in the same manner as in Example 1, except that SF3900C (manufactured by KCC Corporation: 0.07 mol% of vinyl groups) was added in a content of 2 wt%.
  • SF3900C manufactured by KCC Corporation: 0.07 mol% of vinyl groups
  • Copolycarbonate resin composition was prepared in the same manner as in Example 1 except that SF3900CXKCC Co., Ltd. product: vinyl group content 0.07 mol%) was added in a 3 wt% content. .
  • Copolycarbonate resin prepared in Preparation Example 5 was used. Comparative Example 4
  • a copolycarbonate resin composition was prepared in the same manner as in Example 1, except that the polycarbonate resin prepared in Preparation Example 4 was used instead of the copolycarbonate resin prepared in Preparation Example 3.
  • the Agilent 1200 series was used to measure GPC using PC Standard.
  • the time of denaturation by the solvent is longer than 1 hour, and has excellent chemical resistance, while no additive is included.
  • the copolycarbonate resin composition of the comparative example has a time denatured by a solvent
  • the melt index is not only high. It was found that the chemical resistance was bad.
  • the copolycarbonate resin composition of Comparative Example 4 even though it contains an additive with the copolycarbonate resin prepared in Preparation Example 4, by using the polycarbonate resin obtained in Preparation Example 4, 1 / Low temperature impact strength at 8 inch, -30 ° C was measured low, and the melt index was increased. Accordingly, the copolycarbonate resin composition, as the additive is added together with a specific copolycarbonate resin, with improved properties of the copolycarbonate resin (eg, melt index), impact resistance and chemical resistance depending on the additive It was confirmed that this is increased.

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  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne une composition de résine de copolycarbonate ayant des propriétés mécaniques améliorées, telles que la résistance chimique et la résistance aux chocs, tout en maintenant l'aptitude à l'écoulement de la résine, et un article la comprenant.
PCT/KR2015/013157 2014-12-04 2015-12-03 Composition de résine de copolycarbonate et article la comprenant WO2016089135A2 (fr)

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EP15864965.7A EP3159367B1 (fr) 2014-12-04 2015-12-03 Composition de résine de copolycarbonate et article la comprenant
PL15864965T PL3159367T3 (pl) 2014-12-04 2015-12-03 Kompozycja żywicy kopoliwęglanowej i obejmujący ją wyrób
JP2017503823A JP6649356B2 (ja) 2014-12-04 2015-12-03 コポリカーボネート樹脂組成物およびこれを含む物品
US15/500,242 US10196516B2 (en) 2014-12-04 2015-12-03 Copolycarbonate resin composition and article including the same
CN201580039083.8A CN106661219B (zh) 2014-12-04 2015-12-03 共聚碳酸酯树脂组合物和包含该共聚碳酸酯树脂组合物的制品

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KR1020150170782A KR101803960B1 (ko) 2014-12-04 2015-12-02 코폴리카보네이트 수지 조성물 및 이를 포함하는 물품

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020256494A1 (fr) * 2019-06-20 2020-12-24 주식회사 엘지화학 Procédé d'analyse de copolycarbonate
KR20200145751A (ko) * 2019-06-20 2020-12-30 주식회사 엘지화학 코폴리카보네이트의 분석 방법

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Publication number Priority date Publication date Assignee Title
DE69211382T2 (de) * 1991-02-22 1996-11-28 Mitsubishi Gas Chemical Co Thermoplastische Harzzusammensetzung von Siloxan-Polycarbonat
JP3457805B2 (ja) * 1996-06-28 2003-10-20 三菱エンジニアリングプラスチックス株式会社 ポリカーボネート系樹脂組成物
EP2042931A1 (fr) * 2007-09-27 2009-04-01 Mitsubishi Gas Chemical Company, Inc. Composition de résine pour photoconducteur électrophotographique et photoconducteur électrophotographique l'utilisant
US20130317141A1 (en) * 2012-05-24 2013-11-28 Sabic Innovative Plastics Ip B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
KR101534336B1 (ko) * 2012-12-11 2015-07-06 제일모직주식회사 내광성 및 난연성이 우수한 폴리카보네이트 수지 조성물

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020256494A1 (fr) * 2019-06-20 2020-12-24 주식회사 엘지화학 Procédé d'analyse de copolycarbonate
KR20200145751A (ko) * 2019-06-20 2020-12-30 주식회사 엘지화학 코폴리카보네이트의 분석 방법
KR102554769B1 (ko) * 2019-06-20 2023-07-12 주식회사 엘지화학 코폴리카보네이트의 분석 방법

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