JPS6142748B2 - - Google Patents
Info
- Publication number
- JPS6142748B2 JPS6142748B2 JP53111846A JP11184678A JPS6142748B2 JP S6142748 B2 JPS6142748 B2 JP S6142748B2 JP 53111846 A JP53111846 A JP 53111846A JP 11184678 A JP11184678 A JP 11184678A JP S6142748 B2 JPS6142748 B2 JP S6142748B2
- Authority
- JP
- Japan
- Prior art keywords
- composition according
- aromatic
- weight
- component
- polycarbonate
- 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
- 239000000203 mixture Substances 0.000 claims description 41
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 229920000515 polycarbonate Polymers 0.000 claims description 26
- 239000004417 polycarbonate Substances 0.000 claims description 26
- -1 vinyl compound Chemical class 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000004431 polycarbonate resin Substances 0.000 claims description 8
- 229920005668 polycarbonate resin Polymers 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 3
- 229920005992 thermoplastic resin Polymers 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims 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 claims description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims 1
- 229920005684 linear copolymer Polymers 0.000 claims 1
- 239000012763 reinforcing filler Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 20
- 229920001400 block copolymer Polymers 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 11
- 229920002633 Kraton (polymer) Polymers 0.000 description 9
- 238000005336 cracking Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000012744 reinforcing agent Substances 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 229920004142 LEXAN™ Polymers 0.000 description 5
- 239000004418 Lexan Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000006353 environmental stress Effects 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920013623 Solprene Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920006285 olefinic elastomer Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- GWWBILGABMLVTN-UHFFFAOYSA-N 1-but-1-enyl-2,3-dimethylbenzene Chemical group CCC=CC1=CC=CC(C)=C1C GWWBILGABMLVTN-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- DTOMAXGIWFLDMR-UHFFFAOYSA-N 4-[(4-hydroxy-3-nitrophenyl)methyl]-2-nitrophenol Chemical compound C1=C([N+]([O-])=O)C(O)=CC=C1CC1=CC=C(O)C([N+]([O-])=O)=C1 DTOMAXGIWFLDMR-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- PWGQHOJABIQOOS-UHFFFAOYSA-N copper;dioxido(dioxo)chromium Chemical compound [Cu+2].[O-][Cr]([O-])(=O)=O PWGQHOJABIQOOS-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004616 structural foam Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08L69/005—Polyester-carbonates
Description
本発明は新規な樹脂組成物に係わり、殊に芳香
族ポリカーボネート樹脂と、ビニル芳香族化合物
とオレフイン系エラストマーからなる選択的に水
素添加されたエラストマー性ブロツクコポリマー
単独、あるいは更に添加剤例えば補強剤、発泡
剤、顔料及び火炎遅延剤を組み合わせたものとか
らなる重合体組成物に係わる。
芳香族ポリカーボネート重合体はプラスチツク
工業界に種々の用途を有する周知の市販されてい
る材料である。かかるカーボネート重合体は、酸
結合剤の存在下にて２価フエノール例えば２，２
−ビス（４−ヒドロキシフエニル）プロパンをカ
ーボネート先駆体例えばホスゲンと反応させて調
製しうる。これについては、the Encyclopedia
of Polymer Science and Technology，Vol.10，
pp.710−764，Interscience，New York，1969を
見られたい。一般的に言つて、芳香族ポリカーボ
ネート樹脂は鉱酸による侵食に対して高い抵抗を
もたらし、生理学的に無害であると共に汚染抵抗
性がある。加えて、かかるポリカーボネート重合
体類から成形された物品は高い引張強度、厚い断
面を除いた部分での高衝撃強度、高い熱抵抗、及
び殆んどの他の熱可塑性物質に遥かに勝る寸法安
定性を有する。しかしながら、或る種の用途に於
いては、芳香族ポリカーボネート樹脂の用途には
次の理由によつて制限がある。(i)融解物としての
粘度が高く（複雑で大きなそして特に発泡した部
分の成形を困難にしている。(ii)厚い断面に於ける
急激な衝撃条件下、及び少量の補強剤例えばガラ
スや顔料例えば二酸化テタンを慣用の目的として
加えるときには厚さに無関係に脆性を示す。(iii)厳
しい環境応力下に於いてヒビや割れを示す。用語
“環境応力ヒビ割れ”は、有機溶媒例えばアセト
ン、ヘブタン及び四塩化炭素が存在しこれ等の溶
媒の芳香族ポリカーボネート樹脂から製造された
応力を受けている部品と接触しているときに促進
されるタイプの損傷を言う。かかる接触は、例え
ば、溶媒を使つて、ポリカーボネートから製造さ
れた応力を受けた部品を清浄にし又は脱脂した
り、あるいはかかる部品を自動車、特にほろの下
に使つたりしたときに起りうる。
比較的高い溶融粘度と軟化点と芳香族ポリカー
ボネートの溶融処理を難しくし、この為、溶融流
れを改善する為にいくつかの対応策が提案された
が、これ等には欠点があつた。可塑性を添加でき
るが、これにより他の重要な特性が損なわれ、部
品は脆くなつて熱により歪みに対する抵抗能力が
実質的に失われてしまう。他方、米国特許
3431224号に提案されているように、ポリエチレ
ンを少量添加できるが、これによつて環境応力ヒ
ビ割れに対する抵抗が著しく増大されはするもの
の、ポリエチレンが低濃度では溶融流れを高める
にはあまり効果があるとは言えず効果的な範囲に
まで増量すると層割れを起す成形物品を生ずる傾
向がある。
芳香族ポリカーボネートに水添ブロツクコポリ
マーを少量添加すると溶融粘度を低下させるが加
熱歪温度は実質的な影響を受けないことがここに
発見された。実際面でも、ブロツクコポリマーを
２，５，10及び20添加すると標準条件下の成形部
品の溶融流れ長さが著しく増大されるが末変性ポ
リカーボネートでは特に生産の難しい大きな発泡
部品が容易に製造される。結果は驚く程であり、
芳香族ポリカーボネート自体が高い粘度を有し剪
断速度に余り依存することがなく他方ブロツクコ
ポリマー自体も又溶解粘度が高いが剪断速度に非
常に依存しているが、これ第２者を混合後に於い
ては融解粘度はいずれの成分よりも非常に実質的
に低下する。既に述べたとおり、後記に定義され
るタイプの水添ブロツクコポリマーはこの用途に
特異な適性があるようであり、ポリエチレン４％
では芳香族ポリカーボネートの流れが300℃で13
℃程度改善されるのに対し、水添ブロツクコポリ
マーでは５％で45％程も流れが改善され、従つて
後者ではずつと少ない量でも有用である。
水添ブロツクコポリマーをポリカーボネートに
加えることの第２の主たる利点は、厚壁成形部品
に於ける衝撃抵抗の改善である。通常、薄壁では
完全に満足のいく樹脂から製造されたとしても芳
香族ポリカーボネートから形成された厚壁加工品
は脆い。例えば、0.32cm（1/8インチ）厚試験片
に対するアイゾツト衝撃値76Kg／cm（14ft.・lbs.
／in.）ノツチは厚さを0.64cm（1/4インチ）の倍
加するだけで14Kg／cm（2.5ft.・lbs.／in.）低下
する。上述の米国特許3431224に記載されている
如きポリオレフインはこうした状況を幾分改善す
るが、層割れの傾向の為にその使用は３％より上
に制限されており、いずれにしても、ポリエチレ
ンでは衝撃強度は約33Kg／cmノツチ（1/4インチ
断面）に高められるにすぎない。驚くべきこと
に、水添ブロツクコポリマーのほんの３重量％で
も1/4インチ厚試験片の衝撃強度14Kg／cmを約
11ft.lbs.／in.ノツチまで上昇せしめる効果があ
り、この値は薄壁の末変性ポリカーボネートの値
に近い。
ポリカーボネートに水添ブロツクコポリマーを
加える第三の主たる利点は環境抵抗の改善であ
る。即ち、成形部品はその望ましい特性の外のど
の特性にも認められる程の影響を及ぼすことな
く、割れが始まる前により大きな歪みにかけるこ
とができる。米国特許3431224ではポリオレフイ
ン類及びその他の樹脂がこの目的に有用である旨
開示しており、独国特許公告2329585は芳香族ポ
リカーボネートの或る種の特性を高めるのにゴム
質のランダム重合体及び共重合体を添加すること
を開示してはいるが、例えばガソリン及び四塩化
炭素の如き侵食性の溶媒中に浸漬する等の緊張下
での部品の応力割れにかかる時間をほどよく延長
させるのに水添ブロツクコポリマーが優れかつ独
特の適性を示すことがわかつた。ここに論じた刊
行物及び特許のすべてを参考までにここに掲げ
る。
本発明の新規な組成物は例えば繊維質のガラス
を使つて強化したり、芳香族ポリカーボネート樹
脂成分の全てあるいは一部としてハロゲン化芳香
族ポリカーボネートを使うか、及び／又は火炎遅
延剤添加剤を使つて耐炎性にしたり、あるいは既
知の方法によつて顔料着色したり及び／又は発泡
させたりして融解処理した製品でのその使用分野
を拡張することができる。
従来技術の組成物に比較して、本発明の新規な
組成物は一般に又高いコワサと強度を有し、優れ
た表面外観、及び熱による変退色に優れた抵抗を
示す。
本発明によれば、(a)芳香族ポリカーボネート樹
脂と、(b)重合されたビニル芳香族化合物(A)o及び
(A)１ ｏ並びにオレフイン系エラストマー(B)より成り
Ａo−Ｂ−Ａ１ ｏ、Ａo−（Ｂ−Ａ−Ｂ）o−Ａo、Ａo
（BA）oＢ、（Ａ）4B、Ｂ（Ａ）４又はＢ〔（AB））o
Ｂ〕タイプ（但し、ｎは１〜10の整数である）の
選択的に水素添加された線状、セクアンシヤル又
はラジアルテレブロツクコポリマーと、の緊密な
配合物から成る高衝撃強度熱可塑性樹脂組成物が
提供される。
好適な組成物では、成分(a)及び(b)の全重量に基
づいて、成分(a)が99.5〜50重量部そして成分(b)が
0.5〜50重量部をなす。殊に好ましい組成物に於
いては、成分(a)及び(b)の全重量に基づいて、成分
(a)が99.5〜90重量部そして成分(b)が0.5〜10重量
部をなす。
好ましい組成物に於いては、芳香族ポリカーボ
ネート成分(a)は、２価フエノールとカーボネート
先駆体例えばホスゲン、ハロホメート又は炭酸エ
ステルとの芳香族ポリカーボネートである。一般
的に言えば、かかるカーボネート重合体類は典型
的には式
の反復構造単位を有するものである。式中、Ａは
重合体生成反応で使われた２価フエノールの２価
芳香族基である。好ましくは、カーボネート重合
体はｐ−ジオキサン中30℃にてdl.／ｇ．単位で
測定して約0.35〜約0.75の固有粘度を有する。こ
うした芳香族ポリカーボネート重合体類をもたら
すのに使われる２価フエノールは単核及び多核芳
香族化合物で、該化合物中には官能基として２個
のヒドロキシル基が含まれ、そのそれぞれが芳香
族核の炭素原子に直接結合されている。２価フエ
ノールの例としては、２，２−ビス（４−ヒドロ
キシフエニル）プロパン（別名ビスフエノール−
Ａ）、レゾルシン、ビス−（４−ヒドロキシ−５−
ニトロフエニル）メタン、２，2′−ジヒドロキシ
−ジフエニル、２，６−ジヒドロキシナフタリ
ン、ビス−（４−ヒドロキシフエニルスルホン）、
5′−クロロ−２，4′−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、及び４，4′−ジヒドロキシ−２，５−ジエト
キシジフエニルエーテルがある。
かかるカーボネート重合体を提供するのに使用
できる種々のその外の２価フエノール類が米国特
許2999835に開示されている。ホモポリマーより
むしろカーボネートコポリマー、例えば、ビスフ
エノールＡとチトラブロモビスフエノールＡから
なる火炎遅延特性をもつたコポリマーが本発明の
組成物中に成分(a)として使うのに望まれている場
合には、２種又はそれ以上の異種の２価フエノー
ルを使つたり、あるいは、２価フエノールとグリ
コール、ヒドロキシ末端ポリエステル又は２塩基
酸との組合せを使うことも勿論既知である。
成分(b)については、水素添加ブロツクコポリマ
ーは当該技術界で既知の手段によつて製造され市
販されている。
水素添加前に於いては、これ等の共重合体類の
末端ブロツクは、好ましくはアルケニル芳香族炭
化水素そして殊にビニル芳香族炭化水素（ここ
に、芳香族成分は単環あるいは多環のいずれでも
よい）から調製されたホモポリマーがコポリマー
から成つている。典型的な単量体にはスチレン、
α−メチルスチレン、ビニルトルエン、ビニルキ
シレン、エチルビニルキシレン、及びビニルナフ
タレンが含まれ、特にスチレン又はその混合物が
よい。末端ブロツク（Ａ）o及び（A1）oは同じでも
異つていてもよい。中央ブロツク(B)は例えばブタ
ジエン、イソプレン、１，３−ペンタジエン及び
２，３−ジメチルブタジエンから誘導することが
でき、線状、セクアンシヤル（遂次）又はテレラ
ジアル（遠放射）型構造を持ちうる。
選択的に水添された線状ブロツクコポリマー類
が米国特許3333024に記載されている。
コポリマー類の比率及び平均分子量は広く変動
できるが、中央ブロツクの分子量は末端ブロツク
を合わせた分子量より大きいべきである。平均分
子量2000〜100000の末端ブロツクＡ及び平均分子
量25000〜1000000の中央ブロツクＢ例えば水添ポ
リブタジエンブロツクを形成するのが好ましい。
更に一層好ましくは、末端ブロツクの平均分子量
は8000〜60000であり水素添加ポリブタジエン重
合体ブロツクの平均分子量は50000〜300000であ
る。末端ブロツクは全ブロツクコポリマーの２〜
60重量％あるいはそれ以上、好ましくは15〜40重
量％をなすのが好ましい。好ましいコポリマーは
水添／飽和ポリブタジエン中央ブロツクを有し、
ブタジエン炭素原子の５〜55％又はそれ以上好ま
しくは30〜50％がビニル側鎖であるコポリマーか
ら形成されるものである。
水添コポリマーの平均不飽和度は初期値の20％
未満にまで減少される。中央ブロツクＢの不飽和
度が当初の値の10％又はそれ以下、好ましくは５
％にまで減少されているのが好ましい。
ブロツクコポリマー類は当業者に周知の技術に
よつて形成される。水素添加の実施には、種々の
水添触媒例えばニツケル、ケイソウ土、ラニーニ
ツケル、クロム酸銅、酸化モリブデン、並びに低
表面積キヤリア上に担持した微分割白金又は他の
貴金属を使うことができる。
水素添加は任意所望の温度又は圧力にて、即
ち、大気圧〜300psig、通常100〜1000psigの範囲
にて、75〓〜600〓の温度で、0.1〜24時間好まし
くは0.2〜８時間行うことができる。
本発明によれば、水添ブロツクコポリマー例え
ばKratonG−6500、KratonG−6521、KratonG−
1650及びDratonG−1652（いずれもShell
Chemical Company，Polymers Division）が使
用できることがわかつた。KratonG−1650が好ま
しい。同じく使用できるものにはいわゆる
Phillipsの水添Solprene類があり、殊にSolprene
−512と称する製品がある。
Splprene類を代表的な例とするラジルアルテ
レブロツクコポリマーは少なくとも３つの重合体
分枝を有することを特徴とされ、このラジアルブ
ロツクポリマーの各分枝は上記定義の(A)及び
（A1）の如き末端非エラストマー性セグメントを
含んでいる。このラジアルブロツクポリマーの分
枝は末端非エラストマー性セグメントを含み、こ
れに上記定義のの如きエラストマー性重合体セ
グメントが結合されている。これ等のコポリマー
は米国特許3753936及び3281383に記載されており
既知の方法によつて選択的に水添されている。こ
こで使われる用語「選択的水素添加（水添、水素
化）」により意図される重合体は、エラストマー
(B)が水添されており、非エラストマーブロツク(A)
及び（A′）は水添されないままの芳香族であ
る。
上述したように、組成物中には他の添加剤が存
在でき、例えば顔料例えば二酸化チタン、火炎遅
延剤及び発泡剤例えば５−フエニルテトラゾール
が組成物中の全樹脂成分(a)及び(b)の約0.1〜100重
量部の量で存在しうる。
本発明の好ましい特徴に入る強化組成物には強
化量の強化剤が含まれており、この強化剤として
は例えば金属類例えばアルミニウム、青銅、鉄又
はニツケルの粉末、ウイスカー、繊維又は小板並
びに非金属例えば炭素フイラメント、針状
CaSiO3、アスベスト、TiO2、チタン酸塩ウイス
カー及びガラスフレークがある。かかる強化剤は
例えば２〜60重量％、好ましくは５〜40重量％の
量で存在する。特に好ましい強化剤は繊維質のグ
ラスである。
重合体組成物を形成する方法は重要でない。任
意の従来技術の配合技術が一般に適する。
好ましい方法の重合体類と添加剤類例えば場合
に応じて粉末、粒状及びフイラメント形態の強化
剤を配合し、配合物を押し出し、そして通常固体
の熱可塑性樹脂組成物を成形するのに慣用されて
いる手段により成形するのに適したペレツトに切
断することによる。
芳香族ポリカーボネート樹脂と選択的に水添さ
れたエラストマー性ビニル芳香族−オレフインＡ
−Ｂ−A′ブロツクコポリマーとの組成物を提供
することによつて得られる利点が以下の実施中に
例示されており、これ等実施例は本発明を更に記
述するものとして開示されており本発明をこれ等
実施例に限定する意図はない。
諸成分を機械的に配合し、次いで125℃で４時
間予備乾燥し、それから300℃の二軸スクリユ
Werner Pfleiderer（WP）中で押し出すという
一般手順によつて以下の組成物を生成する。押出
後、この材料を125℃で４時間にわたり乾燥し、
次いで260〜320℃（シリンダー）及び20〜115℃
（型）の往復スクリユー射出成形機中で試験片に
成形する。発泡性組成物を製造する為、ペレツト
化した押出物を(一)及び(b)100部あたり0.25部の５
−フエニルテトラゾールと乾燥配合する。可塑化
酸／蓄電池を備えたSiemag装置内で発泡成形を
行う。あらゆる条件をポリカーボネート自体に対
する標準とする。ポリカーボネート成分の全ては
小量、例えば、0.1％の安定化剤組合せ、即ち、
慣用のホスフアイト／立体障害フエノールを含ん
でいる。以下の手順によつて物性試験を行う。
0.64cm及び0.32cm試験片に対するノツチ付きアイ
ゾツト衝撃強度、0.32cm円板試験片に対する落槍
衝撃試験、引張強度及びモジユラス、抗折強度及
びモジユラス、加熱歪温度、1500／秒及び300℃
での見掛溶融粘度、そして発泡体の場合に於ける
ガードナー衝撃及びシヤルピー衝撃値。調製した
組成物及び成形物品に対する物理的特性は次のと
おりである。
実施例 １
組成物を調製し、成形しそして比較した。
The present invention relates to a novel resin composition, in particular a selectively hydrogenated elastomeric block copolymer consisting of an aromatic polycarbonate resin, a vinyl aromatic compound and an olefinic elastomer alone, or in addition to additives such as reinforcing agents. The present invention relates to a polymeric composition comprising a blowing agent, a pigment, and a combination of a flame retardant. Aromatic polycarbonate polymers are well known commercially available materials that have a variety of uses in the plastics industry. Such carbonate polymers contain dihydric phenols such as 2,2 in the presence of an acid binder.
-Bis(4-hydroxyphenyl)propane may be prepared by reacting with a carbonate precursor such as phosgene. For more information, see the Encyclopedia
of Polymer Science and Technology, Vol.10,
See pp. 710-764, Interscience, New York, 1969. Generally speaking, aromatic polycarbonate resins provide high resistance to attack by mineral acids, are physiologically harmless and stain resistant. In addition, articles molded from such polycarbonate polymers exhibit high tensile strength, high impact strength except for thick sections, high thermal resistance, and dimensional stability far superior to most other thermoplastics. has. However, in certain applications, the use of aromatic polycarbonate resins is limited due to the following reasons. (i) high viscosity as a melt (making it difficult to mold complex, large and especially foamed parts; (ii) under conditions of sharp impact in thick sections and with small amounts of reinforcing agents such as glass or pigments). For example, when tethane dioxide is added for conventional purposes, it exhibits brittleness regardless of thickness. (iii) It exhibits cracking and cracking under severe environmental stress. refers to the type of damage that is promoted when carbon tetrachloride is present and in contact with stressed parts made from aromatic polycarbonate resins of these solvents. Such contact may e.g. This can occur when polycarbonate is used to clean or degrease stressed parts made from polycarbonate, or when such parts are used in automobiles, especially under hollows.The relatively high melt viscosity and softening point This makes the melt processing of aromatic polycarbonates difficult, and several countermeasures have been proposed to improve melt flow, but these have drawbacks. Critical properties are compromised, and the part becomes brittle and loses its ability to effectively resist thermal distortion.On the other hand, U.S. Pat.
Small amounts of polyethylene can be added, as proposed in No. 3431224, but although this significantly increases resistance to environmental stress cracking, low concentrations of polyethylene are less effective in enhancing melt flow. However, increasing the amount beyond the effective range tends to result in molded articles that exhibit delamination. It has now been discovered that the addition of small amounts of hydrogenated block copolymers to aromatic polycarbonates reduces the melt viscosity, but has no substantial effect on the heat strain temperature. In practice, additions of 2, 5, 10 and 20 block copolymers significantly increase the melt flow length of molded parts under standard conditions, but facilitate the production of large foamed parts, which are particularly difficult to produce with terminally modified polycarbonates. . The results are surprising;
The aromatic polycarbonate itself has a high viscosity and is not very dependent on the shear rate, while the block copolymer itself also has a high melt viscosity but is very dependent on the shear rate; has a very substantially lower melt viscosity than either component. As already mentioned, hydrogenated block copolymers of the type defined below appear to be uniquely suited for this application, and polyethylene 4%
In this case, the flow of aromatic polycarbonate is 13 at 300℃.
℃, while the hydrogenated block copolymer improves the flow by as much as 45% at 5%, so even smaller amounts of the latter are useful. The second major benefit of adding hydrogenated block copolymers to polycarbonate is improved impact resistance in thick wall molded parts. Typically, thick wall fabrications made from aromatic polycarbonates are brittle even if made from resins that are perfectly acceptable for thin walls. For example, the Izotsu impact value for a 0.32 cm (1/8 inch) thick test piece is 76 Kg/cm (14 ft.・lbs.
/in.) The notch will be reduced by 14 kg/cm (2.5 ft.・lbs./in.) by doubling the thickness by 0.64 cm (1/4 inch). Polyolefins, such as those described in the above-mentioned U.S. Pat. The strength is only increased to about 33 kg/cm notch (1/4 inch cross section). Surprisingly, just 3% by weight of the hydrogenated block copolymer can increase the impact strength of a 1/4-inch specimen to approximately 14 kg/cm.
It is effective to increase the notch up to 11 ft.lbs./in., which is close to that of thin-walled, non-modified polycarbonate. The third major benefit of adding hydrogenated block copolymers to polycarbonate is improved environmental resistance. That is, the molded part can be subjected to greater strains before cracking begins without appreciably affecting any of its properties other than its desired properties. U.S. Pat. No. 3,431,224 discloses that polyolefins and other resins are useful for this purpose, and German Patent Publication No. 2,329,585 discloses the use of rubbery random polymers and copolymers to enhance certain properties of aromatic polycarbonates. The addition of polymers is disclosed to moderately prolong the time it takes for parts to stress crack under stress, such as when immersed in aggressive solvents such as gasoline and carbon tetrachloride. It has been found that hydrogenated block copolymers exhibit excellent and unique suitability. All publications and patents discussed herein are incorporated by reference. The novel compositions of the present invention may be reinforced, for example, with fibrous glass, halogenated aromatic polycarbonates as all or part of the aromatic polycarbonate resin component, and/or flame retardant additives. Their field of use can be extended in melt-processed products by making them flame-resistant or pigmented and/or foamed by known methods. Compared to prior art compositions, the novel compositions of the present invention also generally have high stiffness and strength, exhibit excellent surface appearance, and excellent resistance to thermal fading. According to the present invention, (a) an aromatic polycarbonate resin, (b) a polymerized vinyl aromatic compound (A) and
(A) 1 o and an olefinic elastomer (B) A o -B-A 1 o , A o -(B-A-B) o -A o , A o
(BA) o B, (A) 4 B, B (A) 4 or B [(AB)) o
A high impact strength thermoplastic resin composition comprising an intimate blend of a selectively hydrogenated linear, sequential or radial teleblock copolymer of the type B], where n is an integer from 1 to 10. is provided. In a preferred composition, component (a) is comprised between 99.5 and 50 parts by weight, based on the total weight of components (a) and (b), and component (b) is
0.5 to 50 parts by weight. In particularly preferred compositions, based on the total weight of components (a) and (b),
(a) constitutes 99.5 to 90 parts by weight and component (b) constitutes 0.5 to 10 parts by weight. In preferred compositions, aromatic polycarbonate component (a) is an aromatic polycarbonate of dihydric phenol and a carbonate precursor such as phosgene, halofomate or carbonate ester. Generally speaking, such carbonate polymers typically have the formula It has a repeating structural unit of. In the formula, A is a divalent aromatic group of divalent phenol used in the polymer production reaction. Preferably, the carbonate polymer has a dl./g. It has an intrinsic viscosity of about 0.35 to about 0.75, measured in units. The dihydric phenols used to produce these aromatic polycarbonate polymers are mononuclear and polynuclear aromatic compounds containing two hydroxyl groups as functional groups, each of which is attached to the aromatic nucleus. Bonded directly to a carbon atom. Examples of dihydric phenols include 2,2-bis(4-hydroxyphenyl)propane (also known as bisphenol-
A), resorcinol, bis-(4-hydroxy-5-
nitrophenyl)methane, 2,2'-dihydroxy-diphenyl, 2,6-dihydroxynaphthalene, bis-(4-hydroxyphenylsulfone),
These include 5'-chloro-2,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxy-2,5-diethoxydiphenyl ether. A variety of other dihydric phenols that can be used to provide such carbonate polymers are disclosed in US Pat. No. 2,999,835. If a carbonate copolymer rather than a homopolymer is desired for use as component (a) in the compositions of the present invention, for example a copolymer with flame retardation properties consisting of bisphenol A and titrabromo bisphenol A It is of course also known to use two or more different dihydric phenols, or to use combinations of dihydric phenols with glycols, hydroxy-terminated polyesters or dibasic acids. For component (b), hydrogenated block copolymers are made by means known in the art and are commercially available. Before hydrogenation, the end blocks of these copolymers are preferably alkenyl aromatic hydrocarbons and especially vinyl aromatic hydrocarbons, where the aromatic component is either monocyclic or polycyclic. homopolymers prepared from (which may also be) copolymers. Typical monomers include styrene,
Included are alpha-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, and vinylnaphthalene, especially styrene or mixtures thereof. The terminal blocks (A) o and (A 1 ) o may be the same or different. The central block (B) can be derived, for example, from butadiene, isoprene, 1,3-pentadiene and 2,3-dimethylbutadiene and can have a linear, secantial or teleradial structure. . Selectively hydrogenated linear block copolymers are described in US Pat. No. 3,333,024. The proportions and average molecular weight of the copolymers can vary widely, but the molecular weight of the central block should be greater than the combined molecular weight of the end blocks. It is preferred to form terminal blocks A with an average molecular weight of 2,000 to 100,000 and central blocks B with an average molecular weight of 25,000 to 1,000,000, such as hydrogenated polybutadiene blocks.
Even more preferably, the average molecular weight of the terminal block is from 8,000 to 60,000 and the average molecular weight of the hydrogenated polybutadiene polymer block is from 50,000 to 300,000. The terminal block is 2 to 2 of the total block copolymer.
Preferably it constitutes 60% by weight or more, preferably 15-40% by weight. Preferred copolymers have a hydrogenated/saturated polybutadiene center block;
It is formed from a copolymer in which 5 to 55% or more preferably 30 to 50% of the butadiene carbon atoms are vinyl side chains. The average degree of unsaturation of the hydrogenated copolymer is 20% of the initial value
reduced to less than The degree of unsaturation in the central block B is 10% or less of the original value, preferably 5.
Preferably, it is reduced to %. Block copolymers are formed by techniques well known to those skilled in the art. Various hydrogenation catalysts can be used to carry out the hydrogenation, such as nickel, diatomaceous earth, Raney nickel, copper chromate, molybdenum oxide, as well as finely divided platinum or other noble metals supported on low surface area carriers. Hydrogenation can be carried out at any desired temperature or pressure, i.e., in the range of atmospheric pressure to 300 psig, usually 100 to 1000 psig, at a temperature of 75 to 600 psig, for 0.1 to 24 hours, preferably 0.2 to 8 hours. can. According to the invention, hydrogenated block copolymers such as Kraton G-6500, Kraton G-6521, Kraton G-
1650 and DratonG−1652 (both Shell
Chemical Company, Polymers Division) can be used. Kraton G-1650 is preferred. Things that can also be used include the so-called
Phillips hydrogenated Solprenes, especially Solprene
There is a product called -512. Radial altere block copolymers, of which Splprenes are representative examples, are characterized by having at least three polymer branches, each branch of which is defined above as (A) and (A 1 ). It contains a terminal non-elastomeric segment such as. The branches of the radial block polymer include terminal non-elastomeric segments to which are attached elastomeric polymer segments as defined above. These copolymers are described in US Pat. Nos. 3,753,936 and 3,281,383 and are selectively hydrogenated by known methods. The polymers contemplated by the term "selective hydrogenation" as used herein are elastomers.
(B) is hydrogenated and the non-elastomeric block (A)
and (A') are unhydrogenated aromatics. As mentioned above, other additives may be present in the composition, such as pigments such as titanium dioxide, flame retardants and blowing agents such as 5-phenyltetrazole, which may be added to all resin components (a) and (b) in the composition. ) may be present in an amount of about 0.1 to 100 parts by weight. Reinforced compositions which fall within a preferred feature of the invention include reinforcing amounts of reinforcing agents, such as metals such as aluminum, bronze, iron or nickel powders, whiskers, fibers or platelets, as well as non-woven materials. Metals e.g. carbon filaments, needles
There are CaSiO 3 , asbestos, TiO 2 , titanate whiskers and glass flakes. Such reinforcing agents are present in amounts of, for example, 2 to 60% by weight, preferably 5 to 40% by weight. A particularly preferred reinforcing agent is fibrous glass. The method of forming the polymer composition is not critical. Any conventional formulation technique is generally suitable. The preferred method of compounding the polymers and additives, such as reinforcing agents optionally in powder, granular and filament form, extruding the formulation and forming the normally solid thermoplastic compositions is conventional. by cutting into pellets suitable for molding by any suitable means. Elastomeric vinyl aromatic-olefin A selectively hydrogenated with aromatic polycarbonate resin
The advantages obtained by providing compositions with -B-A' block copolymers are illustrated in the following examples, which are disclosed as further descriptions of the invention and which are incorporated herein by reference. It is not intended that the invention be limited to these embodiments. The ingredients were mechanically blended, then pre-dried at 125°C for 4 hours, then dried in a twin-screw tube at 300°C.
The following composition is produced by the general procedure of extrusion in a Werner Pfleiderer (WP). After extrusion, the material was dried at 125°C for 4 hours,
Then 260-320℃ (cylinder) and 20-115℃
(mold) into a test specimen in a reciprocating screw injection molding machine. To produce a foamable composition, the pelletized extrudate is mixed with (1) and (b) 0.25 parts of 5 per 100 parts.
- Dry blending with phenyltetrazole. Foam molding is carried out in a Siemag machine equipped with a plasticizing acid/accumulator. All conditions are standard for the polycarbonate itself. All of the polycarbonate components contain small amounts, e.g. 0.1% of the stabilizer combination, i.e.
Contains conventional phosphites/sterically hindered phenols. Perform physical property tests using the following procedure.
Notched isot impact strength for 0.64 cm and 0.32 cm test pieces, falling spear impact test for 0.32 cm disc test pieces, tensile strength and modulus, bending strength and modulus, heating strain temperature, 1500/sec and 300°C
apparent melt viscosity, and Gardner impact and Charpy impact values in the case of foams. Physical properties for the prepared compositions and molded articles are as follows. Example 1 Compositions were prepared, molded and compared.
【表】
＊ 対照例
a Lexan 160 General Electric Co.
b Kraton G1650 Shell Chemical Co.
実施例１の組成物にあつては、溶融粘度が目立
つて低下し、厚部衝撃強度が実質的に改善され、
しかも他の特性に損失は認められないのがわか
る。
実施例 ２
更に高い分子量の芳香族ポリカーボネートによ
り組成物を調製する。[Table] * Control example
a Lexan 160 General Electric Co.
b Kraton G1650 Shell Chemical Co.
For the composition of Example 1, the melt viscosity was noticeably reduced, the thick section impact strength was substantially improved, and
Moreover, it can be seen that no loss is observed in other characteristics. Example 2 A composition is prepared with a higher molecular weight aromatic polycarbonate.
【表】
＊ 対照例
a Lexan 100 General Electric Co.
b Kraton G1650 Shell Chemical Co.
本実施例に於いても、溶融粘度の著しい低下と
厚部衝撃抵抗の増大が見られる。
実施例 ３
ガラス強化組成物を調製し比較する。[Table] * Control example
a Lexan 100 General Electric Co.
b Kraton G1650 Shell Chemical Co.
In this example as well, a significant decrease in melt viscosity and an increase in thick part impact resistance are observed. Example 3 Glass reinforced compositions are prepared and compared.
【表】
＊ 対照例
a Lexan 100 General Electric Co.
b Kraton G1650 Shell Chemical Co.
単に流れ特性が著しく改善されるだけでなく、
厚壁及び薄壁のいずれに対しても問題となるガラ
スによる脆化作用がなくなる。
実施例 ４
顔料着色組成物を調製し比較する。[Table] * Control example
a Lexan 100 General Electric Co.
b Kraton G1650 Shell Chemical Co.
Not only the flow properties are significantly improved;
The problematic embrittlement effect of glass on both thick and thin walls is eliminated. Example 4 Pigmented coloring compositions are prepared and compared.
【表】
＊ 対照例
a Lexan 100 General Electric Co.
b Kraton G1650 Shell Chemical Co.
流れ特性及び衝撃強度が改善され、他の重要な
特性に損傷はなかつた。
実施例 ５
強化した火炎遅延性の発泡組成物を調製し、成
形し、比較した。[Table] * Control example
a Lexan 100 General Electric Co.
b Kraton G1650 Shell Chemical Co.
Flow properties and impact strength were improved with no damage to other important properties. Example 5 Reinforced flame retardant foam compositions were prepared, molded, and compared.
【表】
し し
＊ 対照例
a Lexan 100 General Electric Co.
b Kraton G1650 Shell Chemical Co.
処理加工性が改善されている為、重量３〜４キ
ロ、最適密度0.7〜0.9ｇ／c.c.３のような大きな部
品が本発明の組成物から発泡でき、しかも表面は
勝れた光沢を有している。構造発泡体の成形に対
する典型的な特徴は滞留時間が長く温度が高いこ
とであり、これ等は流動性の要件にとつて必要で
ある。この点は化学的発泡剤が存在すると重合体
の破壊によつて厳しい技術的問題が引き起こされ
る結果となる。本発明による実施例はあらゆる点
でこれ等の問題を克服している。
実施例 ６〜９
一連の組成物を調製し成形し、自体既知の手段
により四塩化炭素に浸漬後0.25％歪による抗折負
荷の環境応力割れを測定する。[Table]
* Control example
a Lexan 100 General Electric Co.
b Kraton G1650 Shell Chemical Co.
Due to the improved processability, large parts such as weight 3-4 kg and optimum density 0.7-0.9 g/ cc3 can be foamed from the compositions of the present invention, yet the surface has excellent gloss. ing. Typical characteristics for molding structural foams are long residence times and high temperatures, which are necessary for flowability requirements. In this respect, the presence of chemical blowing agents results in severe technical problems due to destruction of the polymer. Embodiments according to the invention overcome these problems in all respects. Examples 6 to 9 A series of compositions are prepared and molded, and after immersion in carbon tetrachloride, the environmental stress cracking at a bending load of 0.25% strain is measured by means known per se.
【表】
本発明の組成物は応力ヒビ割れ抵抗を目立つて
改善しているのが認められる。
別の試験では、組成物６及び6Aのそれぞれか
ら成形された引張試験棒を2.8％の一定引張変形
下に24時間おく。試料6Aは多くのヒビを示して
いるのに対し、実施例６はヒビを示さず環境空気
中の応力弛緩に対し勝れた抵抗を示している。
実施例 10
実施例１による組成物（ポリ（2.2−ジフエニ
ルプロパン）カーボネート97部と水添スチレン−
ブタジエン−スチレンブロツクコポリマー３部）
を0.32cm厚の円板に成形し落槍衝撃試験にかけ
る。次いでこの円板を環境応力割れ抵抗につき試
験し次の結果を得る。Table: The compositions of the present invention are seen to have significantly improved stress cracking resistance. In another test, tensile test bars molded from each of Compositions 6 and 6A are subjected to a constant tensile deformation of 2.8% for 24 hours. Sample 6A shows many cracks, whereas Example 6 shows no cracks and excellent resistance to stress relaxation in ambient air. Example 10 Composition according to Example 1 (97 parts of poly(2,2-diphenylpropane) carbonate and hydrogenated styrene)
butadiene-styrene block copolymer (3 parts)
was formed into a 0.32cm thick disk and subjected to a falling spear impact test. The discs were then tested for environmental stress cracking resistance with the following results.
【表】
じない。
実施例 11
火炎遅延性で発泡されたガラス強化組成物（実
施例５）を試験棒に成形し、ガソリリン（Super
Pertol）に浸漬し、そして最高抗折力を50分まで
時間の関数として測定し発泡ポリカーボネート対
照例から成形した棒と比較する。初期に於ける、
両方の棒の最高抗折力は560Kgｆ／cm2である。対
照例は２分以内に100まで減少しここで安定にな
つた。本発明の組成物は20分間でゆつくりと250
Kgｆ／cmまで減少し、50分の浸漬時間までこの値
以下に落ち込まない。
前記のデータから、ブロツクコポリマーを芳香
族ポリカーボネートに添加すると壁厚が厚くても
脆性変形せずかえつて延性を増す。
こうして為された有益な延性変形と同じものが
顔料やガラス補強によつても得られるが、これ等
は芳香族ポリカーボネートの脆化をきたすことで
よく知られている。
同じく脆化しない火炎遅延変性物も生成され、
これは発泡時にも勝れている。
環境応力割れ抵抗は中実体並びに発泡体に対し
ても大いに改善されている。[Table] Jinai.
Example 11 A flame retardant foamed glass reinforced composition (Example 5) was molded into test bars and treated with gasoline (Super
Pertol) and the maximum transverse rupture strength is measured as a function of time for up to 50 minutes and compared to bars molded from expanded polycarbonate controls. In the early days,
The maximum transverse rupture strength of both bars is 560 Kgf/cm 2 . The control value decreased to 100 within 2 minutes and became stable at this point. The composition of the present invention slowly produces 250 ml of water in 20 minutes.
Kgf/cm and does not fall below this value until a soaking time of 50 minutes. From the above data, it can be seen that when a block copolymer is added to an aromatic polycarbonate, it does not undergo brittle deformation even when the wall thickness is large, but rather increases its ductility. The same beneficial ductile deformation thus achieved can be achieved by pigment and glass reinforcement, which are well known to cause embrittlement of aromatic polycarbonates. Similarly, non-embrittling flame-retardant modified products are also produced,
This is also superior when foaming. Environmental stress cracking resistance is greatly improved for solid bodies as well as foams.
Claims (1)
ポリマーを(a)と(b)の合計100重量部につき3.5重
量部以下の割合で密接混合してなる熱可塑性樹
脂組成物であつて、 (A)と（A1）は重合した芳香族ビニル化合物のブ
ロツクであり、(B)はオレフイン性エラストマーブ
ロツクである熱可塑性樹脂組成物。 ２ 芳香族ポリカーボネートがビスフエノールＡ
のポリカーボネートである特許請求の範囲第１項
記載の組成物。 ３ 成分(b)に於いて、(A)と（A1）はスチレン、α
−メチルスチレン、ビニルトルエン、ビニルキシ
レン及びビニルナフタリンから選ばれ、(B)は重合
されたブタジエン、イソプレン、１，３−ペンタ
ジエン及び２，３−ジメチルブタジエンから選ば
れる特許請求の範囲第１項または第２項記載の組
成物。 ４ 成分(b)に於いて、(A)及び（A1）がスチレンブ
ロツクである特許請求の範囲第３項記載の組成
物。 ５ 成分(b)に於いて、末端ブロツク(A)及び
（A1）がそれぞれ2000〜100000の分子量を有し、
中央ブロツク(B)が25000〜1000000の分子量を有す
る特許請求の範囲第４項記載の組成物。 ６ 強化性充填剤を更に含んだ特許請求の範囲第
１項乃至第５項のいずれかに記載の組成物。 ７ 火炎遅延剤を更に含んだ特許請求の範囲第１
項乃至第６項のいずれかに記載の組成物。 ８ 発泡剤を更に含んだ特許請求の範囲第１項乃
至７項のいずれかに記載の組成物。[Scope of Claims] 1 (a) An aromatic polycarbonate resin, (b) A-B-A 1 type selectively hydrogenated linear copolymer in a total of 100% of (a) and (b). A thermoplastic resin composition formed by intimately mixing 3.5 parts by weight or less per part by weight, wherein (A) and (A 1 ) are blocks of polymerized aromatic vinyl compounds, and (B) is an olefinic vinyl compound. A thermoplastic resin composition that is an elastomer block. 2 Aromatic polycarbonate is bisphenol A
The composition according to claim 1, which is a polycarbonate. 3 In component (b), (A) and (A 1 ) are styrene, α
- selected from methylstyrene, vinyltoluene, vinylxylene and vinylnaphthalene, and (B) selected from polymerized butadiene, isoprene, 1,3-pentadiene and 2,3-dimethylbutadiene; or The composition according to item 2. 4. The composition according to claim 3, wherein in component (b), (A) and (A 1 ) are styrene blocks. 5 In component (b), the terminal blocks (A) and (A 1 ) each have a molecular weight of 2000 to 100000,
5. A composition according to claim 4, wherein the central block (B) has a molecular weight of 25,000 to 1,000,000. 6. The composition according to any one of claims 1 to 5, further comprising a reinforcing filler. 7 Claim 1 further including a flame retardant
The composition according to any one of items 6 to 6. 8. The composition according to any one of claims 1 to 7, further comprising a blowing agent.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US83336477A | 1977-09-14 | 1977-09-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5453161A JPS5453161A (en) | 1979-04-26 |
| JPS6142748B2 true JPS6142748B2 (en) | 1986-09-24 |
Family
ID=25264220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11184678A Granted JPS5453161A (en) | 1977-09-14 | 1978-09-13 | Thermoplastic resin composition |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5453161A (en) |
| AU (1) | AU530369B2 (en) |
| DE (1) | DE2839356A1 (en) |
| FR (1) | FR2403365B1 (en) |
| GB (1) | GB2004284B (en) |
| MX (1) | MX149349A (en) |
| NL (1) | NL7809361A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6339838U (en) * | 1986-08-30 | 1988-03-15 |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4267096A (en) * | 1979-11-09 | 1981-05-12 | General Electric Company | Composition of a selectively hydrogenated block copolymer of a vinyl aromatic compound and a diolefin, a polycarbonate and an amorphous polyester |
| US4532283A (en) * | 1982-09-23 | 1985-07-30 | General Electric Company | Aromatic carbonate polymer composition |
| US4481331A (en) * | 1983-03-22 | 1984-11-06 | Gen Electric | Polycarbonate resin mixture |
| US4513119A (en) * | 1983-04-21 | 1985-04-23 | General Electric Company | Polycarbonate resin mixtures |
| DE3324906A1 (en) * | 1983-07-09 | 1985-01-17 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS |
| DE3347071A1 (en) * | 1983-08-31 | 1985-03-14 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS BASED ON POLYSILOXANE-POLYCARBONT BLOCK COPOLYMERS |
| EP0141197A3 (en) * | 1983-09-26 | 1986-09-10 | General Electric Company | Copolycarbonate resin impact modified with diblock copolymer |
| NL8402555A (en) * | 1984-08-20 | 1986-03-17 | Gen Electric | POLYMER MIXTURE, CONTAINING AN AROMATIC POLYCARBONATE RESIN AND AN IMPACT STRENGTH ENHANCING AGENT. |
| US4652602A (en) * | 1985-06-04 | 1987-03-24 | General Electric Company | Blow-moldable polycarbonate resin compositions |
| US4767818A (en) * | 1987-03-23 | 1988-08-30 | General Electric Company | Low gloss, flame retardant polycarbonate compositions |
| US5049615A (en) * | 1989-12-11 | 1991-09-17 | Hercules Incorporated | Polyindanes as processing aid for engineering thermoplastics |
| EP0893476A1 (en) * | 1997-07-23 | 1999-01-27 | Daicel Chemical Industries, Ltd. | Thermoplastic resin composition |
| NL1020568C2 (en) | 2002-05-08 | 2003-11-11 | Dsm Nv | Fiberglass-reinforced polycarbonate composition with improved toughness. |
| WO2023175076A1 (en) * | 2022-03-17 | 2023-09-21 | Sabic Global Technologies B.V. | Low volatile organic compound (voc) thermoplastic composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52117940A (en) * | 1976-03-27 | 1977-10-03 | Bayer Ag | Thermoplastic rubber |
| JPS52150464A (en) * | 1976-06-07 | 1977-12-14 | Shell Int Research | Composition containing hydrogenated block copolymers and process for producing polymer of mutually invaded and crossslinked structure |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2643757C2 (en) * | 1976-09-29 | 1985-10-10 | Bayer Ag, 5090 Leverkusen | Mixtures of hydrogenated styrene-butadiene block polymers with polycarbonates, processes for their preparation and their use |
-
1978
- 1978-08-24 GB GB7834453A patent/GB2004284B/en not_active Expired
- 1978-09-09 DE DE19782839356 patent/DE2839356A1/en active Granted
- 1978-09-13 AU AU39826/78A patent/AU530369B2/en not_active Expired
- 1978-09-13 FR FR7826299A patent/FR2403365B1/en not_active Expired
- 1978-09-13 JP JP11184678A patent/JPS5453161A/en active Granted
- 1978-09-14 NL NL7809361A patent/NL7809361A/en not_active Application Discontinuation
- 1978-09-14 MX MX174887A patent/MX149349A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52117940A (en) * | 1976-03-27 | 1977-10-03 | Bayer Ag | Thermoplastic rubber |
| JPS52150464A (en) * | 1976-06-07 | 1977-12-14 | Shell Int Research | Composition containing hydrogenated block copolymers and process for producing polymer of mutually invaded and crossslinked structure |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6339838U (en) * | 1986-08-30 | 1988-03-15 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2004284B (en) | 1982-04-07 |
| FR2403365A1 (en) | 1979-04-13 |
| GB2004284A (en) | 1979-03-28 |
| AU3982678A (en) | 1980-03-20 |
| JPS5453161A (en) | 1979-04-26 |
| MX149349A (en) | 1983-10-26 |
| AU530369B2 (en) | 1983-07-14 |
| FR2403365B1 (en) | 1985-09-20 |
| DE2839356C2 (en) | 1991-09-19 |
| DE2839356A1 (en) | 1979-03-22 |
| NL7809361A (en) | 1979-03-16 |
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