JPS6261062B2 - - Google Patents
Info
- Publication number
- JPS6261062B2 JPS6261062B2 JP55127539A JP12753980A JPS6261062B2 JP S6261062 B2 JPS6261062 B2 JP S6261062B2 JP 55127539 A JP55127539 A JP 55127539A JP 12753980 A JP12753980 A JP 12753980A JP S6261062 B2 JPS6261062 B2 JP S6261062B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- ethylene
- propylene
- parts
- resin composition
- 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
- 239000005062 Polybutadiene Substances 0.000 claims description 17
- 229920002857 polybutadiene Polymers 0.000 claims description 17
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 15
- 239000011342 resin composition Substances 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 229920001400 block copolymer Polymers 0.000 claims description 9
- 229920001169 thermoplastic Polymers 0.000 claims description 9
- 239000004416 thermosoftening plastic Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 8
- -1 Polypropylene Polymers 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 238000011282 treatment Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000010422 painting Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- UIERETOOQGIECD-ARJAWSKDSA-N angelic acid Chemical compound C\C=C(\C)C(O)=O UIERETOOQGIECD-ARJAWSKDSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は塗装性の改善された樹脂組成物に関
し、詳しくはエチレン−プロピレンブロツク共重
合体、エチレン−プロピレン弾性共重合体および
変性ポリブタジエンを一定割合で配合してなる塗
装性の改善された樹脂組成物に関する。
ポリプロピレン系樹脂は、機械的特性にすぐれ
また安価で成形しやすいため、広範な用途に供さ
れている。しかしながら、このポリプロピレン系
樹脂は化学的に不活性で分子構造中に極性基を持
たず、また溶剤に対する溶解性が乏しいことか
ら、接着、印刷、塗装などの成形品表面への二次
加工が困難である。
そのため従来は、かかる成形品の表面にサンド
ブラスト処理、火炎処理、コロナ放電処理あるい
はクロム酸硫酸混液による酸化処理などの特殊な
前処理を施してから塗装を行なうのが一般的であ
つた。しかしこれらの前処理は、いずれも煩雑な
操作を必要とし、しかも効果が充分でないという
欠点があり、実用性に乏しいものである。
このような状況下において最近、ポリプロピレ
ン系樹脂の塗装性を改善するために様々な方法が
開発されている。その例としては、(1)高度に結晶
化したポリプロピレンにエチレン−プロピレンラ
バーを加える方法（特公昭48−23535）、(2)ポリプ
ロピレンにポリブタジエンを加える方法（特公昭
52−42568）、(3)ポリプロピレンに１，２−ポリブ
タジエン樹脂を加える方法（特開昭54−
153854）、(4)ポリプロピレンにポリブタジエンと
スチレン系樹脂あるいはアクリル系樹脂を加える
方法（特開昭55−789、特開昭52−141854）、(5)前
記(4)の系にさらに末端に水酸基、カルボキシル
基、グリシジル基、アミノ基、アミド基等の官能
基を有するポリブタジエンを加える方法（特開昭
52−141854）および(6)ポリプロピレンにポリブタ
ジエンと末端に前述の官能基を有する１，２−ポ
リブタジエンを加える方法（特開昭52−27453）
などをあげることができる。
しかし、上記(1)の方法はさらに低温下でクロム
酸混液処理を行なわなければ塗装性の改善効果が
充分でないという欠点があり、また(2)〜(6)の方法
はいずれも塗装前にさらに溶剤による脱脂処理が
必要不可欠であるという欠点がある。
そこで本発明者らは、上記従来技術の諸問題を
解決し、特殊な前処理および脱脂処理を施さずと
も成形品表面にすぐれた塗装性を発現させること
ができ、しかも成形時の流動性が良好であると同
時に機械的強度の大きい成形品を製造することが
できる樹脂組成物を開発すべく鋭意研究を重ね
た。その結果、特定のエチレン−プロピレン共重
合体とムーニー粘度の低いエチレン−プロピレン
弾性共重合体（エチレン−プロピレンラバー）お
よび変性ポリブタジエンを一定割合で混練するこ
とにより目的とする樹脂組成物が得られることを
見出し、本発明を完成するに至つた。
すなわち本発明は(A)エチレン−プロピレン熱可
塑性非弾性ブロツク共重合体67〜91重量部、(B)ム
ーニー粘度18〜34ML1+4（100℃）のエチレン−
プロピレン弾性共重合体33〜９重量部および(C)不
飽和カルボン酸変性ポリブタジエンを前記(A)，(B)
両成分の合計100重量部に対して３〜15重量部を
混練してなる塗装性が改善された樹脂組成物を提
供するものである。
本発明の組成物の(A)成分であるエチレン−プロ
ピレン熱可塑性非弾性ブロツク共重合体のエチレ
ン単位含有量、メルトインデツクス等については
目的に応じて適宜定めればよいが、通常はエチレ
ン単位含有量20重量％以下、好ましくは６〜10重
量％とし、またメルトインデツクスは1.8〜10
ｇ／10分の範囲とするのが好ましい。メルトイン
デツクスが1.8ｇ／10分未満では流動性が小さす
ぎて不適当であり、10ｇ／10分を超えると成形品
に光沢むらが生じるという難点がある。従つてメ
ルトインデツクスは前述の如く1.8〜10ｇ／10分
が好ましいが、特に８〜10ｇ／10分のものは流動
性が適度にあつて成形品の外観が非常に美麗なも
のとなり、また1.8〜４ｇ／10分のものは成形品
の塗装後の低温耐衝撃強度が著しく大きい。
なお上述の(A)成分としてプロピレンホモポリマ
ーやエチレンとプロピレンのランダム共重合体を
用いると、得られる成形品の低温下での耐衝撃性
が劣り、本発明の目的を達成することはできな
い。
次に、本発明の組成物の(B)成分であるエチレン
−プロピレン弾性共重合体（エチレン−プロピレ
ンラバー）は、ムーニー粘度が18〜34ML1+4
（100℃）のものでなければならない。このムーニ
ー粘度が18ML1+4（100℃）未満のものでは低温
耐衝撃強度に劣り、34ML1+4（100℃）を超える
ものでは成形品表面の塗装性が悪くなる。またこ
のエチレン−プロピレンラバーのプロピレン単位
含有量は特に制限はないが通常は20〜50重量％の
範囲のものとし、好ましくは20〜35重量％のもの
とすべきである。なおこのエチレン−プロピレン
ラバーは、エチレンとプロピレンの二成分からな
る共重合体のみでなく、さらにエチリデンノルボ
ルネン、１，４−ヘキサジエンあるいはジシクロ
ペンタジエン等を含んだ三元共重合体であつても
差支えない。
さらに、本発明の組成物の(C)成分である不飽和
カルボン酸変性ポリブタジエンは、成形品の塗装
性の向上に著しく貢献するものであり、この(C)成
分の代わりに未変性のポリブタジエンを加えても
成形品の塗装性はほとんど改善されない。上記不
飽和カルボン酸変性ポリブタジエンとしては各種
のものが考えられ、ここで用いる不飽和カルボン
酸としてもマレイン酸、無水マレイン酸、無水ナ
ジツク酸、シトラコン酸、クロトン酸、イソクロ
トン酸、メサコン酸、イタコン酸、アンゲリカ
酸、ソルビン酸、無水イタコン酸、無水シトラコ
ン酸あるいはアクリル酸など様々なものをあげる
ことができる。これらのうち、特に無水マレイン
酸変性ポリブタジエンが好ましい。
上記(C)成分である不飽和カルボン酸変性ポリブ
タジエンは、様々な方法で製造することができ、
また既に市販されているものを利用してもよい。
本発明の組成物は前述した(A)，(B)，(C)の各成分
を、(A)成分67〜91重量部、(B)成分33〜９重量部お
よび(C)成分を(A)，(B)両成分の合計100重量部に対
して３〜15重量部の割合で配合し混練することに
よつて調製する。ここで(B)成分の配合量が９重量
部未満では、得られる成形品の低温耐衝撃強度が
低下し、33重量部を超えると成形性が低下すると
共に成形品の剛性ならびに耐熱性が著しく低下す
る。
また、(C)成分の配合量が上記(A)，(B)両成分の合
計量100重量部に対して３重量部未満では成形品
の塗装性向上に充分な効果がなく、一方15重量部
を超えると耐熱性が低下することとなり好ましく
ない。
本発明の組成物は、上記(A)，(B)，(C)の各成分を
一定割合で配合すればよいが、通常は一段溶融混
合法、多段溶融混合法、ドライブレンド・溶融混
合併用法等の溶融混合操作を含む様々な方法で配
合し、さらにバンバリーミキサー、コニーダー等
の各種混合機あるいは押出機等を用いて混練する
ことにより得ることができる。
このようにして得られる樹脂組成物を用いて、
射出成形、押出成形等により各成形品を製造すれ
ば、得られる成形品は、特殊な前処理を施す必要
がないのみならず、溶剤による脱脂処理さえも不
要であり、直ちに塗装可能であり、また低温下で
の耐衝撃強度もすぐれたものである。さらにこの
樹脂組成物は、適度な流動性を有するため成形性
においてもすぐれたものである。
従つて本発明の樹脂組成物は成形性（流動性）
ならびに成形品の塗装性、耐衝撃性のいずれにお
いてもバランスのとれたきわめて有用なものであ
る。また、本発明の組成物から得られる成形品
は、塗装性のみならず接着性、染色性ならびに乾
式メツキ性においてもすぐれたものである。
それ故、本発明の樹脂組成物は、電気、自動車
等の工業部品、一般機器の部品、表面装飾を施す
雑貨ならびに包装などの材料として広くかつ有効
に利用することができる。
次に本発明を実施例によりさらに詳しく説明す
る。
実施例 １
(A)成分としてエチレン−プロピレン熱可塑性非
弾性ブロツク共重合体（メルトインデツクス
（MI）9.3ｇ／10分、エチレン単位含有量9.0重量
％）を77重量部、(B)成分としてエチレン−プロピ
レンラバー（ムーニー粘度23ML1+4（100℃）、プ
ロピレン単位含有量25重量％）を23重量部および
(C)成分として無水マレイン酸変性ポリブタジエン
（出光石油化学(株)製）を前記(A)，(B)両成分の合計
100重量部に対して５重量部加え、インターミツ
クスを用いて混練し、シートペレタイザーにて粒
状物を得た。これを射出成形により板状試験片を
成形し、成形品をアクリルウレタン系塗料により
塗装し、次いでその塗装性能と耐衝撃強度を各種
実験により評価した。結果を第１表に示す。ま
た、塗装前の成形品の脱脂処理前後における臨界
表面張力の結果を第２表に示す。
実施例 ２
実施例１において使用した(A)成分であるエチレ
ン−プロピレン熱可塑性非弾性ブロツク共重合体
（MI9.3ｇ／10分、エチレン単位含有量9.0重量
％）の代わりに、MI2.5ｇ／10分、エチレン単位
含有量9.0重量％のエチレン−プロピレン熱可塑
性非弾性ブロツク共重合体を使用し、他は実施例
１と同様の操作を行なつた。結果を第１表および
第２表に示す。
比較例 １
エチレン−プロピレン熱可塑性非弾性ブロツク
共重合体（MI2.5ｇ／10分、エチレン単位含有量
9.0重量％）を77重量部およびエチレン−プロピ
レンラバー（ムーニー粘度23ML1+4（100℃）、プ
ロピレン単位含有量25重量％）を23重量部を加
え、タンブラーで混合後、単軸押出機を用い設定
温度220℃にて混練して粒状物を得た。これを実
施例１と同様に成形し塗装した。塗装性能と耐衝
撃強度および塗装前の成形品の脱脂処理前後にお
ける臨界表面張力についての実験結果を第１表お
よび第２表に示す。
比較例 ２
エチレン−プロピレン熱可塑性非弾性ブロツク
共重合体（MI9.3ｇ／10分、エチレン単位含有量
9.0重量％）を67重量部およびエチレン−プロピ
レンラバー（ムーニー粘度23ML1+4（100℃）、プ
ロピレン単位含有量25重量％）を33重量部加え、
以下は比較例１と同様の操作を行なつた。塗装性
能と耐衝撃強度および塗装前の成形品の脱脂処理
前後における臨界表面張力についての実験結果を
第１表および第２表に示す。
The present invention relates to a resin composition with improved paintability, and more particularly to a resin composition with improved paintability, which is made by blending an ethylene-propylene block copolymer, an ethylene-propylene elastic copolymer, and a modified polybutadiene in a certain proportion. relating to things. Polypropylene resins have excellent mechanical properties, are inexpensive, and are easy to mold, so they are used in a wide range of applications. However, this polypropylene resin is chemically inert, has no polar groups in its molecular structure, and has poor solubility in solvents, making it difficult to perform secondary processing on the surface of molded products such as adhesion, printing, and painting. It is. Conventionally, therefore, it has been common practice to apply special pretreatment to the surface of such molded products, such as sandblasting, flame treatment, corona discharge treatment, or oxidation treatment with a chromic acid/sulfuric acid mixture, before painting. However, all of these pretreatments require complicated operations and are not sufficiently effective, making them impractical. Under these circumstances, various methods have recently been developed to improve the paintability of polypropylene resins. Examples include (1) a method of adding ethylene-propylene rubber to highly crystallized polypropylene (Japanese Patent Publication No. 48-23535), and (2) a method of adding polybutadiene to polypropylene (Japanese Patent Publication No. 48-23535).
52-42568), (3) Method of adding 1,2-polybutadiene resin to polypropylene (Japanese Unexamined Patent Application Publication No. 1989-1999-
153854), (4) Adding polybutadiene and styrene resin or acrylic resin to polypropylene (Japanese Unexamined Patent Publication No. 55-789, Unexamined Japanese Patent Publication No. 52-141854), (5) Adding a hydroxyl group at the terminal to the system of (4) above. , a method of adding polybutadiene having functional groups such as carboxyl groups, glycidyl groups, amino groups, amide groups, etc.
52-141854) and (6) a method of adding polybutadiene and 1,2-polybutadiene having the above-mentioned functional group at the end to polypropylene (JP-A-52-27453)
etc. can be given. However, method (1) above has the disadvantage that the paintability improvement effect is not sufficient unless a chromic acid mixture treatment is performed at a low temperature, and methods (2) to (6) all require treatment before painting. A further drawback is that degreasing treatment with a solvent is essential. Therefore, the present inventors have solved the problems of the above-mentioned prior art, and have been able to achieve excellent paintability on the surface of a molded product without special pretreatment or degreasing treatment, while also improving fluidity during molding. We have conducted extensive research to develop a resin composition that can produce molded products that are both good and have high mechanical strength. As a result, the desired resin composition can be obtained by kneading a specific ethylene-propylene copolymer, an ethylene-propylene elastic copolymer with low Mooney viscosity (ethylene-propylene rubber), and modified polybutadiene at a certain ratio. They discovered this and completed the present invention. That is, the present invention comprises (A) 67 to 91 parts by weight of an ethylene-propylene thermoplastic inelastic block copolymer, and (B) ethylene-propylene having a Mooney viscosity of 18 to 34 ML 1+4 (100°C).
33 to 9 parts by weight of propylene elastic copolymer and (C) unsaturated carboxylic acid-modified polybutadiene were added to the above (A) and (B).
A resin composition with improved paintability is provided by kneading 3 to 15 parts by weight with respect to a total of 100 parts by weight of both components. The ethylene unit content, melt index, etc. of the ethylene-propylene thermoplastic inelastic block copolymer which is the component (A) of the composition of the present invention may be determined as appropriate depending on the purpose, but usually the ethylene unit content, melt index, etc. The content is 20% by weight or less, preferably 6 to 10% by weight, and the melt index is 1.8 to 10.
It is preferable to set it as the range of g/10 minutes. If the melt index is less than 1.8 g/10 minutes, the fluidity is too low and is inappropriate, and if it exceeds 10 g/10 minutes, there is a problem that uneven gloss will occur in the molded product. Therefore, as mentioned above, a melt index of 1.8 to 10 g/10 minutes is preferable, but a melt index of 8 to 10 g/10 minutes in particular has appropriate fluidity and gives a molded product a very beautiful appearance. ~4g/10min has a significantly high low-temperature impact strength after coating of the molded product. Note that if a propylene homopolymer or a random copolymer of ethylene and propylene is used as the above-mentioned component (A), the resulting molded product will have poor impact resistance at low temperatures, making it impossible to achieve the object of the present invention. Next, the ethylene-propylene elastic copolymer (ethylene-propylene rubber), which is the component (B) of the composition of the present invention, has a Mooney viscosity of 18 to 34 ML 1+4.
(100℃). If the Mooney viscosity is less than 18ML 1+4 (100°C), the low-temperature impact strength will be poor, and if it exceeds 34ML 1+4 (100°C), the paintability of the molded product surface will be poor. The content of propylene units in this ethylene-propylene rubber is not particularly limited, but it should normally be in the range of 20 to 50% by weight, preferably 20 to 35% by weight. Note that this ethylene-propylene rubber is not only a copolymer consisting of two components of ethylene and propylene, but also a terpolymer containing ethylidene norbornene, 1,4-hexadiene, dicyclopentadiene, etc. do not have. Furthermore, unsaturated carboxylic acid-modified polybutadiene, which is component (C) of the composition of the present invention, significantly contributes to improving the paintability of molded products, and unmodified polybutadiene can be used instead of component (C). Even if it is added, the paintability of the molded product will hardly be improved. Various types of unsaturated carboxylic acid-modified polybutadiene can be considered as the unsaturated carboxylic acid-modified polybutadiene, and the unsaturated carboxylic acids used here include maleic acid, maleic anhydride, nadic anhydride, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid, and itaconic acid. , angelic acid, sorbic acid, itaconic anhydride, citraconic anhydride or acrylic acid. Among these, maleic anhydride-modified polybutadiene is particularly preferred. The unsaturated carboxylic acid-modified polybutadiene, component (C) above, can be produced by various methods.
Alternatively, those already commercially available may be used. The composition of the present invention contains each of the above-mentioned components (A), (B), and (C), 67 to 91 parts by weight of component (A), 33 to 9 parts by weight of component (B), and component (C) ( It is prepared by blending and kneading 3 to 15 parts by weight based on a total of 100 parts by weight of both components A) and (B). If the amount of component (B) is less than 9 parts by weight, the low-temperature impact strength of the resulting molded product will decrease, and if it exceeds 33 parts by weight, the moldability will decrease and the rigidity and heat resistance of the molded product will significantly decrease. descend. Furthermore, if the blending amount of component (C) is less than 3 parts by weight with respect to the total amount of both components (A) and (B) above 100 parts by weight, it will not be sufficiently effective in improving the paintability of the molded product; If it exceeds 50%, the heat resistance will deteriorate, which is not preferable. The composition of the present invention may be prepared by blending each of the above components (A), (B), and (C) in a fixed ratio, but usually a single-stage melt mixing method, a multi-stage melt mixing method, or a combination of dry blending and melt mixing is used. It can be obtained by blending by various methods including a melt mixing operation such as a method, and further kneading using various mixers such as a Banbury mixer or a co-kneader, or an extruder. Using the resin composition obtained in this way,
If each molded product is manufactured by injection molding, extrusion molding, etc., the resulting molded product not only does not require special pretreatment, but also does not require degreasing with a solvent, and can be painted immediately. It also has excellent impact resistance at low temperatures. Furthermore, this resin composition has appropriate fluidity and therefore has excellent moldability. Therefore, the resin composition of the present invention has good moldability (fluidity).
In addition, it is extremely useful in terms of both the paintability and impact resistance of molded products, which are well-balanced. Moreover, the molded articles obtained from the composition of the present invention are excellent not only in paintability but also in adhesion, dyeability and dry plating properties. Therefore, the resin composition of the present invention can be widely and effectively used as a material for industrial parts such as electrical equipment and automobiles, parts for general equipment, miscellaneous goods with surface decoration, and packaging. Next, the present invention will be explained in more detail with reference to Examples. Example 1 77 parts by weight of ethylene-propylene thermoplastic inelastic block copolymer (melt index (MI) 9.3 g/10 min, ethylene unit content 9.0% by weight) as component (A), and as component (B) 23 parts by weight of ethylene-propylene rubber (Mooney viscosity 23ML 1+4 (100℃), propylene unit content 25% by weight) and
As component (C), maleic anhydride-modified polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.) is added to the sum of both components (A) and (B) above.
5 parts by weight per 100 parts by weight were added, kneaded using an intermix, and granules were obtained using a sheet pelletizer. This was molded into a plate-shaped test piece by injection molding, and the molded product was painted with an acrylic urethane paint, and then its coating performance and impact resistance strength were evaluated by various experiments. The results are shown in Table 1. Further, Table 2 shows the results of the critical surface tension before and after the degreasing treatment of the molded product before painting. Example 2 Instead of the ethylene-propylene thermoplastic inelastic block copolymer (MI9.3g/10 min, ethylene unit content 9.0% by weight) used in Example 1 as component (A), MI2.5g/1 was used. The same procedure as in Example 1 was carried out except that an ethylene-propylene thermoplastic inelastic block copolymer having an ethylene unit content of 9.0% by weight was used. The results are shown in Tables 1 and 2. Comparative Example 1 Ethylene-propylene thermoplastic inelastic block copolymer (MI2.5g/10min, ethylene unit content
Add 77 parts by weight of 9.0% by weight) and 23 parts by weight of ethylene-propylene rubber (Mooney viscosity 23ML 1+4 (100℃), propylene unit content 25% by weight), mix in a tumbler, and then use a single screw extruder. The mixture was kneaded at a set temperature of 220°C to obtain granules. This was molded and painted in the same manner as in Example 1. Tables 1 and 2 show the experimental results regarding coating performance, impact strength, and critical surface tension before and after degreasing of the molded product before coating. Comparative Example 2 Ethylene-propylene thermoplastic inelastic block copolymer (MI9.3g/10min, ethylene unit content
9.0% by weight) and 33 parts by weight of ethylene-propylene rubber (Mooney viscosity 23ML 1+4 (100°C), propylene unit content 25% by weight),
The following operations were the same as in Comparative Example 1. Tables 1 and 2 show the experimental results regarding coating performance, impact strength, and critical surface tension before and after degreasing of the molded product before coating.
【表】【table】
Claims (1)
ツク共重合体67〜91重量部、(B)ムーニー粘度18〜
34ML1+4（100℃）のエチレン−プロピレン弾性
共重合体33〜９重量部および(C)不飽和カルボン酸
変性ポリブタジエンを前記(A)，(B)両成分の合計
100重量部に対して３〜15重量部を混練してなる
塗装性が改善された樹脂組成物。 ２ (A)エチレン−プロピレン熱可塑性非弾性ブロ
ツク共重合体が、エチレン単位含有量20重量％以
下であり、かつメルトインデツクス1.8〜10ｇ／
10分である特許請求の範囲第１項記載の樹脂組成
物。 ３ (B)エチレン−プロピレン弾性共重合体が、プ
ロピレン単位含有量20〜50重量％である特許請求
の範囲第１項記載の樹脂組成物。 ４ (C)不飽和カルボン酸変性ポリブタジエンが、
無水マレイン酸変性ポリブタジエンである特許請
求の範囲第１項記載の樹脂組成物。[Claims] 1 (A) ethylene-propylene thermoplastic inelastic block copolymer 67 to 91 parts by weight, (B) Mooney viscosity 18 to 91 parts by weight
Add 33 to 9 parts by weight of 34ML 1+4 (100℃) ethylene-propylene elastic copolymer and (C) unsaturated carboxylic acid-modified polybutadiene to the total of both components (A) and (B).
A resin composition with improved paintability obtained by kneading 3 to 15 parts by weight per 100 parts by weight. 2 (A) The ethylene-propylene thermoplastic inelastic block copolymer has an ethylene unit content of 20% by weight or less and a melt index of 1.8 to 10 g/
The resin composition according to claim 1, which takes 10 minutes. 3. The resin composition according to claim 1, wherein the ethylene-propylene elastic copolymer (B) has a propylene unit content of 20 to 50% by weight. 4 (C) unsaturated carboxylic acid-modified polybutadiene,
The resin composition according to claim 1, which is maleic anhydride-modified polybutadiene.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12753980A JPS5751734A (en) | 1980-09-13 | 1980-09-13 | Resin composition with improved paintability |
| US06/294,399 US4371662A (en) | 1980-09-01 | 1981-08-19 | Three-component resin compositions having improved coating properties |
| CA000384319A CA1174783A (en) | 1980-09-01 | 1981-08-20 | Resin composition including ethylene-propylene block copolymer, ethylene-propylene rubber and styrene- based elastomer or unsaturated carboxylic acid- modified polybutadiene |
| DE3133510A DE3133510C2 (en) | 1980-09-01 | 1981-08-25 | Resin composition with improved coating properties |
| GB8126131A GB2085451B (en) | 1980-09-01 | 1981-08-27 | Paintable ethylene-polypropylene resin moulding compositions |
| FR8116556A FR2489348B1 (en) | 1980-09-01 | 1981-08-31 | RESIN COMPOSITIONS HAVING IMPROVED COATING PROPERTIES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12753980A JPS5751734A (en) | 1980-09-13 | 1980-09-13 | Resin composition with improved paintability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5751734A JPS5751734A (en) | 1982-03-26 |
| JPS6261062B2 true JPS6261062B2 (en) | 1987-12-19 |
Family
ID=14962509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12753980A Granted JPS5751734A (en) | 1980-09-01 | 1980-09-13 | Resin composition with improved paintability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5751734A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2541387B2 (en) * | 1991-01-29 | 1996-10-09 | 豊田合成株式会社 | Polypropylene resin molded product with excellent coating film adhesion |
| JP2009173761A (en) * | 2008-01-23 | 2009-08-06 | Kurako:Kk | Method for preparing modified polyolefin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948469A (en) * | 1972-02-07 | 1974-05-10 | ||
| JPS5113192A (en) * | 1974-07-23 | 1976-02-02 | Yoshio Sugo | REEZAGENOKOGENTOSHITEMOCHIITA TANSHOTO |
| JPS5318652A (en) * | 1976-08-05 | 1978-02-21 | Idemitsu Petrochemical Co | Thermoplastic resin composition |
-
1980
- 1980-09-13 JP JP12753980A patent/JPS5751734A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948469A (en) * | 1972-02-07 | 1974-05-10 | ||
| JPS5113192A (en) * | 1974-07-23 | 1976-02-02 | Yoshio Sugo | REEZAGENOKOGENTOSHITEMOCHIITA TANSHOTO |
| JPS5318652A (en) * | 1976-08-05 | 1978-02-21 | Idemitsu Petrochemical Co | Thermoplastic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5751734A (en) | 1982-03-26 |
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