JPH05311079A - Aromatic polycarbonate resin composition - Google Patents
Aromatic polycarbonate resin compositionInfo
- Publication number
- JPH05311079A JPH05311079A JP11481392A JP11481392A JPH05311079A JP H05311079 A JPH05311079 A JP H05311079A JP 11481392 A JP11481392 A JP 11481392A JP 11481392 A JP11481392 A JP 11481392A JP H05311079 A JPH05311079 A JP H05311079A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polycarbonate
- group
- weight
- resin
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 25
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000003365 glass fiber Substances 0.000 claims abstract description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- -1 phenylphosphonic acid ester Chemical class 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 4
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical class OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 abstract 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 abstract 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- 241001550224 Apha Species 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- KDRBAEZRIDZKRP-UHFFFAOYSA-N 2,2-bis[3-(aziridin-1-yl)propanoyloxymethyl]butyl 3-(aziridin-1-yl)propanoate Chemical compound C1CN1CCC(=O)OCC(COC(=O)CCN1CC1)(CC)COC(=O)CCN1CC1 KDRBAEZRIDZKRP-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- HXLLCROMVONRRO-UHFFFAOYSA-N 2-butoxyethenylbenzene Chemical compound CCCCOC=CC1=CC=CC=C1 HXLLCROMVONRRO-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical class C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical class C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- BKTRENAPTCBBFA-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-phenylphenyl)propan-2-yl]-2-phenylphenol Chemical compound C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C)(C)C(C=1)=CC=C(O)C=1C1=CC=CC=C1 BKTRENAPTCBBFA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、芳香族ポリカーボネー
ト樹脂系組成物に関する。更に詳しくは、色相、耐衝撃
性共に優れたガラス繊維強化芳香族ポリカーボネート樹
脂系組成物に関する。FIELD OF THE INVENTION The present invention relates to an aromatic polycarbonate resin composition. More specifically, it relates to a glass fiber reinforced aromatic polycarbonate resin composition having excellent hue and impact resistance.
【0002】[0002]
【従来の技術】芳香族ポリカーボネート樹脂は多くの優
れた特性を有するがゆえに広い分野で使用されている。
更にその耐熱性や剛性を向上させ、成形収縮率や熱膨脹
係数を小さくするするためにガラス繊維で強化すること
が行われている。しかしながらガラス繊維で強化する
と、芳香族ポリカーボネート樹脂は、その特徴である耐
衝撃性が低下する。Aromatic polycarbonate resins are used in a wide variety of fields because they have many excellent properties.
Further, in order to improve its heat resistance and rigidity, and to reduce the molding shrinkage rate and the thermal expansion coefficient, it is reinforced with glass fiber. However, when reinforced with glass fiber, the aromatic polycarbonate resin has its characteristic impact resistance lowered.
【0003】従来、ガラス繊維強化芳香族ポリカーボネ
ート樹脂に、ポリカーボネート−ポリオルガノシロキサ
ン共重合体(コポリシロキサンカーボネート樹脂)を添
加して耐衝撃性を改良することは知られている(特開昭
55−160052号公報、特開平2−173061号
公報)。しかしながら、この方法では耐衝撃性は改善さ
れるが、色相が悪化して無色乃至淡色系の着色成形品と
しては実用性がなかった。Conventionally, it has been known that a polycarbonate-polyorganosiloxane copolymer (copolysiloxane carbonate resin) is added to a glass fiber reinforced aromatic polycarbonate resin to improve impact resistance (JP-A-55-55). 160052, Japanese Patent Laid-Open No. 2-173061). However, although the impact resistance is improved by this method, the hue is deteriorated and it is not practical as a colorless or light-colored colored molded article.
【0004】[0004]
【発明が解決しようとする課題】本発明の目的は、無色
乃至淡色系の成形品として有用な色相、耐衝撃性共に優
れたガラス繊維強化芳香族ポリカーボネート樹脂系組成
物を提供するにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a glass fiber reinforced aromatic polycarbonate resin composition which is useful as a colorless or light-colored molded article and is excellent in both hue and impact resistance.
【0005】本発明者は、この目的を達成せんとして鋭
意研究を重ねた結果、ガラス繊維強化芳香族ポリカーボ
ネート樹脂組成物に、特定のポリシロキサンジフェノー
ルと二価フェノールとポリカーボネート前駆物質とを反
応させて得られるコポリシロキサンカーボネート樹脂と
特定のリン系安定剤の特定量を添加すれば、上記目的が
達成し得ることを見出した。本発明はこの知見に基づき
更に検討を重ねた結果完成したものである。The present inventor has conducted extensive studies to achieve this object, and as a result, made a specific polysiloxane diphenol, a dihydric phenol and a polycarbonate precursor react with a glass fiber reinforced aromatic polycarbonate resin composition. It has been found that the above object can be achieved by adding a specific amount of the resulting copolysiloxane carbonate resin and a specific phosphorus stabilizer. The present invention has been completed as a result of further studies based on this finding.
【0006】[0006]
【課題を解決するための手段】本発明は、下記式[1]The present invention provides the following formula [1]:
【0007】[0007]
【化4】 [Chemical 4]
【0008】[式中、R1 は−CH2 CH2 −又は[In the formula, R 1 is --CH 2 CH 2 --or
【0009】[0009]
【化5】 [Chemical 5]
【0010】であり、nは1〜300の整数である。]
で表される構成単位及び下記式[2]Where n is an integer from 1 to 300. ]
The structural unit represented by and the following formula [2]
【0011】[0011]
【化6】 [Chemical 6]
【0012】[式中、Wは単結合、アルキレン基、アル
キリデン基、シクロアルキレン基、シクロアルキリデン
基またはベンゼン置換アルキリデン基であり、R2 〜R
5 は水素、ハロゲン、炭素原子数1〜6のアルキル基、
シクロアルキル基、フェニル基であり、R2 〜R5 は同
一であっても、異なっていてもよい。]で表される構成
単位からなり、式[1]で表される構成単位が20〜7
0モル%で且つ0.7gを塩化メチレン100mlに溶解
した溶液の比粘度が0.275〜0.952であるコポ
リシロキサンカーボネート樹脂0.3〜100重量%及
び芳香族ポリカーボネート樹脂0〜99.7重量%より
なる樹脂成分100重量部に、リン酸トリアルキルエス
テル、フェニルホスホン酸エステル及びフェニル亜ホス
ホン酸エステルから選ばれた少なくとも一種の安定剤
0.001〜0.1重量部及びガラス繊維5〜120重
量部を配合してなる芳香族ポリカーボネート樹脂系組成
物に係るものである。[Wherein W represents a single bond, an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group or a benzene-substituted alkylidene group, and R 2 to R 2
5 is hydrogen, halogen, an alkyl group having 1 to 6 carbon atoms,
It is a cycloalkyl group or a phenyl group, and R 2 to R 5 may be the same or different. ] The constitutional unit represented by the formula [1] is 20 to 7
0.3 to 100% by weight of a copolysiloxane carbonate resin and 0 to 99.7% of a polypolycarbonate carbonate resin having a specific viscosity of 0.275 to 0.952 in a solution of 0 mol% and 0.7 g dissolved in 100 ml of methylene chloride. 0.001 to 0.1 part by weight of at least one stabilizer selected from trialkyl phosphate, phenylphosphonic acid ester and phenylphosphonous acid ester and 100 parts by weight of glass fiber The present invention relates to an aromatic polycarbonate resin composition containing 120 parts by weight.
【0013】本発明で使用するコポリシロキサンカーボ
ネート樹脂を構成する単位[1]の製造に用いるシロキ
サン含有二価フェノールは、例えば塩化白金酸触媒の存
在下に、Si−H基含有シロキサンとp-tert−ブトキシ
スチレンを付加反応させ、次いでtert−ブトキシ基を塩
酸で加水分解して得られる。ジメチルシロキサン単位の
繰り返し数nは、好ましくは1〜100,さらには1〜
60がより好ましい。The siloxane-containing dihydric phenol used for the production of the unit [1] constituting the copolysiloxane carbonate resin used in the present invention is, for example, a Si-H group-containing siloxane and a p-tert. It is obtained by addition-reacting with butoxystyrene and then hydrolyzing the tert-butoxy group with hydrochloric acid. The number n of repeating dimethylsiloxane units is preferably 1 to 100, more preferably 1 to
60 is more preferred.
【0014】コポリシロキサンカーボネート樹脂は、上
記シロキサン含有二価フェノールと他の二価フェノール
を溶媒の存在下にホスゲンと反応させることによって容
易に得ることができる。シロキサン含有二価フェノール
以外の二価フェノールとしては、例えばハイドロキノ
ン、レゾルシン、ビフェノール、ビス(4−ヒドロキシ
フェニル)メタン、1,1−ビス(4−ヒドロキシフェ
ニル)エタン、1,1−ビス(4−ヒドロキシフェニ
ル)−1−フェニルエタン、2,2−ビス(4−ヒドロ
キシフェニル)プロパン[通称ビスフェノールA]、
1,1−ビス(4−ヒドロキシフェニル)シクロヘキサ
ン、2,2−ビス(3−メチル−4−ヒドロキシフェニ
ル)プロパン、2,2−ビス(3,5−ジメチル−4−
ヒドロキシフェニル)プロパン、2,2−ビス(3−フ
ェニル−4−ヒドロキシフェニル)プロパン、ビス(4
−ヒドロキシフェニル)ケトン、ビス(4−ヒドロキシ
フェニル)スルホン、ビス(4−ヒドロキシフェニル)
オキサイド、ビス(4−ヒドロキシフェニル)スルフィ
ド又はこれらのハロゲン化物が用いられる。中でもビス
フェノールAが最も好ましい。また少量の三価以上のフ
ェノール系化合物を分岐剤として用いてもよい。The copolysiloxane carbonate resin can be easily obtained by reacting the siloxane-containing dihydric phenol with another dihydric phenol in the presence of a solvent with phosgene. Examples of the dihydric phenol other than the siloxane-containing dihydric phenol include hydroquinone, resorcin, biphenol, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4- Hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A],
1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-)
Hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, bis (4
-Hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl)
Oxides, bis (4-hydroxyphenyl) sulfides or their halides are used. Of these, bisphenol A is most preferable. A small amount of trivalent or higher phenolic compound may be used as a branching agent.
【0015】かかるコポリシロキサンカーボネート樹脂
は、上記式[1]で表される構成単位が20〜70モル
%で且つ0.7g を塩化メチレン100mlに溶解した溶
液の比粘度が0.275〜0.952のものである。式
[1]で表される構成単位が20モル%に達しないもの
では、ガラス繊維強化ポリカーボネート樹脂の耐衝撃性
の改善が充分でなく、70モル%より多いものでは芳香
族ポリカーボネート樹脂本来の優れた特性である透明性
や高いガラス転移温度が損なわれるようになるので適当
でない。また、比粘度が0.275に達しないものでは
強度が弱く、耐衝撃性の改善効果が得られ難く、0.9
52より高いものでは溶融時の流動性が悪化するので適
当でない。The copolysiloxane carbonate resin has a constitutional unit represented by the above formula [1] of 20 to 70 mol%, and a solution of 0.7 g dissolved in 100 ml of methylene chloride has a specific viscosity of 0.275 to 0. 952. If the constitutional unit represented by the formula [1] does not reach 20 mol%, the impact resistance of the glass fiber reinforced polycarbonate resin is not sufficiently improved, and if it exceeds 70 mol%, the aromatic polycarbonate resin is originally excellent. It is not suitable because the transparency and high glass transition temperature, which are the characteristics, are impaired. Further, if the specific viscosity does not reach 0.275, the strength is weak and it is difficult to obtain the effect of improving the impact resistance.
If it is higher than 52, the fluidity at the time of melting is deteriorated, so that it is not suitable.
【0016】上記コポリシロキサンカーボネート樹脂に
配合する安定剤は、リン酸トリアルキルエステル、フェ
ニルホスホン酸エステルおよびフェニル亜ホスホン酸エ
ステルから選ばれる。リン酸トリアルキルエステルとし
ては、例えばリン酸トリメチル、リン酸トリエチル、リ
ン酸トリプロピル、リン酸トリブチルがあげられ、フェ
ニルホスホン酸エステルとしては、例えばフェニルホス
ホン酸ジメチルエステル、フェニルホスホン酸ジエチル
エステル、フェニルホスホン酸ジフェニルエステル、
3,5−ジ−tert−ブチル−4−ヒドロキシベンジルホ
スホン酸ジエチルエステルがあげられ、フェニル亜ホス
ホン酸エステルとしては、例えばテトラキス(2,4−
ジ−tert−ブチルフェニル)−4,4′−ビフェニレン
ジホスホナイトがあげられる。これらの安定剤は単独で
使用しても、二種以上併用してもよい。The stabilizer to be added to the copolysiloxane carbonate resin is selected from phosphoric acid trialkyl ester, phenylphosphonic acid ester and phenylphosphonous acid ester. Examples of the phosphoric acid trialkyl ester include trimethyl phosphate, triethyl phosphate, tripropyl phosphate and tributyl phosphate, and examples of the phenylphosphonic acid ester include phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester and phenyl. Phosphonic acid diphenyl ester,
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester may be mentioned, and examples of the phenylphosphonous acid ester include tetrakis (2,4-
Di-tert-butylphenyl) -4,4'-biphenylene diphosphonite. These stabilizers may be used alone or in combination of two or more.
【0017】かかる安定剤の使用量は、樹脂成分100
重量部に対して0.001〜0.1重量部である。0.
001重量部に達しない量では十分な色相改善効果が得
られ難く、0.1重量部以上加えても最早色相改善効果
は飽和し、逆に物性に悪影響を与えるようになるので適
当でない。The amount of the stabilizer used is 100 parts by weight of the resin component.
It is 0.001 to 0.1 parts by weight with respect to parts by weight. 0.
If the amount is less than 001 parts by weight, it is difficult to obtain a sufficient hue improving effect, and even if 0.1 part by weight or more is added, the hue improving effect is saturated at the earliest and adversely affects the physical properties.
【0018】また、上記安定剤と共に配合するガラス繊
維は、芳香族ポリカーボネート樹脂に使用されるガラス
繊維であれば任意に使用される。好ましいガラス繊維の
径は3〜20μであり、成形品中のガラス繊維の長さは
0.02〜0.5mm程度である。またガラス繊維には、
樹脂との親和性を向上させる目的でシランカップリング
剤等の表面処理を施したり、取扱性をを向上させる目的
でアクリル系樹脂やウレタン系樹脂等で集束処理を施し
てもよい。Further, the glass fiber to be blended with the above stabilizer may be any glass fiber used in the aromatic polycarbonate resin. The preferable diameter of the glass fiber is 3 to 20 μm, and the length of the glass fiber in the molded product is about 0.02 to 0.5 mm. In addition, glass fiber,
A surface treatment of a silane coupling agent or the like may be performed for the purpose of improving the affinity with the resin, or a focusing treatment may be performed with an acrylic resin or a urethane resin for the purpose of improving the handleability.
【0019】ガラス繊維の使用量は、樹脂成分100重
量部に対して5〜120重量部である。5重量部に達し
ない量では、充分なガラス繊維補強効果が得られ難く、
120重量部より多くなると成形性が低下するので適当
でない。The amount of glass fiber used is 5 to 120 parts by weight per 100 parts by weight of the resin component. When the amount is less than 5 parts by weight, it is difficult to obtain a sufficient glass fiber reinforcing effect,
If it is more than 120 parts by weight, the moldability is deteriorated, which is not suitable.
【0020】以上コポリシロキサンカーボネート樹脂
に、安定剤とガラス繊維を配合する系について説明した
が、本発明のガラス繊維強化樹脂組成物にあっては、樹
脂成分としてコポリシロキサンカーボネート樹脂と芳香
族ポリカーボネート樹脂との混合樹脂も対象とする。即
ち、芳香族ポリカーボネート樹脂に上記コポリシロキサ
ンカーボネート、ガラス繊維及び上記安定剤を配合した
ガラス繊維強化樹脂組成物である。The system in which the stabilizer and the glass fiber are blended with the copolysiloxane carbonate resin has been described above. In the glass fiber reinforced resin composition of the present invention, the copolysiloxane carbonate resin and the aromatic polycarbonate resin are used as resin components. Resins mixed with are also included. That is, it is a glass fiber reinforced resin composition in which an aromatic polycarbonate resin is blended with the copolysiloxane carbonate, glass fibers and the stabilizer.
【0021】ここで対象とする芳香族ポリカーボネート
樹脂は、二価フェノールとポリカーボネート前駆物質と
を反応させて得られる通常の芳香族ポリカーボネート樹
脂である。ここで使われる二価フェノールとしては、先
にコポリシロキサンカーボネート樹脂の説明のところで
述べた二価フェノールがあげられ、特にビスフェノール
Aが好ましく使用される。The aromatic polycarbonate resin of interest here is a usual aromatic polycarbonate resin obtained by reacting a dihydric phenol with a polycarbonate precursor. Examples of the dihydric phenol used here include the dihydric phenol described above in the description of the copolysiloxane carbonate resin, and bisphenol A is particularly preferably used.
【0022】芳香族ポリカーボネート樹脂とコポリシロ
キサンカーボネート樹脂との混合割合は、芳香族ポリカ
ーボネート樹脂が99.7重量%以下、コポリシロキサ
ンカーボネート樹脂が0.3重量%以上である。コポリ
シロキサンカーボネート樹脂が0.3重量%に達しない
量では得られるガラス繊維強化樹脂組成物の耐衝撃性が
劣るようになる。特にガラス繊維強化した芳香族ポリカ
ーボネート樹脂組成物の耐衝撃性を改善する目的のとき
はコポリシロキサンカーボネート樹脂が0.5〜80重
量%の範囲になる量が好ましい。The mixing ratio of the aromatic polycarbonate resin and the copolysiloxane carbonate resin is 99.7 wt% or less for the aromatic polycarbonate resin and 0.3 wt% or more for the copolysiloxane carbonate resin. When the amount of the copolysiloxane carbonate resin does not reach 0.3% by weight, the glass fiber-reinforced resin composition obtained has poor impact resistance. Particularly for the purpose of improving the impact resistance of the glass fiber reinforced aromatic polycarbonate resin composition, the amount of the copolysiloxane carbonate resin is preferably in the range of 0.5 to 80% by weight.
【0023】本発明のガラス繊維強化樹脂組成物を製造
するには任意の方法が採用される。例えば、各成分をタ
ンブラー、スーパーミキサー、ナウタミキサー等を用い
てドライブレンドし、押出機によりペレット化する方
法、芳香族ポリカーボネート樹脂、コポリシロキサンカ
ーボネート樹脂及び安定剤を予め混合した後、ガラス繊
維と共に押出してペレット化する方法等いずれでもよ
い。Any method may be used to produce the glass fiber reinforced resin composition of the present invention. For example, a method of dry blending each component using a tumbler, a super mixer, a Nauta mixer, etc., and pelletizing with an extruder, an aromatic polycarbonate resin, a copolysiloxane carbonate resin, and a stabilizer are mixed in advance, and then extruded with glass fiber. Any method such as pelletizing may be used.
【0024】なおペレット化や成形に際しては、本発明
のガラス繊維強化樹脂組成物をそのままペレット化や成
形してもよいが、必要に応じて更に光安定剤、着色剤、
帯電防止剤、滑剤、離型剤等の添加剤を加えてもよい。At the time of pelletizing or molding, the glass fiber reinforced resin composition of the present invention may be pelletized or molded as it is, but if necessary, a light stabilizer, a coloring agent,
You may add additives, such as an antistatic agent, a lubricant, and a mold release agent.
【0025】[0025]
【実施例】以下に実施例をあげて本発明を更に説明す
る。なお、実施例中の部は重量部であり、%は重量%で
ある。色相(b値)はJIS K 7105に準拠して測定
し、衝撃強さは ASTM D 256に準拠して測定した。EXAMPLES The present invention will be further described with reference to the following examples. In addition, the part in an Example is a weight part and% is weight%. The hue (b value) was measured according to JIS K 7105, and the impact strength was measured according to ASTM D 256.
【0026】[0026]
【合成例1】 <コポリシロキサンカーボネート樹脂の合成> 温度
計、撹拌機付き反応器にイオン交換水530部、48%
苛性ソーダ水溶液96.8部を入れ、ビスフェノールA
94.2部、ハイドロサルファイト0.2部を溶解した
後、塩化メチレン749部に式[1]の構成単位を与え
るポリシロキサンビスフェノール(n=20、R1がエ
チレン基とエチリデン基の混合物でありその比が85:
15,APHA:20)114.8部を溶解して加え、撹拌
下15〜25℃でホスゲン55.5部を60分を要して
吹込んだ。次いでp-tert−ブチルフェノール0.05部
及び48%苛性ソーダ水溶液19.3部を添加し、乳化
した後トリエチルアミン0.32部を添加して28〜3
3℃で2時間撹拌して反応を終了した。反応終了後、生
成物を塩化メチレンで希釈して水洗した後、塩酸酸性に
して水洗し、水相の導電率がイオン交換水と殆ど同じに
なったところで塩化メチレンを蒸発除去してコポリシロ
キサンカーボネート樹脂210部を得た(収率95
%)。このポリマ−の塩化メチレンを溶媒とする0.7
g /100ml濃度の溶液の比粘度は0.671であっ
た。[Synthesis Example 1] <Synthesis of copolysiloxane carbonate resin> 530 parts of ion-exchanged water, 48% in a reactor equipped with a thermometer and a stirrer
Add 96.8 parts of aqueous caustic soda solution and add bisphenol A.
After dissolving 94.2 parts and 0.2 parts of hydrosulfite, polysiloxane bisphenol (n = 20, R 1 is a mixture of ethylene group and ethylidene group) giving 749 parts of methylene chloride to the constitutional unit of the formula [1]. Yes The ratio is 85:
(15, APHA: 20) 114.8 parts was dissolved and added, and 55.5 parts of phosgene was blown thereinto under stirring at 15 to 25 ° C. over 60 minutes. Then, p-tert-butylphenol (0.05 parts) and a 48% aqueous sodium hydroxide solution (19.3 parts) were added, and the mixture was emulsified, followed by addition of triethylamine (0.32 part) to give 28-3.
The reaction was completed by stirring at 3 ° C. for 2 hours. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was removed by evaporation to remove copolysiloxane carbonate. 210 parts of resin was obtained (yield 95
%). 0.7 of this polymer using methylene chloride as a solvent
The specific viscosity of the solution with a concentration of g / 100 ml was 0.671.
【0027】[0027]
【合成例2】 <コポリシロキサンカーボネート樹脂の合成> 合成例
1と同様の装置を使用し、ポリシロキサンビスフェノー
ル(n=40,R1がエチレン基とエチリデン基の混合
物でありその比が85:15,APHA:15)を119.
8部、ビスフェノールA98.2部、p-tert−ブチルフ
ェノールを0.68部とする以外は合成例1と同様に実
施してコポリシロキサンカーボネート樹脂221部を得
た(収率96%)。このポリマーの比粘度は0.692
であった。[Synthesis Example 2] <Synthesis of copolysiloxane carbonate resin> Using the same apparatus as in Synthesis Example 1, polysiloxane bisphenol (n = 40, R 1 is a mixture of ethylene group and ethylidene group and the ratio is 85:15). , APHA: 15) 119.
221 parts of copolysiloxane carbonate resin was obtained in the same manner as in Synthesis Example 1 except that 8 parts, 98.2 parts of bisphenol A, and 0.68 part of p-tert-butylphenol were used (yield 96%). The specific viscosity of this polymer is 0.692.
Met.
【0028】[0028]
【実施例1】ポリカーボネートパウダー[帝人化成
(株)製パンライトL-1250 WP ]79.5部、合成
例1にて合成したコポリシロキサンカーボネート樹脂
0.5部、ガラスファイバーチョップドストランド20
部及びテトラキス(2,4−ジ−t−ブチルフェニル)
−4,4′−ビフェニレンジホスホナイト0.03部を
タンブラーでドライブレンドし、280℃の温度で押出
機によりペレット化した。このものを120℃で6時間
乾燥した後、射出成形機[住友重機(株)ネスタールサ
イキャップ480/150]により50×90×2mm、
63×12.7×3.2mm及び6.4mmの試験片を射出
成形し、色相及び衝撃強さを評価し、結果を表1に示し
た。Example 1 79.5 parts of polycarbonate powder [Panlite L-1250 WP manufactured by Teijin Chemicals Ltd.], 0.5 part of the copolysiloxane carbonate resin synthesized in Synthesis Example 1, and glass fiber chopped strand 20
Parts and tetrakis (2,4-di-t-butylphenyl)
0.03 parts of -4,4'-biphenylene diphosphonite was dry blended in a tumbler and pelletized by an extruder at a temperature of 280 ° C. This product was dried at 120 ° C. for 6 hours, and then 50 × 90 × 2 mm by an injection molding machine [Sumitomo Heavy Industries Ltd. Nestal Sai Cap 480/150].
63 × 12.7 × 3.2 mm and 6.4 mm test pieces were injection-molded, the hue and impact strength were evaluated, and the results are shown in Table 1.
【0029】[0029]
【実施例2】実施例1のポリカーボネートパウダーを7
9部、コポリシロキサンカーボネート樹脂として合成例
2で合成したポリマー1.0部とし、テトラキス(2,
4−ジ−t−ブチルフェニル)−4,4′−ビフェニレ
ンジホスホナイトに代えてリン酸トリメチルエステルを
0.03部用いる以外は実施例1と同様に実施し、評価
結果を表1に示した。Example 2 The polycarbonate powder of Example 1 was added to 7
9 parts, 1.0 part of the polymer synthesized in Synthesis Example 2 as a copolysiloxane carbonate resin, and tetrakis (2,
4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite was replaced by 0.03 part of phosphoric acid trimethyl ester, and the same operation as in Example 1 was carried out, and the evaluation results are shown in Table 1. It was
【0030】[0030]
【実施例3】実施例2のポリカーボネートパウダーを7
5部、コポリシロキサンカーボネート樹脂を5.0部と
する以外は実施例2と同様に実施し、評価結果を表1に
示した。Example 3 The polycarbonate powder of Example 2 was added
Example 1 was repeated except that 5 parts and 5.0 parts of the copolysiloxane carbonate resin were used, and the evaluation results are shown in Table 1.
【0031】[0031]
【比較例1】実施例1のポリカーボネートパウダーを8
0部、コポリシロキサンカーボネート樹脂を用いず且つ
安定剤も用いない以外は実施例1と同様に実施し、評価
結果を表1に示した。[Comparative Example 1] The polycarbonate powder of Example 1 was 8
Example 1 was repeated except that 0 part of the copolysiloxane carbonate resin was not used and no stabilizer was used, and the evaluation results are shown in Table 1.
【0032】[0032]
【比較例2】実施例1のテトラキス(2,4−ジ−t−
ブチルフェニル)−4,4−ビフェニレンジホスホナイ
トを用いない以外は実施例1と同様に実施し、評価結果
を表1に示した。Comparative Example 2 Tetrakis (2,4-di-t-) of Example 1
(Butylphenyl) -4,4-biphenylene diphosphonite was used in the same manner as in Example 1 except that the evaluation results were shown in Table 1.
【0033】[0033]
【比較例3】実施例3のコポリシロキサンカーボネート
樹脂を用いない以外は実施例3と同様に実施し、評価結
果を表1に示した。Comparative Example 3 The procedure of Example 3 was repeated except that the copolysiloxane carbonate resin of Example 3 was not used, and the evaluation results are shown in Table 1.
【0034】[0034]
【表1】 [Table 1]
【0035】[0035]
【発明の効果】本発明の樹脂組成物は表1からも明らか
なように色相、耐衝撃性共に優れており、特に電気電子
分野、機械分野等の部品又はハウジング等に有用であ
る。As is apparent from Table 1, the resin composition of the present invention is excellent in both hue and impact resistance, and is particularly useful for parts or housings in the fields of electrical and electronic and mechanical fields.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 C08K 7/14 C08L 69/00 LPS 8416−4J ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C08K 7/14 C08L 69/00 LPS 8416-4J
Claims (1)
成単位及び下記式[2] 【化3】 [式中、Wは単結合、アルキレン基、アルキリデン基、
シクロアルキレン基、シクロアルキリデン基またはベン
ゼン置換アルキリデン基であり、R2 〜R5 は水素、ハ
ロゲン、炭素原子数1〜6のアルキル基、シクロアルキ
ル基、フェニル基であり、R2 〜R5 は同一であって
も、異なっていてもよい。]で表される構成単位からな
り、式[1]で表される構成単位が20〜70モル%で
且つ0.7gを塩化メチレン100mlに溶解した溶液の
比粘度が0.275〜0.952であるコポリシロキサ
ンカーボネート樹脂0.3〜100重量%及び芳香族ポ
リカーボネート樹脂0〜99.7重量%よりなる樹脂成
分100重量部に、リン酸トリアルキルエステル、フェ
ニルホスホン酸エステル及びフェニル亜ホスホン酸エス
テルから選ばれた少なくとも一種の安定剤0.001〜
0.1重量部及びガラス繊維5〜120重量部を配合し
てなる芳香族ポリカーボネート樹脂系組成物。1. The following formula [1]: [In the formula, R 1 is —CH 2 CH 2 — or And n is an integer of 1 to 300. ] And a structural unit represented by the following formula [2] [In the formula, W is a single bond, an alkylene group, an alkylidene group,
A cycloalkylene group, a cycloalkylidene group or a benzene-substituted alkylidene group, R 2 to R 5 are hydrogen, halogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, a phenyl group, and R 2 to R 5 are It may be the same or different. ] The constitutional unit represented by the formula [1] is 20 to 70 mol% and the specific viscosity of a solution of 0.7 g dissolved in 100 ml of methylene chloride is 0.275 to 0.952. 100 parts by weight of a resin component consisting of 0.3 to 100% by weight of a copolysiloxane carbonate resin and 0 to 99.7% by weight of an aromatic polycarbonate resin, and a trialkyl phosphate, a phenylphosphonic acid ester, and a phenylphosphonous acid ester. 0.001 to at least one stabilizer selected from
An aromatic polycarbonate resin composition comprising 0.1 part by weight and 5 to 120 parts by weight of glass fiber.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11481392A JPH05311079A (en) | 1992-05-07 | 1992-05-07 | Aromatic polycarbonate resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11481392A JPH05311079A (en) | 1992-05-07 | 1992-05-07 | Aromatic polycarbonate resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH05311079A true JPH05311079A (en) | 1993-11-22 |
Family
ID=14647330
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP11481392A Pending JPH05311079A (en) | 1992-05-07 | 1992-05-07 | Aromatic polycarbonate resin composition |
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JP (1) | JPH05311079A (en) |
Cited By (3)
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US9580597B2 (en) | 2014-12-04 | 2017-02-28 | Lg Chem, Ltd. | Polycarbonate composition and article comprising the same |
US9732186B2 (en) | 2014-09-05 | 2017-08-15 | Lg Chem, Ltd. | Copolycarbonate and composition comprising the same |
US9969841B2 (en) | 2014-12-04 | 2018-05-15 | Lg Chem, Ltd. | Copolycarbonate and composition comprising the same |
-
1992
- 1992-05-07 JP JP11481392A patent/JPH05311079A/en active Pending
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US9868818B2 (en) | 2014-12-04 | 2018-01-16 | Lg Chem, Ltd. | Copolycarbonate and composition containing the same |
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