JPH0217583B2 - - Google Patents
Info
- Publication number
- JPH0217583B2 JPH0217583B2 JP55108194A JP10819480A JPH0217583B2 JP H0217583 B2 JPH0217583 B2 JP H0217583B2 JP 55108194 A JP55108194 A JP 55108194A JP 10819480 A JP10819480 A JP 10819480A JP H0217583 B2 JPH0217583 B2 JP H0217583B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- aromatic polycarbonate
- resin
- acrylic acid
- 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 - Lifetime
Links
- 125000003118 aryl group Chemical group 0.000 claims description 34
- 239000004431 polycarbonate resin Substances 0.000 claims description 25
- 229920005668 polycarbonate resin Polymers 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 16
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 15
- 239000011342 resin composition Substances 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- -1 carbonyl halide Chemical class 0.000 description 6
- 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 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004419 Panlite Substances 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 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
- 238000004898 kneading Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は樹脂組成物に関するものである。更に
詳しくは本発明は芳香族ポリカーボネート樹脂と
特定のアクリル酸エステル系２段グラフト弾性重
合体よりなる機械的物性特に耐衝撃性、ウエルド
強度の優れた樹脂組成物に関する。
周知のように芳香族ポリカーボネート樹脂は、
強靭で耐衝撃性、寸法安定性、電気的特性に優れ
ていることから、有用なエンジニアリングプラス
チツクスとして広範囲に利用されている。
このように優れた性質をもつエンジニアリング
プラスチツクスであるが、一方では溶融粘度が高
く、成形加工性が悪いこと、耐衝撃性にあつては
成形品の厚さによる依存性が高く、例えば3.2mm
厚さ（1/8インチ厚さ）のアイゾツト（Izod）ノ
ツチ付きインパクト値は延性破壊を示すのに対
し、6.4mm厚さ（1/4インチ厚さ）の場合には脆性
破壊を示し、厚さが厚い領域で衝撃強度が低下す
るという問題がある。
これら加工性、衝撃強度の厚さ依存性を改良す
るために種々の提案がなされている。例えば特公
昭40−13663号公報には芳香族ポリカーボネート
樹脂とポリオレフインとのブレンド樹脂が、特公
昭40―24191号公報には芳香族ポリカーボネート
樹脂とエチレン―プロピレンブロツク共重合体と
のブレンド樹脂が、特公昭38−15225号公報には
芳香族ポリカーボネート樹脂とABS樹脂とのブ
レンド樹脂が、特公昭39−71号公報には芳香族ポ
リカーボネート樹脂とMBS樹脂とのブレンド樹
脂が、また特公昭48−29308号公報には芳香族ポ
リカーボネート樹脂とアクリレート系グラフト重
合体とのブレンド樹脂が提案され、更にその他３
成分以上のブレンド樹脂についても数多くの提案
がなされている。
しかしながら、いずれのブレンド樹脂について
も加工性、耐衝撃性の改良はなされているが、こ
れらの複合樹脂において本質的と思われる問題
点、例えば熱変形温度のような耐熱性の低下、相
溶性不良に伴う表面剥離現象、ウエルド部分の弱
さが発生し、充分な結果が得られていないためそ
の用途が制限されている。
本発明者は、前記芳香族ポリカーボネート系複
合樹脂の問題点を解決すべく検討を加えた結果、
特定割合のアクリル酸エステル系２段グラフト弾
性重合体を芳香族ポリカーボネート樹脂にブレン
ドすることにより加工性、耐衝撃性は勿論のこ
と、特にウエルド強度の優れた樹脂組成物が得ら
れることを見出し、本発明に到達した。
即ち、本発明は芳香族ポリカーボネート樹脂80
〜97重量％及びアクリル酸エステル系２段グラフ
ト弾性重合体３〜20重量％よりなる樹脂組成物で
ある。
本発明に使用される芳香族ポリカーボネート樹
脂は、芳香族ジヒドロキシ化合物とカーボネート
前駆体とを溶液法又は溶融法で製造される芳香族
ポリカーボネート樹脂である。前記芳香族ジヒド
ロキシ化合物の代表的な例としてはビスフエノー
ルＡ［２，２―ビス（４―ヒドロキシフエニル）
プロパン］、ビス（４―ヒドロキシフエニル）メ
タン、２，２―ビス（４―ヒドロキシ―３―メチ
ルフエニル）プロパン、２，２―ビス（４―ヒド
ロキシ―３，５―ジメチルフエニル）プロパン、
２，２―ビス（４―ヒドロキシ―３，５―ジブロ
ムフエニル）プロパン、ビス（４―ヒドロキシフ
エニル）サルフアイド、ビス（４―ヒドロキシフ
エニル）スルホン等があげられる。
好ましいのはビス（４―ヒドロキシフエニル）
アルカン系特にビスフエノールＡを主成分とする
芳香族ポリカーボネート樹脂である。本発明に使
用される芳香族ポリカーボネート樹脂は前記芳香
族ジヒドロキシ化合物とカーボネート前駆体との
反応によつて製造されるが、前記芳香族ジヒドロ
キシ化合物を単独で又は２種以上で使用すること
ができる。また、かくして得られた芳香族ポリカ
ーボネート樹脂の２種以上を混合して使用しても
差支えない。
前記カーボネート前駆体としてはカルボニルハ
ライド、カルボニルエステル又はハロホルメート
等いずれであつてもよい。代表的な例としてはホ
スゲン、ジフエニルカーボネート、芳香族ジヒド
ロキシ化合物のジハロホルメート又はそれらの混
合物等があげられる。
芳香族ポリカーボネート樹脂は、通常芳香族ジ
ヒドロキシ化合物とホスゲンから溶液法で、又は
芳香族ジヒドロキシ化合物とジフエニルカーボネ
ートから溶融法で製造される。また、使用される
芳香族ポリカーボネート樹脂の分子量は、一般に
10000〜100000、好ましくは15000〜60000である。
これらの分子量の芳香族ポリカーボネート樹脂を
製造するに際し、適当な分子量調節剤を使用して
もよいし、分岐剤を用いることもできる。また、
反応を促進するための触媒を使用してもよい。
一方、本発明に使用されるアクリル酸エステル
系２段グラフト弾性重合体は、２―エチルヘキシ
ルアクリレート35〜60重量部、ブタジエン５〜20
重量部、メチルメタクリレート０〜10重量部及び
架橋剤（例えばエチレンジメタクリレート等）
0.65重量部を乳化重合させて得られるゴムラテツ
クスに凝集剤を加えて平均粒径を0.13〜0.20μに
調整したラテツクス状ゴム65重量部に対して、第
１グラフト成分としてスチレン５〜15重量部、メ
チルメタクリレート５〜10重量部及び架橋剤（例
えばエチレンジメタクリレート、ジビニルベンゼ
ン等）0.1〜0.3重量部よりなる混合モノマー20〜
25重量部をグラフト重合させ、更に第２グラフト
成分としてメチルメタクリレート10〜15重量部及
び架橋剤（例えばエチレンジメタクリレート、ジ
ビニルベンゼン等）0.1〜0.3重量部よりなる混合
モノマー10〜15重量部をグラフト重合させること
によつて製造される多成分系共重合体である。か
かるアクリル酸エステル系２段グラフト弾性重合
体は呉羽化学工業(株)から製品名HIA―15として
市販されている。
アクリル酸エステル系２段グラフト弾性重合体
は、芳香族ポリカーボネート樹脂とのブレンド物
の総量に対して３〜20重量％占めるように添加さ
れる。この添加量が３重量％未満の場合には1/4
インチ厚さにおける耐衝撃性向上効果が充分でな
く、20重量％を越えると耐熱性（例えば熱変形温
度）の低下をもたらし、耐衝撃性の向上効果が小
さくなり、成形品の色相、外観が悪化するように
なる。
本発明の芳香族ポリカーボネート樹脂とアクリ
ル酸エステル系２段グラフト弾性重合体との樹脂
組成物は耐衝撃性が著しく改善されており、耐熱
性、ウエルド強度、成形品の色相、外観も良好で
ある。
一般に耐衝撃性を改善することを目的とした芳
香族ポリカーボネート樹脂とゴム変性ビニル系重
合体の組成物は、両成分の相溶性が不充分である
ため、押出成形や射出成形による成形品は剥離を
生じたり、ウエルド部の引張り強度が劣るという
問題があつて商品化が困難であるが、本発明の組
成物は予想に反してこれらの欠点が解消されてい
ることは驚くべきことである。その理由は明らか
でないが、本発明において使用するアクリル酸エ
ステル系２段グラフト弾性重合体が、スチレンを
共重合成分として含有し、また幹に相当するゴム
成分が、通常耐候性を阻害するものとして敬遠さ
れるブタジエン単位を比較的多量に含有し、且つ
枝に相当するグラフト部分にも通常行なわれない
架橋が施されていることが総合されて、剥離を押
えウエルド強度を改善するという良好な結果をも
たらすものと推定される。かくして本発明の樹脂
組成物から得られる成形品は、外観的にも機械的
特性にも優れた、バランスのとれた性能を発揮す
ることができる。
本発明の樹脂組成物を製造するに当たつて既知
の如何なる方法を利用しても差支えない。一例を
あげると芳香族ポリカーボネート樹脂とアクリル
酸エステル系２段グラフト弾性重合体をタンブラ
ーでブレンドし、押出機にて溶融混練する方法、
バンバリミキサー、ロール等で混練する方法等の
混練方法によつてブレンド樹脂をペレツト化し、
更に成形加工する方法があげられる。また、芳香
族ポリカーボネート樹脂とアクリル酸エステル系
２段グラフト弾性重合体を混合した後、直ちに射
出成形機で製品を成形する方法等があげられる
が、いずれの方法を用いても、本発明の樹脂組成
物の特徴である耐熱性、耐衝撃性及び光沢が優
れ、ウエルド強度の強い成形品を与える。
本発明の樹脂組成物には、必要に応じて適当な
安定剤（例えば酸化防止剤、熱安定剤、紫外線吸
収剤等）、可塑剤、難燃剤、帯電防止剤、離型剤、
発泡剤等を添加してもよいし、更にガラス繊維、
ガラスパウダー、無機フイラー等の如き補強用充
填材も添加することができる。
本発明の樹脂組成物は前記のように優れた特性
を有し、特にウエルド強度が高いというユニーク
な樹脂組成物であり、従来使用されなかつた領域
へ利用される工業的に有用な樹脂組成物である。
以下に実施例をあげて本発明を説明するが、必
ずしもこれに限定されない。
実施例１〜３及び比較例１，２
ビスフエノールＡを原料とする芳香族ポリカー
ボネート（帝人化成(株)製：パンライトＬ―1250、
分子量24800）とアクリル酸エステル系２段グラ
フト弾性重合体（呉羽化学工業(株)製：商品名
HIA―15）とを夫々所定の割合に計量し、ブレ
ンダーで30分間混合した。得られた混合物を30mm
ベント式押出し機（中央機械(株)製：VSK―30）
でシリンダー温度280℃で押出し、ペレツト化し
た。得られたペレツトを120℃、２時間熱風乾燥
機で乾燥した後射出成形機（新潟スチユーベ：
S150／235）で物性試験片を作成した。
物性試験は20℃、50％RHで調湿した後所定の
試験機で物性を測定し、結果を第１表に示した。
また、比較のため上記実施例１のアクリル酸エ
ステル系２段グラフト弾性重合体に代えてポリエ
チレンを使用した場合の結果を第１表に併記し
た。
The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition comprising an aromatic polycarbonate resin and a specific acrylic acid ester two-stage grafted elastic polymer, which has excellent mechanical properties, particularly impact resistance and weld strength. As is well known, aromatic polycarbonate resin is
Due to its toughness, impact resistance, dimensional stability, and excellent electrical properties, it is widely used as a useful engineering plastic. Engineering plastics have such excellent properties, but on the other hand, they have high melt viscosity, poor moldability, and impact resistance is highly dependent on the thickness of the molded product, such as 3.2 mm.
The Izod notched impact value for thickness (1/8 inch thick) indicates ductile failure, whereas for 6.4 mm thickness (1/4 inch thickness) it indicates brittle failure, There is a problem that the impact strength decreases in the thick region. Various proposals have been made to improve the thickness dependence of these processability and impact strength. For example, Japanese Patent Publication No. 40-13663 discloses a blend resin of aromatic polycarbonate resin and polyolefin, and Japanese Patent Publication No. 40-24191 discloses a blend resin of aromatic polycarbonate resin and ethylene-propylene block copolymer. Publication No. 38-15225 discloses a blend resin of aromatic polycarbonate resin and ABS resin, Japanese Patent Publication No. 39-71 discloses a blend resin of aromatic polycarbonate resin and MBS resin, and Japanese Patent Publication No. 48-29308 discloses a blend resin of aromatic polycarbonate resin and MBS resin. The publication proposes a blend resin of an aromatic polycarbonate resin and an acrylate graft polymer, and three others.
Many proposals have also been made regarding blend resins containing more than just the components. However, although improvements have been made in the processability and impact resistance of all blended resins, there are problems that seem to be essential to these composite resins, such as a decrease in heat resistance such as heat distortion temperature, and poor compatibility. Due to this, surface peeling phenomenon and weakness of the weld portion occur, and sufficient results have not been obtained, which limits its use. As a result of the inventor's studies to solve the problems of the aromatic polycarbonate composite resin,
We have discovered that by blending a specific proportion of an acrylic acid ester-based two-stage grafted elastic polymer with an aromatic polycarbonate resin, a resin composition with excellent processability, impact resistance, and especially weld strength can be obtained. We have arrived at the present invention. That is, the present invention uses aromatic polycarbonate resin 80
This is a resin composition consisting of ~97% by weight and 3~20% by weight of an acrylic acid ester two-stage grafted elastic polymer. The aromatic polycarbonate resin used in the present invention is an aromatic polycarbonate resin produced by a solution method or a melt method using an aromatic dihydroxy compound and a carbonate precursor. A typical example of the aromatic dihydroxy compound is bisphenol A [2,2-bis(4-hydroxyphenyl)].
propane], bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,
Examples include 2,2-bis(4-hydroxy-3,5-dibromphenyl)propane, bis(4-hydroxyphenyl)sulfide, and bis(4-hydroxyphenyl)sulfone. Preferred is bis(4-hydroxyphenyl)
It is an aromatic polycarbonate resin whose main component is alkane, especially bisphenol A. The aromatic polycarbonate resin used in the present invention is produced by reacting the aromatic dihydroxy compound with a carbonate precursor, and the aromatic dihydroxy compounds can be used alone or in combination of two or more. Furthermore, two or more of the aromatic polycarbonate resins thus obtained may be used in combination. The carbonate precursor may be carbonyl halide, carbonyl ester, haloformate, or the like. Typical examples include phosgene, diphenyl carbonate, dihaloformates of aromatic dihydroxy compounds, and mixtures thereof. Aromatic polycarbonate resins are usually produced by a solution method from an aromatic dihydroxy compound and phosgene, or by a melt method from an aromatic dihydroxy compound and diphenyl carbonate. In addition, the molecular weight of the aromatic polycarbonate resin used is generally
10,000 to 100,000, preferably 15,000 to 60,000.
When producing aromatic polycarbonate resins having these molecular weights, an appropriate molecular weight regulator or branching agent may be used. Also,
Catalysts may be used to accelerate the reaction. On the other hand, the acrylic acid ester-based two-stage grafted elastic polymer used in the present invention contains 35 to 60 parts by weight of 2-ethylhexyl acrylate and 5 to 20 parts by weight of butadiene.
parts by weight, 0 to 10 parts by weight of methyl methacrylate and a crosslinking agent (e.g. ethylene dimethacrylate, etc.)
5 to 15 parts by weight of styrene as the first graft component to 65 parts by weight of latex-like rubber obtained by emulsion polymerization of 0.65 parts by weight of rubber latex and adjusting the average particle size to 0.13 to 0.20μ by adding a coagulant. 20 to 20 parts by weight of a mixed monomer consisting of 5 to 10 parts by weight of methyl methacrylate and 0.1 to 0.3 parts by weight of a crosslinking agent (e.g. ethylene dimethacrylate, divinylbenzene, etc.)
25 parts by weight are graft-polymerized, and further 10-15 parts by weight of a mixed monomer consisting of 10-15 parts by weight of methyl methacrylate and 0.1-0.3 parts by weight of a crosslinking agent (e.g. ethylene dimethacrylate, divinylbenzene, etc.) are grafted as a second graft component. It is a multicomponent copolymer produced by polymerization. Such an acrylic acid ester-based two-stage grafted elastic polymer is commercially available from Kureha Chemical Industry Co., Ltd. under the product name HIA-15. The acrylic acid ester two-stage grafted elastic polymer is added in an amount of 3 to 20% by weight based on the total amount of the blend with the aromatic polycarbonate resin. If the amount added is less than 3% by weight, 1/4
The effect of improving impact resistance at inch thickness is not sufficient, and if it exceeds 20% by weight, the heat resistance (e.g. heat distortion temperature) will decrease, the effect of improving impact resistance will become smaller, and the hue and appearance of the molded product will deteriorate. It starts to get worse. The resin composition of the present invention of an aromatic polycarbonate resin and an acrylic acid ester-based two-stage grafted elastic polymer has significantly improved impact resistance, and has good heat resistance, weld strength, color and appearance of molded products. . In general, compositions of aromatic polycarbonate resin and rubber-modified vinyl polymer intended to improve impact resistance have insufficient compatibility between the two components, resulting in extrusion or injection molded products peeling. However, it is surprising that the composition of the present invention overcomes these drawbacks, contrary to expectations. The reason for this is not clear, but the acrylic acid ester-based two-stage grafted elastic polymer used in the present invention contains styrene as a copolymer component, and the rubber component corresponding to the backbone usually inhibits weather resistance. The fact that it contains a relatively large amount of butadiene units, which are avoided, and that the graft portions corresponding to the branches are also cross-linked, which is not normally done, gives good results in suppressing peeling and improving weld strength. It is estimated that this will result in In this way, the molded article obtained from the resin composition of the present invention can exhibit well-balanced performance with excellent appearance and mechanical properties. Any known method may be used to produce the resin composition of the present invention. One example is a method in which an aromatic polycarbonate resin and an acrylic acid ester two-stage grafted elastic polymer are blended in a tumbler and then melt-kneaded in an extruder.
The blended resin is pelletized by a kneading method such as a Banbury mixer, a roll, etc.
Furthermore, there is a method of molding. Another method is to mold the product using an injection molding machine immediately after mixing the aromatic polycarbonate resin and the acrylic acid ester-based two-stage grafted elastic polymer. The composition has excellent heat resistance, impact resistance, and gloss, and provides molded products with strong weld strength. The resin composition of the present invention may contain appropriate stabilizers (for example, antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, flame retardants, antistatic agents, mold release agents,
A foaming agent etc. may be added, and glass fiber,
Reinforcing fillers such as glass powder, inorganic fillers, etc. can also be added. The resin composition of the present invention has excellent properties as described above, and is a unique resin composition in that it has especially high weld strength, and is an industrially useful resin composition that can be used in areas where it has not been used conventionally. It is. The present invention will be explained below with reference to Examples, but it is not necessarily limited thereto. Examples 1 to 3 and Comparative Examples 1 and 2 Aromatic polycarbonate made from bisphenol A (manufactured by Teijin Chemicals Ltd.: Panlite L-1250,
molecular weight 24,800) and acrylic acid ester-based two-stage grafted elastic polymer (manufactured by Kureha Chemical Industry Co., Ltd.: product name)
HIA-15) were weighed out at a predetermined ratio, and mixed in a blender for 30 minutes. 30mm of the resulting mixture
Vented extruder (manufactured by Chuo Kikai Co., Ltd.: VSK-30)
It was extruded at a cylinder temperature of 280°C and pelletized. After drying the obtained pellets in a hot air dryer at 120°C for 2 hours, an injection molding machine (Niigata Stube:
S150/235) was used to prepare physical property test pieces. In the physical property test, the humidity was adjusted at 20°C and 50% RH, and then the physical properties were measured using a specified testing machine, and the results are shown in Table 1. For comparison, Table 1 also shows the results obtained when polyethylene was used in place of the acrylic acid ester two-stage grafted elastic polymer of Example 1.
【表】【table】
【表】
実施例４，５及び比較例３〜９
芳香族ポリカーボネート樹脂（帝人化成(株)製：
パンライト、分子量25000）とアクリル酸エステ
ル系２段グラフト弾性重合体（呉羽化学工業(株)
製：商品名HIA―15）を所定量計量混合し、射
出成形機（東芝(株)製：90BV）を用いてシリンダ
ー温度270〜280℃、金型温度70〜80℃で物性試験
片を作成した。得られた試験片について実施例１
と同様にして物性を測定し、その結果を第２表に
示した。
また、比較のため上記アクリル酸エステル系２
段グラフト弾性重合体に代えて別のアクリル系重
合体（呉羽化学工業(株)製：商品名HIA―28）、
MBS樹脂（呉羽化学工業(株)製：BTA―3N2）又
はポリエチレン（三井石油化学(株)製：ハイゼツク
ス）を使用した場合の結果を第２表に併記した。
なお、比較のために用いたHIA―28はアクリ
ロニトリル単位を含有しており、この点でHIA
―15とは明らかに相違するものである。[Table] Examples 4, 5 and Comparative Examples 3 to 9 Aromatic polycarbonate resin (manufactured by Teijin Chemicals Ltd.:
Panlite, molecular weight 25,000) and acrylic acid ester two-stage graft elastic polymer (Kureha Chemical Industry Co., Ltd.)
(product name: HIA-15) was weighed and mixed in a predetermined amount, and a physical property test piece was created using an injection molding machine (manufactured by Toshiba Corporation: 90BV) at a cylinder temperature of 270 to 280℃ and a mold temperature of 70 to 80℃. did. Example 1 regarding the obtained test piece
The physical properties were measured in the same manner as above, and the results are shown in Table 2. In addition, for comparison, the above acrylic ester type 2
Instead of the step-grafted elastic polymer, another acrylic polymer (manufactured by Kureha Chemical Industry Co., Ltd.: trade name HIA-28) was used.
Table 2 also shows the results when MBS resin (manufactured by Kureha Chemical Industries, Ltd.: BTA-3N2) or polyethylene (manufactured by Mitsui Petrochemicals, Ltd.: Hi-Zex) was used. In addition, HIA-28 used for comparison contains acrylonitrile units, and in this respect HIA-28
- This is clearly different from 15.
Claims (1)
びアクリル酸エステル系２段グラフト弾性重合体
３〜20重量％よりなる樹脂組成物。 ［ここでアクリル酸エステル系２段グラフト弾
性重合体は、２―エチルヘキシルアクリレート35
〜60重量部、ブタジエン５〜20重量部、メチルメ
タクリレート０〜10重量部及び架橋剤0.65重量部
を乳化重合させて得られるゴムラテツクスに凝集
剤を加えて平均粒径を0.13〜0.20μに調整したラ
テツクス状ゴム65重量部に対して、第１グラフト
成分としてスチレン５〜15重量部、メチルメタク
リレート５〜10重量部及び架橋剤0.1〜0.3重量部
よりなる混合モノマー20〜25重量部をグラフト重
合させ、更に第２グラフト成分としてメチルメタ
クリレート10〜15重量部及び架橋剤0.1〜0.3重量
部よりなる混合モノマー10〜15重量部をグラフト
重合させることによつて製造された多成分系共重
合体である。］[Scope of Claims] 1. A resin composition comprising 80 to 97% by weight of an aromatic polycarbonate resin and 3 to 20% by weight of an acrylic acid ester two-stage grafted elastic polymer. [Here, the acrylic acid ester-based two-stage grafted elastic polymer is 2-ethylhexyl acrylate 35
~60 parts by weight, 5 to 20 parts by weight of butadiene, 0 to 10 parts by weight of methyl methacrylate, and 0.65 parts by weight of a crosslinking agent, and a flocculant was added to a rubber latex obtained by emulsion polymerization to adjust the average particle size to 0.13 to 0.20μ. 20 to 25 parts by weight of a mixed monomer consisting of 5 to 15 parts by weight of styrene, 5 to 10 parts by weight of methyl methacrylate, and 0.1 to 0.3 parts by weight of a crosslinking agent are graft-polymerized to 65 parts by weight of latex rubber as the first graft component. It is a multicomponent copolymer produced by further graft polymerizing 10 to 15 parts by weight of a mixed monomer consisting of 10 to 15 parts by weight of methyl methacrylate and 0.1 to 0.3 parts by weight of a crosslinking agent as a second graft component. . ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10819480A JPS5734153A (en) | 1980-08-08 | 1980-08-08 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10819480A JPS5734153A (en) | 1980-08-08 | 1980-08-08 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5734153A JPS5734153A (en) | 1982-02-24 |
| JPH0217583B2 true JPH0217583B2 (en) | 1990-04-20 |
Family
ID=14478386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10819480A Granted JPS5734153A (en) | 1980-08-08 | 1980-08-08 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5734153A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5987395U (en) * | 1982-12-03 | 1984-06-13 | 株式会社シマノ | bicycle control lever |
| JPS59166556A (en) * | 1983-03-14 | 1984-09-19 | Mitsubishi Gas Chem Co Inc | Resin composition having improved low-temperature impact resistance |
| JPS6099159A (en) * | 1983-11-04 | 1985-06-03 | Mitsubishi Gas Chem Co Inc | Thermoplastic resin composition |
| CA2027381A1 (en) * | 1989-10-14 | 1991-04-15 | Junji Oshima | Core-shell polymer, resin composition and molded article thereof |
| DE69024779T2 (en) * | 1989-10-23 | 1996-07-18 | Takeda Chemical Industries Ltd | Core-shell polymer and its application |
| US20050147571A1 (en) * | 2003-11-05 | 2005-07-07 | Loyd Dennis D. | Ultraviolet absorption |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4842450A (en) * | 1971-10-01 | 1973-06-20 | ||
| JPS4999152A (en) * | 1972-12-06 | 1974-09-19 | ||
| JPS5085651A (en) * | 1973-11-30 | 1975-07-10 | ||
| JPS5358554A (en) * | 1976-11-05 | 1978-05-26 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
-
1980
- 1980-08-08 JP JP10819480A patent/JPS5734153A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4842450A (en) * | 1971-10-01 | 1973-06-20 | ||
| JPS4999152A (en) * | 1972-12-06 | 1974-09-19 | ||
| JPS5085651A (en) * | 1973-11-30 | 1975-07-10 | ||
| JPS5358554A (en) * | 1976-11-05 | 1978-05-26 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5734153A (en) | 1982-02-24 |
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