JPS6131144B2 - - Google Patents
Info
- Publication number
- JPS6131144B2 JPS6131144B2 JP10657777A JP10657777A JPS6131144B2 JP S6131144 B2 JPS6131144 B2 JP S6131144B2 JP 10657777 A JP10657777 A JP 10657777A JP 10657777 A JP10657777 A JP 10657777A JP S6131144 B2 JPS6131144 B2 JP S6131144B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- formula
- aromatic
- resin composition
- component
- 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.)
- Expired
Links
- 125000003118 aryl group Chemical group 0.000 claims description 27
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 24
- 229920000515 polycarbonate Polymers 0.000 claims description 20
- 239000004417 polycarbonate Substances 0.000 claims description 20
- 239000011342 resin composition Substances 0.000 claims description 16
- 229920000578 graft copolymer Polymers 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229920005992 thermoplastic resin Polymers 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 150000008360 acrylonitriles Chemical class 0.000 claims description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims 1
- -1 vinyl cyanide compound Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000002845 discoloration Methods 0.000 description 9
- 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 7
- 238000000465 moulding Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- ZTHJQCDAHYOPIK-UHFFFAOYSA-N 3-methylbut-2-en-2-ylbenzene Chemical compound CC(C)=C(C)C1=CC=CC=C1 ZTHJQCDAHYOPIK-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
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical group C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003901 ceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 229920000874 polytetramethylene terephthalate Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は熱安定性及び諸特性に優れた熱可塑性
樹脂組成物に関するものであり、更に詳しくは優
れた成形性、耐熱変色及び耐衝撃性を有するポリ
カーボネート系樹脂組成物に関するものである。
４・4′−ジヒドロキシジフエニルアルカン系ポ
リカーボネート（以下、単にポリカーボネートと
いう）は機械的および熱的特性にすぐれた性能を
有しているが、溶融粘度が高いため、射出成形に
際して若干の成形困難を伴なうとともに成形後に
クラツキングを起こし易い欠点がある。さらに前
記の衝撃強度においても、樹脂片の厚みを増すと
極端に衝撃強度が低下するという欠点を有する。
（例えばASTM−256試験法によるアイゾツト、
ノツチ付衝撃強度は1/8インチ棒では約90Kgcm/cm
と高いが、1/4インチ棒では僅かに15Kgcm/cmと著
しく低下する）。
従来、ポリカーボネートの成形性の改良法とし
てポリカーボネートとポリブタジエン系グラフト
共重合体とからなる熱可塑性樹脂組成物が提案さ
れているが（例えば特公昭38−15225号公報、特
公昭39−71号公報および特公昭42−11496号公報
参照）、これらの樹脂組成物においても、前記の
衝撃強度の低下を改善することができなかつた。
また、芳香族ポリカーボネートの有する欠点を
解決するために、芳香族ポリカーボネートと可燃
性を有する熱可塑性樹脂、例えば芳香族ポリエス
テルとを溶融状態において均一に混合し、両重合
体相互の加工性や物性を補う試み（例えば特公昭
36−14035号公報参照）がなされている。
この試みのように、芳香族ポリカーボネートに
可燃性を有する熱可塑性樹脂である芳香族ポリエ
ステルを混合することは、該芳香族ポリカーボネ
ートの溶融粘度が低下し、成形性が容易になると
ともに芳香族ポリカーボネートの耐溶剤性が向上
するという利点があるが、得られた樹脂組成物は
耐衝撃性が不十分であるために耐衝撃性の要求さ
れる用途への進出ができない欠点がある。
更に、かかる欠点を改善する目的で上記組成物
に、ブタジエン系重合体にメタクリル酸エステ
ル、芳香族モノビニル化合物およびシアン化ビニ
ル化合物の１種以上をグラフト共重合せしめたブ
タジエン系グラフト共重合体を特定割合で混合す
ると、得られる熱可塑性樹脂組成物が上記グラフ
ト共重合体を含有しない組成物のすぐれた成形
性、及び寸法安定性を保持すると共に更にすぐれ
た機械的特性、特に衝撃強度を有するものが得ら
れることも提案されている（特開昭49−41442号
公報参照）。しかし、該組成物は、配合組成の１
成分であるポリブタジエン系グラフト共重合体に
２重結合が残存しているため、成形時の熱安定
性、乾熱処理時の成形ペレツト及び成形品の熱変
色が大きくしかも物性低下が著しくなるという欠
点がある。
本発明者は上記の樹脂組成物の熱安定性及び熱
変色の改良を主目的として鋭意研究した結果、芳
香族ポリカーボネート(A)、芳香族ポリエステル(B)
並びにブタジエン系重合体(イ)にメタクリル酸エス
テル(ロ)、芳香族モノビニル化合物(ハ)及びシアン化
ビニル化合物(ニ)より成る群から選ばれたビニル系
単体の１種以上をグラフト共重合せしめたブタジ
エン系グラフト共重合体(C)からなる熱可塑性樹脂
組成物において、特定のリン酸エステル・金属塩
を特定の割合で混合することにより成形時の溶融
安定性及びペレツト、成形片の乾熱変色が著しく
改善されることを見出し、本発明に到達したもの
である。
すなわち、本発明は、
(A)芳香族ポリカーボネート４〜95重量％、(B)芳
香族ポリエステル０〜91重量％、及び(C)ブタジエ
ン系重合体に、メタクリル酸エステル、芳香族モ
ノビニル化合物及びシアン化ビニル化合物よりな
る群から選ばれるビニル系単量体の１種以上をグ
ラフト共重合せしめたブタジエン系グラフト共重
合体５〜50重量％より成る樹脂組成物100重量部
当り、0.01〜10重量部の(D)一般式
及び
〔但し、式中のＭはアルカリ土類金属、アルミニ
ウム又は亜鉛であり、Ｒは炭素数５〜30のアルキ
ル基であり、またｎはＭの原子価を表わす整数で
ある。〕
で示されるリン酸エステル・金属塩の少くとも１
種を含有せしめてなる耐熱性の優れた熱可塑性樹
脂組成物に関する。
本発明に用いられる芳香族ポリカーボネート(A)
は種々のタイプの芳香族ポリカーボネートが採用
できるが、特に４・4′−ジヒドロキシジフエニル
アルカン系ポリカーボネートが好ましく、更に具
体的には２・２−（４・4′−ジヒドロキシジフエ
ニル）−プロパン（以下ビスフエノールＡと略記
する）をジヒドロキシ成分として用い、エステル
交換法あるいはホスゲン法により得られたポリカ
ーボネートが好ましい。更に芳香族ポリカーボネ
ートはビスフエノールＡの１部または全部を他の
４・4′−ジヒドロキシジフエニルアルカンあるい
は４・4′−ジヒドロキシジフエニルアルカンある
いは４・4′−ジヒドロキシジフエニルスルホン、
４・4′−ジヒドロキシジフエニルエーテルなどに
置換したものでもよく、また２種以上の芳香族ポ
リカーボネートを混合して用いてもよい。
本発明に用いられる(B)成分の芳香族ポリエステ
ルの好ましいものとしてはポリエチレンテレフタ
レート、ポリトリメチレンテレフタレート、ポリ
テトラメチレンテレフタレート、ポリエチレン−
２・６−ナフタレート及びポリテトラメチレン−
２・６−ナフタレート等が例示でき、これらのう
ち特にポリエチレンテレフタレートが好ましい。
本発明に用いられる(C)成分はブタジエン系グラ
フト共重合体であり、特にポリブタジエン系グラ
フト共重合体が好ましく、このグラフト共重合体
はポリブタジエン(イ)もしくはブタジエンを50重量
％以上含有するブタジエン共重合体(イ)′にメタク
リル酸エステル単量体(ロ)、芳香族ビニル単量体(ハ)
及びシアン化ビニル化合物からなるビニール系単
量体の１種以上を任意の割合でグラフト共重合し
て得ることができる。前記(C)成分の製造の際のブ
タジエン系共重合体、特にブタジエン系重合体(イ)
成分（ゴム成分）の量は１〜80重量％、好ましく
は５〜70重量％、特に好ましくは５〜70重量％を
用いる。
前記ゴム成分にグラフト重合するビニル系単量
体は、メタクリル酸エステル単量体（例えばメタ
クリル酸メチル、メタクリル酸エチル、メタクリ
ル酸プロピル、メタクリル酸イソプロピル、メタ
クリル酸ブチル等）、芳考族ビニール単量体（例
えばスチレン、α−メチルスチレン、ビニルトル
エン、ビニルキシレン、トリメチルスチレン、ハ
ロゲン化スチレン等）及びシアン化ビニル単量体
（例えばアクリロニトリル、メタクリロニトリル
等）であり、そのうちメタクリル酸エステル単量
体としてはメタクリル酸メチル（又はエチル）、
芳香族ビニール単量体としてはスチレン、及びシ
アン化ビニル単量体としてはアクリロニトリルが
それぞれ好ましい。
更に、本発明に用いられる(D)成分のリン酸エス
テル・金属塩は一般式
及び
で示される化合物である。ここで上式中のＭはア
ルカリ土類金属、アルミニウム又は亜鉛であり、
Ｒは炭素数５〜30のアルキル基であり、またｎは
Ｍの原子価を表わす整数である。アルカリ土類金
属としては例えばマグネシウム、カルシウム、バ
リウム、ストロンチウム等が挙げられる。炭素数
５〜30のアルキル基としては、例えばペンチル、
ヘキシル、ヘプチル、オクチル、ノニル、デシ
ル、ウンデシル、ドデシル、トリデシル、テトラ
デシル、ペンタデシル、ヘキサデシル、ヘプタデ
シル、オクタデシル、ノナデシル、エイコシル、
テトラコシル、ヘキサコシル等があげられる。こ
れらのうち炭素数８〜18のアルキルが好ましい。
前記一般式(1)で示される化合物としては、例え
ば
が挙げられる。また前記一般式(2)で示される化合
物としては、例えば
The present invention relates to a thermoplastic resin composition having excellent thermal stability and various properties, and more particularly to a polycarbonate resin composition having excellent moldability, heat discoloration resistance, and impact resistance. 4,4'-Dihydroxydiphenylalkane polycarbonate (hereinafter simply referred to as polycarbonate) has excellent mechanical and thermal properties, but due to its high melt viscosity, it has some difficulty in injection molding. In addition, there is a drawback that cracking is likely to occur after molding. Furthermore, the aforementioned impact strength also has the disadvantage that as the thickness of the resin piece increases, the impact strength decreases extremely.
(For example, Izot according to ASTM-256 test method,
Notched impact strength is approximately 90Kgcm/cm for 1/8 inch rod
However, with a 1/4 inch rod, it is significantly lower at 15Kgcm/cm). Conventionally, thermoplastic resin compositions consisting of polycarbonate and polybutadiene-based graft copolymers have been proposed as a method for improving the moldability of polycarbonate (for example, Japanese Patent Publication No. 38-15225, Japanese Patent Publication No. 39-71, and (See Japanese Patent Publication No. 42-11496), these resin compositions also failed to improve the aforementioned drop in impact strength. In addition, in order to solve the drawbacks of aromatic polycarbonate, aromatic polycarbonate and a flammable thermoplastic resin, such as aromatic polyester, are uniformly mixed in a molten state to improve the processability and physical properties of both polymers. Attempts to supplement (e.g.
36-14035)). Mixing aromatic polyester, which is a flammable thermoplastic resin, with aromatic polycarbonate, as in this attempt, lowers the melt viscosity of the aromatic polycarbonate, making it easier to mold the aromatic polycarbonate. Although it has the advantage of improved solvent resistance, the resulting resin composition has the disadvantage that it cannot be used in applications requiring impact resistance because it has insufficient impact resistance. Furthermore, in order to improve such drawbacks, we have specified a butadiene-based graft copolymer in which one or more of a methacrylic acid ester, an aromatic monovinyl compound, and a vinyl cyanide compound are graft-copolymerized to a butadiene-based polymer to the above composition. When mixed in the same proportions, the resulting thermoplastic resin composition retains the excellent moldability and dimensional stability of the composition not containing the graft copolymer, and also has superior mechanical properties, especially impact strength. It has also been proposed that the following can be obtained (see Japanese Unexamined Patent Publication No. 49-41442). However, the composition is
Because double bonds remain in the polybutadiene-based graft copolymer, which is a component, there are disadvantages such as thermal stability during molding, large thermal discoloration of molded pellets and molded products during dry heat treatment, and a significant decrease in physical properties. be. As a result of intensive research with the main purpose of improving the thermal stability and thermal discoloration of the above resin compositions, the present inventor found that aromatic polycarbonate (A), aromatic polyester (B)
and one or more vinyl-based simple substances selected from the group consisting of methacrylic acid ester (b), aromatic monovinyl compound (c), and vinyl cyanide compound (d) are graft-copolymerized onto the butadiene-based polymer (a). In a thermoplastic resin composition made of a butadiene-based graft copolymer (C), by mixing a specific phosphoric acid ester/metal salt in a specific ratio, the melt stability during molding and the dry heat resistance of pellets and molded pieces can be improved. It was discovered that discoloration was significantly improved, and the present invention was developed. That is, the present invention includes (A) 4 to 95% by weight of aromatic polycarbonate, (B) 0 to 91% by weight of aromatic polyester, and (C) butadiene-based polymer, methacrylic acid ester, aromatic monovinyl compound, and cyanide. 0.01 to 10 parts by weight per 100 parts by weight of a resin composition comprising 5 to 50% by weight of a butadiene-based graft copolymer obtained by graft copolymerizing one or more vinyl monomers selected from the group consisting of vinyl compounds. (D) general formula of as well as [However, in the formula, M is an alkaline earth metal, aluminum or zinc, R is an alkyl group having 5 to 30 carbon atoms, and n is an integer representing the valence of M. ] At least one of the phosphoric acid ester/metal salts represented by
The present invention relates to a thermoplastic resin composition containing seeds and having excellent heat resistance. Aromatic polycarbonate (A) used in the present invention
Although various types of aromatic polycarbonates can be employed, 4,4'-dihydroxydiphenylalkane-based polycarbonates are particularly preferred, and more specifically, 2,2-(4,4'-dihydroxydiphenyl)-propane ( Preferred is a polycarbonate obtained by a transesterification method or a phosgene method using bisphenol A (hereinafter abbreviated as bisphenol A) as a dihydroxy component. Furthermore, the aromatic polycarbonate can be prepared by substituting part or all of the bisphenol A with other 4,4'-dihydroxydiphenylalkane, 4,4'-dihydroxydiphenylalkane, or 4,4'-dihydroxydiphenylsulfone,
It may be substituted with 4,4'-dihydroxydiphenyl ether or the like, or a mixture of two or more aromatic polycarbonates may be used. Preferred aromatic polyesters as component (B) used in the present invention include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, and polyethylene terephthalate.
2,6-naphthalate and polytetramethylene-
Examples include 2,6-naphthalate, and among these, polyethylene terephthalate is particularly preferred. Component (C) used in the present invention is a butadiene-based graft copolymer, and a polybutadiene-based graft copolymer is particularly preferable. Polymer (a)′, methacrylic acid ester monomer (b), aromatic vinyl monomer (c)
It can be obtained by graft copolymerizing one or more types of vinyl monomers consisting of and vinyl cyanide compounds in any proportion. Butadiene-based copolymers, especially butadiene-based polymers (A) in the production of component (C)
The amount of the component (rubber component) used is 1 to 80% by weight, preferably 5 to 70% by weight, particularly preferably 5 to 70% by weight. The vinyl monomer to be graft-polymerized to the rubber component is a methacrylic acid ester monomer (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, etc.), aromatic vinyl monomer (e.g., styrene, α-methylstyrene, vinyltoluene, vinylxylene, trimethylstyrene, halogenated styrene, etc.) and vinyl cyanide monomers (e.g., acrylonitrile, methacrylonitrile, etc.), among which methacrylic acid ester monomers as methyl (or ethyl) methacrylate;
Styrene is preferred as the aromatic vinyl monomer, and acrylonitrile is preferred as the vinyl cyanide monomer. Furthermore, the phosphate ester/metal salt of component (D) used in the present invention has the general formula as well as This is a compound represented by Here, M in the above formula is an alkaline earth metal, aluminum or zinc,
R is an alkyl group having 5 to 30 carbon atoms, and n is an integer representing the valence of M. Examples of alkaline earth metals include magnesium, calcium, barium, and strontium. Examples of the alkyl group having 5 to 30 carbon atoms include pentyl,
Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,
Examples include tetracosyl and hexacosyl. Among these, alkyl having 8 to 18 carbon atoms is preferred. Examples of the compound represented by the general formula (1) include: can be mentioned. Further, as the compound represented by the general formula (2), for example,
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
等が挙げられる。これらの化合物は単独で用いて
もよく、また２種以上を用いてもよいが、混合物
を用いる方が好ましい。これらのうち特にBa、
Mg塩が好ましい。
本発明において、前記(A)、(B)及び(C)成分の使用
割合は、３成分の総量に対し(A)成分が４〜95重量
％（好ましくは20〜80重量％、更に好ましくは30
〜70重量％）であり、(B)成分が０〜91重量％（好
ましくは０〜60重量％、更に好ましくは10〜50重
量％）であり、更に(C)成分が５〜50重量％（好ま
しくは５〜40重量％、更に好ましくは５〜30重量
％）である。
また(D)成分の使用量は、前記(A)、(B)及び(C)成分
からなる組成物100重量部当り、0.01〜10重量
部、好ましくは0.01〜５重量部、特に好ましくは
0.05〜３重量部である。
本発明の耐熱性樹脂組成物を調製する方法は、
固体状物質を混合する任意の方法（例えばバンバ
リーミキサー、加熱ロールや単軸または多軸押出
機による方法）が適用でき、また熱可塑性樹脂組
成物を得る通常の混合が採用できる。例えば(A)成
分の芳香族ポリカーボネート、(B)成分として芳香
族ポリエステル、(C)成分のグラフト共重合体及び
(D)成分のリン酸エステル、金属塩を１回で混合す
る方法、予め３成分を混合し、次いで残りの１成
分を混合する方法、予め２成分を混合し、次いで
残りの２成分を１度に又は別々に混合する方法等
により製造することができる。
本発明の耐熱性樹脂組成物は、通常の樹脂成形
に供される装置及び条件で成形を行うことができ
る。また本発明の組成物には各種の添加剤（例え
ば離型剤、無機充填剤、ガラス繊維等）を添加し
てもよい。
本発明の耐熱性熱可塑性樹脂組成物は特定のグ
ラフト成分によるブタジエン系グラフト共重合体
を含有しているために、例えば芳香族ポリカーボ
ネート−芳香族ポリエステル組成物の優れた特性
を保持すると共に高い耐衝撃性及び優れた耐熱変
色を有する。
以下、実施例を挙げて本発明を詳細に説明す
る。
実施例１〜５及び比較例１
芳香族ポリカーボネートとしてパンライトＬ−
1250（商品名帝人化成KK）55重量％、芳香族ポ
リエステルとしてポリエチレンテレフタレート
（還元比粘度0.68）32.9〜33重量％、ゴム状グラ
フト共重合体としてメチルメタアクリレート、ブ
タジエン、スチレンとの共重合体（MBS樹脂）
12重量％及び熱安定剤のリン酸エステル・金属塩
として[Formula] etc. These compounds may be used alone or in combination of two or more, but it is preferable to use a mixture. Among these, especially Ba,
Mg salts are preferred. In the present invention, the proportion of components (A), (B), and (C) used is such that component (A) is 4 to 95% by weight (preferably 20 to 80% by weight, more preferably 20 to 80% by weight, and more preferably 20 to 80% by weight) based on the total amount of the three components. 30
~70% by weight), component (B) is 0 to 91% by weight (preferably 0 to 60% by weight, more preferably 10 to 50% by weight), and further component (C) is 5 to 50% by weight. (preferably 5 to 40% by weight, more preferably 5 to 30% by weight). The amount of component (D) to be used is 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, particularly preferably
It is 0.05 to 3 parts by weight. The method for preparing the heat-resistant resin composition of the present invention includes:
Any method of mixing solid substances (for example, using a Banbury mixer, heated rolls, or single or multi-screw extruder) can be used, and conventional mixing methods for obtaining thermoplastic resin compositions can be used. For example, aromatic polycarbonate as component (A), aromatic polyester as component (B), graft copolymer as component (C), and
(D) A method of mixing the phosphoric acid ester and metal salt of component at once, a method of mixing three components in advance and then mixing the remaining one component, a method of mixing two components in advance and then mixing the remaining two components in one step. It can be produced by a method of mixing at the same time or separately. The heat-resistant resin composition of the present invention can be molded using equipment and conditions used for ordinary resin molding. Furthermore, various additives (for example, a mold release agent, an inorganic filler, glass fiber, etc.) may be added to the composition of the present invention. Since the heat-resistant thermoplastic resin composition of the present invention contains a butadiene-based graft copolymer with a specific graft component, it retains the excellent properties of, for example, an aromatic polycarbonate-aromatic polyester composition and has high durability. Has excellent impact resistance and heat discoloration resistance. Hereinafter, the present invention will be explained in detail with reference to Examples. Examples 1 to 5 and Comparative Example 1 Panlite L- as aromatic polycarbonate
1250 (trade name Teijin Kasei KK) 55% by weight, polyethylene terephthalate (reduced specific viscosity 0.68) as an aromatic polyester 32.9-33% by weight, copolymer with methyl methacrylate, butadiene, and styrene as a rubbery graft copolymer ( MBS resin)
12% by weight and as a heat stabilizer phosphate ester/metal salt
【式】及び[Formula] and
【式】の混合物（混合
比１：１）〔商品名：Phosle×Ａ−18（LBT−
1812）のMg塩、堺化学製〕を第１表に示す割合
で混合し、押出機により造粒し、次いで射出成形
機により成形し、その際の成形熱安定性を観察す
ると同時に得られた試験片について諸特性を測定
した。それらの結果を第１表に示した。
なお、成形熱安定性については射出成形機にて
シリンダー温度240℃、20分間の滞留試験を行
い、成形再開後の１シヨツト目から３シヨツト目
迄の成形片を観察し、その変色度合により判定し
た。
240℃の連続シヨツトで射出成形したものの成
形片について乾熱試験（130℃、72時間）を行
い、成形片の変色度合をカラーマシン社製色差計
で測定した。
滞留変色の判定基準；
◎〜〇印：全く変化がないか、又は殆んど変化
なし、
△印：やゝ変化、
×印：著しく変化、
乾熱変色の判定基準；
◎印：ｂ値の変化幅（△ｂ値）が７未満であ
る。
〇印：△ｂ値が７〜10未満である
△印：△ｂ値が10〜15未満である
×印：△ｂ値が15以上であるMixture of [formula] (mixing ratio 1:1) [Product name: Phosle×A-18 (LBT-
1812) manufactured by Sakai Chemical Co., Ltd.] were mixed in the proportions shown in Table 1, granulated using an extruder, and then molded using an injection molding machine. At the same time, the thermal stability of the molding was observed. Various properties were measured on the test piece. The results are shown in Table 1. In addition, regarding molding thermal stability, a retention test is conducted in an injection molding machine at a cylinder temperature of 240℃ for 20 minutes, and the molded pieces are observed from the 1st shot to the 3rd shot after restarting molding, and judged by the degree of discoloration. did. A dry heat test (130°C, 72 hours) was conducted on a molded piece that was injection molded using a continuous shot at 240°C, and the degree of discoloration of the molded piece was measured using a color difference meter manufactured by Color Machine Co., Ltd. Judgment criteria for retention discoloration: ◎～〇 marks: No change or almost no change, △ mark: Slight change, × mark: Significant change Judgment criteria for dry heat discoloration; ◎ mark: b value The variation width (Δb value) is less than 7. ○ mark: △b value is 7 to less than 10 △ mark: △b value is 10 to less than 15 × mark: △b value is 15 or more
【表】
実施例 ６〜11
リン酸エステル・金属塩として
[Table] Examples 6 to 11 Phosphate ester/metal salt
【式】及び[Formula] and
【式】の混合物の代り
に、第２表に示す種類及び量のものを用いる以外
は、実施例３又は４と全く同様に行つた。その結
果を第２表に示した。The same procedure as in Example 3 or 4 was carried out, except that instead of the mixture represented by the formula, the types and amounts shown in Table 2 were used. The results are shown in Table 2.
Claims (1)
芳香族ポリエステル０〜91重量％、及び(C)ブタジ
エン系重合体に、メタクリル酸エステル、芳香族
モノビニル化合物及びシアン化ビニル化合物より
なる群から選ばれるビニル系単量体の１種以上を
グラフト共重合せしめたブタジエン系グラフト共
重合体５〜50重量％より成る樹脂組成物100重量
部当り、0.01〜10重量部の(D)一般式 及び 〔但し、式中のＭはアルカリ土類金属、アルミニ
ウム又は亜鉛であり、Ｒは炭素数５〜30のアルキ
ル基であり、またｎはＭの原子価を表わす整数で
ある。〕 で示されるリン酸エステル・金属塩の少くとも１
種を含有せしめてなる耐熱性の優れた熱可塑性樹
脂組成物。 ２ 前記(D)成分が一般式(1)及び(2)で示されるリン
酸エステル・金属塩の混合物であることを特徴と
する特許請求の範囲第１項記載の熱可塑性樹脂組
成物。[Claims] 1 (A) 4 to 95% by weight of aromatic polycarbonate, (B)
One or more vinyl monomers selected from the group consisting of methacrylic acid esters, aromatic monovinyl compounds, and vinyl cyanide compounds are grafted onto 0 to 91% by weight of aromatic polyester and (C) a butadiene polymer. 0.01 to 10 parts by weight of general formula (D) per 100 parts by weight of a resin composition consisting of 5 to 50% by weight of a polymerized butadiene-based graft copolymer. as well as [However, in the formula, M is an alkaline earth metal, aluminum or zinc, R is an alkyl group having 5 to 30 carbon atoms, and n is an integer representing the valence of M. ] At least one of the phosphoric acid ester/metal salts represented by
A thermoplastic resin composition containing seeds and having excellent heat resistance. 2. The thermoplastic resin composition according to claim 1, wherein the component (D) is a mixture of phosphoric acid esters and metal salts represented by general formulas (1) and (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10657777A JPS5440854A (en) | 1977-09-07 | 1977-09-07 | Heat-resistant thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10657777A JPS5440854A (en) | 1977-09-07 | 1977-09-07 | Heat-resistant thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5440854A JPS5440854A (en) | 1979-03-31 |
| JPS6131144B2 true JPS6131144B2 (en) | 1986-07-18 |
Family
ID=14437073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10657777A Granted JPS5440854A (en) | 1977-09-07 | 1977-09-07 | Heat-resistant thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5440854A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5865743A (en) * | 1981-10-14 | 1983-04-19 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
| JPS58183729A (en) * | 1982-04-20 | 1983-10-27 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
| EP0105388A1 (en) * | 1982-09-28 | 1984-04-18 | General Electric Company | Modified thermoplastic polyester molding compositions and articles molded therefrom |
| JPS63168462A (en) * | 1986-12-29 | 1988-07-12 | Sakai Chem Ind Co Ltd | Resin composition |
| JP5103720B2 (en) * | 2005-09-12 | 2012-12-19 | 三菱化学株式会社 | Resin composition |
| KR101274513B1 (en) * | 2005-09-12 | 2013-06-13 | 미쓰비시 엔지니어링-플라스틱스 코포레이션 | Resin compositions and resin moldings |
| JP5040224B2 (en) * | 2005-09-14 | 2012-10-03 | 三菱エンジニアリングプラスチックス株式会社 | Resin composition and resin molded body |
| JP4601536B2 (en) * | 2005-10-20 | 2010-12-22 | 三菱エンジニアリングプラスチックス株式会社 | Light guide plate |
| JP2007291182A (en) * | 2006-04-21 | 2007-11-08 | Mitsubishi Chemicals Corp | Thermoplastic resin composition |
| JP2009001621A (en) * | 2007-06-19 | 2009-01-08 | Mitsubishi Chemicals Corp | Thermoplastic resin composition and resin molded product |
| JP5490402B2 (en) * | 2008-12-24 | 2014-05-14 | テクノポリマー株式会社 | Aromatic vinyl-based graft copolymer for resin blend and thermoplastic resin composition using the same |
| JP2012001609A (en) * | 2010-06-16 | 2012-01-05 | Takemoto Oil & Fat Co Ltd | Polycarbonate resin composition, method for producing polycarbonate resin molded product, and polycarbonate resin molded product |
-
1977
- 1977-09-07 JP JP10657777A patent/JPS5440854A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5440854A (en) | 1979-03-31 |
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