JPS636108B2 - - Google Patents
Info
- Publication number
- JPS636108B2 JPS636108B2 JP10866681A JP10866681A JPS636108B2 JP S636108 B2 JPS636108 B2 JP S636108B2 JP 10866681 A JP10866681 A JP 10866681A JP 10866681 A JP10866681 A JP 10866681A JP S636108 B2 JPS636108 B2 JP S636108B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- weight
- resin
- resin composition
- parts
- 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
- 229920005668 polycarbonate resin Polymers 0.000 claims description 25
- 239000004431 polycarbonate resin Substances 0.000 claims description 25
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 239000011342 resin composition Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229920005992 thermoplastic resin Polymers 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229920003244 diene elastomer Polymers 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- 150000008360 acrylonitriles Chemical class 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 claims 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 claims 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 claims 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 21
- 239000000203 mixture Substances 0.000 description 18
- -1 aliphatic dicarboxylic acids Chemical class 0.000 description 11
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- BZDKYAZTCWRUDZ-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC=C.C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 BZDKYAZTCWRUDZ-UHFFFAOYSA-N 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002170 ethers Chemical class 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
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- WUMVEFJJSIUCJJ-UHFFFAOYSA-N hexyl(trimethyl)silane Chemical compound CCCCCC[Si](C)(C)C WUMVEFJJSIUCJJ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は滞留熱安定性及び低温耐衝撃性に優れ
る熱可塑性樹脂組成物に関する。
特に薄肉部の低温耐衝撃性に優れる熱可塑性樹
脂組成物に関する。
従来からABS系樹脂とポリカーボネート樹脂
との混合物は優れた機械的性質と成形加工性を有
する樹脂組成物として広く知られている。例えば
ABS樹脂とポリカーボネート樹脂との組成物
（特公昭38−15225号及び51−11142号）、MBS樹
脂とポリカーボネート樹脂との組成物（特公昭39
−71号）およびABSM樹脂とポリカーボネート
樹脂との組成物（特公昭42−11496号）が挙げら
る。
然しながら、これらの組成物は成形時シリンダ
ー内に滞留すると非常に短時間で分解を始め良好
な成形品が得られない、さらに短時間の滞留にて
衝撃強度が著しく低下するという滞留熱安定性不
良問題を有している。これらの組成物の滞留熱安
定性は、ABS系樹脂或いはポリカーボネート樹
脂単体に比べはるかに劣るものである。
また、ポリカーボネート樹脂にABS系樹脂を
配合することにより耐衝撃性は改善されるが、低
温下における耐衝撃性、特に成形品の薄肉部にお
ける耐衝撃性が低く実用上大きな問題であつた。
本発明者等は、このようなABS系樹脂とポリ
カーボネート樹脂との組成物の滞留熱安定性及び
低温耐衝撃性について鋭意研究した結果、本発明
に到達したものである。
即ち、本発明は、共役ジエン系ゴムの存在下、
芳香族ビニル化合物、シアン化ビニル化合物およ
びカルボン酸アルキルエステルから選ばれた２種
以上の単量体を重合してなる重合体（以下ABS
系樹脂と記す。）10〜90重量％とポリカーボネー
ト樹脂90〜10重量％よりなる樹脂組成物(A)100重
量部に対して無機酸、有機酸および有機酸無水物
から選択された一種以上の酸化合物(B)0.05〜５重
量部及び有機ケイ素化合物(C)0.05〜５重量部を含
有してなることを特徴とする滞留熱安定性及び低
温耐衝撃性、特に薄肉部の低温耐衝撃性に優れる
熱可塑性樹脂組成物を提供するものである。
次に本発明の熱可塑性樹脂組成物についてさら
に詳しく説明する。
本発明で用いられるABS系樹脂を構成する共
役ジエン系ゴムとしては、ポリブタジエン、ブタ
ジエン−スチレン共重合体、ブタジエン−アクリ
ロニトリル共重合体等々を挙げることができる。
芳香族ビニル化合物としては、スチレン、α−メ
チルスチレン、ジメチルスチレン、ビニルトルエ
ン等々を挙げることができる。シアン化ビニル化
合物としては、アクリロニトリル、メタクリロニ
トリル等々を挙げることができる。さらに、カル
ボン酸アルキルエステルとしては、メチルアクリ
レート、エチルアクリレート、ブチルアクリレー
ト、メチルメタクリレート、エチルメタクリレー
ト、ブチルメタクリレート、ヒドロキシエチルア
クリレート、ヒドロキシエチルメタクリレート、
ヒドロキシプロピルメタクリレート等々を挙げる
ことができる。
共役ジエン系ゴムの存在下、かかる化合物から
選ばれた２種以上の単量体を重合してなるABS
系樹脂は公知の重合方法、例えば乳化重合法、懸
濁重合法、溶液重合法、塊状重合法により得られ
る。
次にポリカーボネート樹脂としては、芳香族ポ
リカーボネート、脂肪族ポリカーボネート、脂肪
族−芳香族ポリカーボネート等々を挙げることが
できる。一般には、２・２−ビス（４−オキシフ
エニル）アルカン系、ビス（４−オキシフエニ
ル）エーテル系、ビス（４−オキシフエニル）ス
ルホン、スルフイド又はスルホキサイド系などの
ビスフエノール類からなる重合体、もしくは共重
合体であり、目的に応じてハロゲンで置換された
ビスフエノール類を用いた重合体である。
ポリカーボネート樹脂の種類、製造法等につい
ては日刊工業発行（昭和44年９月30日発行）の
“ポリカーボネート樹脂”に詳しく記載されてい
る。
本発明におけるABS系樹脂とポリカーボネー
ト樹脂との重量比は、ABS系樹脂10〜90重量％、
ポリカーボネート樹脂90〜10重量％である。
ABS系樹脂が10重量％未満の場合（ポリカー
ボネート樹脂が90重量％を越える）は、機械的性
質、特にABS系樹脂とポリカーボネート樹脂と
の組成物における特徴である常温での衝撃強度向
上の相剰効果が期待できない。またABS系樹脂
が90重量％を越える場合（ポリカーボネート樹脂
が10重量％未満）は、熱的性質、特に耐熱性が著
しく劣り好ましくない。
本発明における無機酸としては、塩酸、硫酸、
硝酸、亜リン酸、リン酸、炭酸等を挙げる事がで
きる。特に硫酸、亜リン酸、リン酸が操作上好ま
しい。有機酸としては、一般にＲ−COOHで表
わされるカルボン酸、Ｒ−SO3Hで表わされるス
ルホン酸、スルフイン酸、フエノール等を挙げる
事ができる。
特に酢酸、高級脂肪酸等のモノカルボン酸、マ
レイン酸、フマール酸等の脂肪族ジカルボン酸、
フタル酸等の芳香族ジカルボン酸等のカルボン酸
が操作上好ましい。更に有機酸無水物としては、
無水マレイン酸、無水フタル酸等のジカルボン酸
無水物が操作上特に好ましい。
これらの無機酸、有機酸および有機酸無水物か
ら選択された一種以上の酸化合物が用いられる。
酸化合物(B)は、ABS系樹脂とポリカーボネー
ト樹脂との組成物100重量部当り0.05〜〜５重量
部必要である。0.05重量部未満の場合は、組成物
に対する分散が悪くなり、滞留熱安定性の改善効
果が期待できない。また５重量部を越える場合
は、組成物の耐熱性が低下し好ましくない。
有機ケイ素化合物(C)としては、一般式
で示されるポリシロキサン（R1〜R4は低級アル
キル、アリル基を示す）、R1R2R3R4Siで示される
シラン化合物（R1〜R4は低級アルキル、アリル
基）あるいはR4−nSiXn（ｎ＝１〜３）で示され
るオルガノハロシラン類（Ｒは低級アルキル、ア
リル基、Ｘはハロゲン）でもよい。具体的にはポ
リジメチルシロキサン、ポリメチルエチルシロキ
サン、ポリジエチルシロキサン、ポリメチルフエ
ニルシロキサン等のポリシロキサン類、テトラエ
チルシラン、トリメチルヘキシルシラン等のシラ
ン類あるいはトリエチルクロルシラン、ジエチル
ジクロルシラン、フエニルトリクロルシラン、ジ
フエニルジクロルシラン等のハロシラン類があ
る。
又、粘度は上式のｎにより異なるが、101〜
105cpsであることが樹脂との混合作業上好まし
い。
有機ケイ素化合物(C)は、ABS系樹脂とポリカ
ーボネート樹脂との組成物100重量部当り0.05〜
５重量部必要である。0.05重量部未満の場合は、
組成物に対する分散が悪くなり低温耐衝撃性の改
善効果が期待できない。また５重量部を越える場
合は、耐熱性が低下し好ましくない。
ABS系樹脂、ポリカーボネート樹脂、酸化合
物および有機ケイ素化合物の混合は、公知の混合
機で行うことができる。また混合方法としては、
ABS系樹脂とポリカーボネート樹脂を予め混合
した後に酸化合物および有機ケイ素化合物を添
加、混合する方法、ABS系樹脂（あるいはポリ
カーボネート樹脂）と酸化合物および／または有
機ケイ素化合物を予め混合した後にポリカーボネ
ート樹脂（あるいはABS系樹脂）と有機ケイ素
化合物または酸化合物を添加、混合する方法、上
記４成分すべてを一括混合する方法等が挙げられ
る。
なお、熱可塑性樹脂組成物に通常用いられる安
定剤、滑剤、充填剤等を添加してもよい。
以下に実施例をあげて説明するが、本発明はこ
れらによつて何ら制限されるものではない。
実施例および比較例
〔ABS系樹脂〕
以下の処方に基づき、アクリロニトリル−ブタ
ジエン−スチレン樹脂（ABS−１）、メチルメタ
クリレート−ブタジエン−スチレン樹脂（MBS）
及びアクリロニトリル−ブタジエン−スチレン−
メチルメタクリレート樹脂（ABSM）を作成し
た。
The present invention relates to a thermoplastic resin composition having excellent residence thermal stability and low-temperature impact resistance. In particular, the present invention relates to a thermoplastic resin composition that has excellent low-temperature impact resistance in thin-walled parts. BACKGROUND ART A mixture of ABS resin and polycarbonate resin has been widely known as a resin composition having excellent mechanical properties and moldability. for example
Compositions of ABS resin and polycarbonate resin (Japanese Patent Publication No. 38-15225 and No. 51-11142), compositions of MBS resin and polycarbonate resin (Japanese Patent Publication No. 39-1973)
-71) and a composition of ABSM resin and polycarbonate resin (Japanese Patent Publication No. 11496/1983). However, when these compositions remain in the cylinder during molding, they begin to decompose in a very short period of time, making it impossible to obtain a good molded product.Furthermore, they suffer from poor thermal stability due to short stays in which the impact strength significantly decreases. I have a problem. The retention thermal stability of these compositions is far inferior to that of ABS resin or polycarbonate resin alone. Although impact resistance is improved by blending ABS resin with polycarbonate resin, the impact resistance at low temperatures, especially in the thin parts of molded products, is low, which is a major problem in practice. The present inventors have arrived at the present invention as a result of extensive research into the residence thermal stability and low-temperature impact resistance of such compositions of ABS resin and polycarbonate resin. That is, the present invention provides, in the presence of a conjugated diene rubber,
A polymer formed by polymerizing two or more monomers selected from aromatic vinyl compounds, vinyl cyanide compounds, and carboxylic acid alkyl esters (hereinafter referred to as ABS)
This is referred to as a type resin. ) One or more acid compounds selected from inorganic acids, organic acids, and organic acid anhydrides (B) based on 100 parts by weight of a resin composition (A) consisting of 10 to 90% by weight and 90 to 10% by weight of a polycarbonate resin. A thermoplastic resin which is characterized by containing 0.05 to 5 parts by weight and 0.05 to 5 parts by weight of an organosilicon compound (C), and which has excellent retention thermal stability and low-temperature impact resistance, particularly low-temperature impact resistance in thin-walled parts. A composition is provided. Next, the thermoplastic resin composition of the present invention will be explained in more detail. Examples of the conjugated diene rubber constituting the ABS resin used in the present invention include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and the like.
Examples of aromatic vinyl compounds include styrene, α-methylstyrene, dimethylstyrene, vinyltoluene, and the like. Examples of vinyl cyanide compounds include acrylonitrile, methacrylonitrile, and the like. Furthermore, carboxylic acid alkyl esters include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate,
Hydroxypropyl methacrylate and the like can be mentioned. ABS made by polymerizing two or more monomers selected from such compounds in the presence of a conjugated diene rubber
The system resin can be obtained by a known polymerization method, such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a bulk polymerization method. Next, examples of the polycarbonate resin include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like. Generally, polymers or copolymers consisting of bisphenols such as 2,2-bis(4-oxyphenyl) alkanes, bis(4-oxyphenyl) ethers, bis(4-oxyphenyl)sulfones, sulfides, or sulfoxides are used. It is a polymer using bisphenols substituted with halogen depending on the purpose. The types of polycarbonate resins, manufacturing methods, etc. are described in detail in "Polycarbonate Resins" published by Nikkan Kogyo (September 30, 1962). The weight ratio of ABS resin and polycarbonate resin in the present invention is 10 to 90% by weight of ABS resin,
Polycarbonate resin is 90-10% by weight. When ABS resin is less than 10% by weight (polycarbonate resin is more than 90% by weight), mechanical properties, especially the mutual improvement in impact strength at room temperature, which is a characteristic of compositions of ABS resin and polycarbonate resin, are The effect cannot be expected. Furthermore, when the ABS resin content exceeds 90% by weight (the polycarbonate resin content is less than 10% by weight), the thermal properties, particularly the heat resistance, are significantly inferior, which is not preferable. Examples of inorganic acids in the present invention include hydrochloric acid, sulfuric acid,
Nitric acid, phosphorous acid, phosphoric acid, carbonic acid, etc. can be mentioned. In particular, sulfuric acid, phosphorous acid, and phosphoric acid are preferred for operational reasons. Examples of the organic acid include carboxylic acid generally represented by R-COOH, sulfonic acid represented by R-SO 3 H, sulfinic acid, and phenol. In particular, monocarboxylic acids such as acetic acid and higher fatty acids, aliphatic dicarboxylic acids such as maleic acid and fumaric acid,
Carboxylic acids such as aromatic dicarboxylic acids such as phthalic acid are operationally preferred. Furthermore, as organic acid anhydrides,
Dicarboxylic acid anhydrides such as maleic anhydride and phthalic anhydride are particularly preferred for operational reasons. One or more acid compounds selected from these inorganic acids, organic acids, and organic acid anhydrides are used. The acid compound (B) is required in an amount of 0.05 to 5 parts by weight per 100 parts by weight of the composition of ABS resin and polycarbonate resin. If the amount is less than 0.05 part by weight, the dispersion in the composition will be poor and no improvement in retention heat stability can be expected. Moreover, if it exceeds 5 parts by weight, the heat resistance of the composition decreases, which is not preferable. As the organosilicon compound (C), the general formula Polysiloxane represented by (R 1 to R 4 are lower alkyl or allyl groups), silane compound represented by R 1 R 2 R 3 R 4 Si (R 1 to R 4 are lower alkyl or allyl groups), or R Organohalosilanes represented by 4 -nSiXn (n=1 to 3) (R is lower alkyl or allyl group, and X is halogen) may also be used. Specifically, polysiloxanes such as polydimethylsiloxane, polymethylethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane, silanes such as tetraethylsilane and trimethylhexylsilane, or triethylchlorosilane, diethyldichlorosilane, and phenyl. There are halosilanes such as trichlorosilane and diphenyldichlorosilane. Also, the viscosity varies depending on n in the above formula, but from 10 1 to
10 5 cps is preferable for mixing with resin. The organosilicon compound (C) is 0.05 to 100 parts by weight of the composition of ABS resin and polycarbonate resin.
5 parts by weight are required. If it is less than 0.05 parts by weight,
Dispersion in the composition becomes poor, and no improvement in low-temperature impact resistance can be expected. Moreover, if it exceeds 5 parts by weight, heat resistance decreases, which is not preferable. The ABS resin, polycarbonate resin, acid compound, and organosilicon compound can be mixed using a known mixer. Also, as a mixing method,
A method of adding and mixing an acid compound and an organosilicon compound after premixing an ABS resin and a polycarbonate resin, or a method of premixing an acid compound and/or an organosilicon compound with an ABS resin (or polycarbonate resin) and then adding a polycarbonate resin (or Examples include a method of adding and mixing ABS-based resin) and an organosilicon compound or an acid compound, and a method of mixing all of the above four components at once. Note that stabilizers, lubricants, fillers, etc. commonly used in thermoplastic resin compositions may be added. Examples will be described below, but the present invention is not limited thereto. Examples and Comparative Examples [ABS resin] Based on the following formulations, acrylonitrile-butadiene-styrene resin (ABS-1), methyl methacrylate-butadiene-styrene resin (MBS)
and acrylonitrile-butadiene-styrene-
Methyl methacrylate resin (ABSM) was created.
市販のポリカーボネート樹脂：パンライトＬ−
1250W（帝人化成社製）
構造式
〔無機酸、有機酸および有機酸無水物〕
硫酸、リン酸、亜リン酸、酢酸、マレイン酸、
フタル酸、無水マレイン酸、無水フタル酸
〔有機ケイ素化物〕
ポリジメチルシロキサン、ポリメチルフエニル
シロキサン
第１表に示される重量比に基づき、各成分を通
常の混合機を用いて混合した。さらにサーモプラ
スチツク社製40mm押出機にてペレツト化した。
高化式フローテスターにて得られた組成物の滞
留熱安定性（発泡分解）を評価、また組成物を射
出成形機のシリンダー内に５分間、260℃で滞留
させた後試験片を成形し、滞留熱安定性（衝撃強
度）を評価した。
得られた組成物（ペレツト）よりさらに日精樹
脂製TS−150射出成形機を用いて260℃で試験片
を成形し、常温ならびに低温における耐衝撃性及
び耐熱性を評価した。
評価結果を第２表に示す。
Commercially available polycarbonate resin: Panlite L-
1250W (manufactured by Teijin Chemicals) Structural formula [Inorganic acids, organic acids and organic acid anhydrides] Sulfuric acid, phosphoric acid, phosphorous acid, acetic acid, maleic acid,
Phthalic acid, maleic anhydride, phthalic anhydride [organosiliconized product] Polydimethylsiloxane, polymethylphenylsiloxane Each component was mixed using a conventional mixer based on the weight ratio shown in Table 1. Furthermore, it was pelletized using a 40 mm extruder manufactured by Thermoplastics. The retention thermal stability (foaming decomposition) of the obtained composition was evaluated using a Koka type flow tester, and the composition was retained at 260°C for 5 minutes in the cylinder of an injection molding machine, and then a test piece was molded. , retention thermal stability (impact strength) was evaluated. The obtained composition (pellet) was further molded into test pieces at 260°C using a TS-150 injection molding machine manufactured by Nissei Plastics Co., Ltd., and the impact resistance and heat resistance at room temperature and low temperature were evaluated. The evaluation results are shown in Table 2.
【表】【table】
【表】【table】
Claims (1)
合物、シアン化ビニル化合物およびカルボン酸ア
ルキルエステルから選ばれた２種以上の単量体を
重合してなる重合体10〜90重量％とポリカーボネ
ート樹脂90〜10重量％よりなる樹脂組成物(A)100
重量部に対して無機酸、有機酸および有機酸無水
物から選択された一種以上の酸化合物(B)0.05〜５
重量部及び有機ケイ素化合物(C)0.05〜５重量部を
含有してなることを特徴とする熱可塑性樹脂組成
物。 ２ 無機酸が硫酸、亜リン酸またはリン酸である
特許請求の範囲第１項記載の熱可塑性樹脂組成
物。 ３ 有機酸がカルボン酸である特許請求の範囲第
１項または第２項記載の熱可塑性樹脂組成物。 ４ 有機酸無水物がジカルボン酸無水物である特
許請求の範囲第１項、第２項または第３項記載の
熱可塑性樹脂組成物。[Claims] 1. Polymers 10 to 90 obtained by polymerizing two or more monomers selected from aromatic vinyl compounds, vinyl cyanide compounds, and carboxylic acid alkyl esters in the presence of a conjugated diene rubber. Resin composition (A) 100 consisting of % by weight and 90 to 10% by weight of polycarbonate resin
One or more acid compounds selected from inorganic acids, organic acids and organic acid anhydrides (B) 0.05 to 5 parts by weight
1. A thermoplastic resin composition comprising 0.05 to 5 parts by weight of an organosilicon compound (C). 2. The thermoplastic resin composition according to claim 1, wherein the inorganic acid is sulfuric acid, phosphorous acid, or phosphoric acid. 3. The thermoplastic resin composition according to claim 1 or 2, wherein the organic acid is a carboxylic acid. 4. The thermoplastic resin composition according to claim 1, 2 or 3, wherein the organic acid anhydride is a dicarboxylic acid anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10866681A JPS5811540A (en) | 1981-07-10 | 1981-07-10 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10866681A JPS5811540A (en) | 1981-07-10 | 1981-07-10 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5811540A JPS5811540A (en) | 1983-01-22 |
| JPS636108B2 true JPS636108B2 (en) | 1988-02-08 |
Family
ID=14490593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10866681A Granted JPS5811540A (en) | 1981-07-10 | 1981-07-10 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5811540A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190126200A (en) | 2010-07-22 | 2019-11-08 | 우베 고산 가부시키가이샤 | Polyimide precursor, polyimide, and materials to be used in producing same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8552096B2 (en) | 2009-07-31 | 2013-10-08 | Sabic Innovative Plastics Ip B.V. | Flame-retardant reinforced polycarbonate compositions |
| JP6723783B2 (en) * | 2016-03-28 | 2020-07-15 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition and molded article |
| KR102360594B1 (en) | 2018-09-21 | 2022-02-09 | 주식회사 엘지화학 | Thermoplastic resin composition, method for producing the same and metal plated molding product therefrom |
| CN109825056B (en) * | 2019-01-21 | 2022-07-19 | 金发科技股份有限公司 | Polycarbonate alloy and preparation method thereof |
-
1981
- 1981-07-10 JP JP10866681A patent/JPS5811540A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190126200A (en) | 2010-07-22 | 2019-11-08 | 우베 고산 가부시키가이샤 | Polyimide precursor, polyimide, and materials to be used in producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5811540A (en) | 1983-01-22 |
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