JPS6342930B2 - - Google Patents
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- Publication number
- JPS6342930B2 JPS6342930B2 JP56112978A JP11297881A JPS6342930B2 JP S6342930 B2 JPS6342930 B2 JP S6342930B2 JP 56112978 A JP56112978 A JP 56112978A JP 11297881 A JP11297881 A JP 11297881A JP S6342930 B2 JPS6342930 B2 JP S6342930B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- weight
- crystalline
- aspect ratio
- average particle
- 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
- 229920000098 polyolefin Polymers 0.000 claims description 28
- 229920001971 elastomer Polymers 0.000 claims description 22
- 239000005060 rubber Substances 0.000 claims description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 19
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 18
- 239000004711 α-olefin Substances 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 claims description 12
- 239000000454 talc Substances 0.000 claims description 11
- 229910052623 talc Inorganic materials 0.000 claims description 11
- 239000010445 mica Substances 0.000 claims description 10
- 229910052618 mica group Inorganic materials 0.000 claims description 10
- 239000000378 calcium silicate Substances 0.000 claims description 8
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 8
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 8
- 229920005604 random copolymer Polymers 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 14
- -1 polyethylene Polymers 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 229920002943 EPDM rubber Polymers 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001179 medium density polyethylene Polymers 0.000 description 3
- 239000004701 medium-density polyethylene Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- 101710143098 Paralytic peptide 1 Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 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
- 238000004519 manufacturing process Methods 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
- 239000003607 modifier Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Description
本発明は、結晶性ポリオレフインの剛性、低温
耐衝撃性、可飾性及び成形寸法精度の改善に関す
る。さらに詳細には、結晶性ポリオレフイン、エ
チレン―α―オレフイン共重合体ゴム、タルク、
マイカまたは繊維結晶性ケイ酸カルシウム及び変
性ポリオレフインとからなるポリオレフイン組成
物に関するものである。
従来、ポリオレフイン、例えばポリエチレン、
ポリプロピレン等は種々の優れた物理的性質、機
械的性質を有する成形品、フイルム、繊維等とし
て一般用から工業用の分野迄広く利用されてい
る。しかしながら、このようなポリオレフインは
その物質自体に起因する欠点があり、そのままで
は利用分野によつては制限されるところがある。
例えば、ポリプロピレンを自動車部品用途等の工
業用の分野で用いる場合には、寸法精度が良好で
高い剛性度と衝撃強度が要求されるために、プロ
ピレン―エチレンブロツクコポリマーあるいは無
機充填剤強化ポリプロピレン等が用いられてい
る。しかしながら、プロピレン―エチレンブロツ
ク共重合体は、常温付近での耐衝撃性は改善され
るものの低温での耐衝撃性は改善されず、塗装、
メツキ、接着等の可飾性及び成形収縮率、ソリ等
の成形時の寸法精度も低い。また、ポリプロピレ
ンに無機充填剤を配合すると剛性や寸法精度は改
善されるが、低温耐衝撃性が著しく低下して脆く
なつてしまうという欠点がある。
したがつて、ポリオレフインに衝撃強度改良材
を配合した組成物の提案がなされている。例え
ば、ポリオレフイン89〜20重量％、合成ゴムまた
は天然ゴム１〜20重量％及び粉末状タルク系充填
剤10〜60重量％からなる熱可塑性樹脂組成物（特
開昭51−136735号公報）、エチレン含有量20重量
％以下、メルトフローインデツクス（以下MI）
0.5〜10の結晶性エチレン―プロピレンブロツク
共重合体50〜90重量％、MI0.2〜10の無定形エチ
レン―α―オレフイン共重合体５〜20重量％及び
タルク５〜40重量％よりなる耐衝撃性樹脂組成物
（特開昭53−64257号公報）等が知られている。
しかしながら、これらの先行技術において耐衝
撃性は改善されてはいるものの剛性、低温耐衝撃
性、塗装性、成形時の寸法精度、ウエルド強度等
は必ずしも十分とはいえない。
本発明者らは、このような特性をさらに向上さ
せるべくポリオレフインの改質方法について種々
の検討を行つた結果、結晶ポリオレフイン、エチ
レン―α―オレフイン共重合体ゴム及びタルク、
マイカ、繊維結晶性ケイ酸カルシウムの充填剤と
からなる組成物に、不飽和カルボン酸またはその
誘導体で変性したポリオレフインを配合すること
により、機械的強度を低下させることなく耐衝撃
性、可飾性、成形時の寸法精度、ウエルド強度等
をさらに向上することを見出したのである。
すなわち、本発明は(1)エチレン含有量20重量％
以下の結晶性エチレン―プロピレンブロツクまた
はランダム共重合体７〜87重量％、(2)エチレン含
有量20〜90重量％でムーニー粘度10〜120のエチ
レン―α―オレフイン共重合体ゴム５〜50重量
％、(3)結晶性ポリオレフインおよび／またはエチ
レン―α―オレフイン共重合体ゴムを不飽和カル
ボン酸またはその誘導体で変性してなる変性ポリ
オレフイン３〜50重量％、および(4)平均粒子径
0.5〜15μでアスペクト比３〜10のタルク、平均粒
子１〜200μでアスペクト比10〜100のマイカまた
は平均粒子径１〜100μでアスペクト比３〜30の
繊維結晶性ケイ酸カルシウム５〜40重量％とから
なるポリオレフイン組成物を提供するものであ
る。
本発明において用いられるエチレン含有量が20
重量％以下の結晶性エチレン―プロピレンブロツ
クまたはランダム共重合体は、MI0.5〜50ｇ／10
分のものが好ましく、必要に応じて低密度ポリエ
チレン（以下LDPEという）、線状低密度ポリエ
チレン（以下Ｌ―LDPEという）、中密度ポリエ
チレン（以下MDPEという）もしくは高密度ポ
リエチレン（以下HDPEという）等のポリエチレ
ンを少量含有してもよい。
本発明に用いられるエチレン―α―オレフイン
共重合体ゴムとしては、、エチレンとα―オレフ
イン、例えばプロピレン、１―ブテン、１―ヘキ
センなどとの共重合体ゴム、またはエチレン―プ
ロピレンの系に第三成分として非共役ジエン類、
例えばエチリデンノルボルネン、ジシクロペンタ
ジエン等を共重合させた三元共重合体ゴム（以下
EPDM）等があげられる。これらのうちでは、
エチレン―プロピレン共重合体ゴム（以下
EPR）、またはEPDMが好ましい。そして、これ
らエチレン―α―オレフイン共重合体ゴムは、エ
チレン含有量が20〜90重量％、ムーニー粘度
（JIS Ｋ―6300 M′L1＋４ 100℃以下同）が10〜
120のものが用いられる。
本発明において不飽和カルボン酸またはその誘
導体で変性されるポリオレフインは、結晶性ポリ
オレフインまたはエチレン―α―オレフイン共重
合体ゴムであり、この結晶性ポリオレフインとし
てはLDPE、Ｌ―LDPE、MDPE、HDPE、ポリ
プロピレン、ポリ―１―ブテン、ポリ―４―メチ
ル―１―ペンテン、エチレン―プロピレンブロツ
クまたはランダム共重合体、エチレン―１―ブテ
ン共重合体、プロピレン―１―ブテン共重合体、
エチレン―酢酸ビニル共重合体及びこれらの混合
物等が用いられ、エチレン―α―オレフイン共重
合体ゴムとしては前記のものが用いられる。これ
ら結晶性ポリオレフインまたはエチレン―α―オ
レフイン共重合体ゴムの好ましい例としては、
LDPE、HDPE、ポリプロピレン、エチレン含有
量20重量％以下のエチレン―プロピレンのブロツ
クまたはランダムの共重合体、EPR EPDM、エ
チレン―１―ブテン共重合体ゴム等があげられ
る。結晶性ポリオレフインまたはエチレン―α―
オレフイン共重合体ゴムの変性に用いられる不飽
和カルボン酸としては、例えばアクリル酸、メタ
クリル酸、マレイン酸、フマル酸、シトラコン
酸、イタコン酸、エンド―ビ―シクロ〔２，２，
１〕―１，４，５，６，７，７―ヘキサクロロ―
５―ヘプテン―２，３ジカルボン酸、エンド―ビ
―シクロ―〔２，２，１〕―５―ヘプテン―２，
３―ジカルボン酸、シス―４―シクロヘキセン―
１，２―ジカルボン酸等があげられる。また、不
飽和カルボン酸の誘導体としては、酸無水物、エ
ステルがあげられ、例えば無水マレイン酸、無水
シトラコン酸、エンドビシクロ―〔２，２，１〕
―１，４，５，６，７，７―ヘキサクロロ―５―
ヘプテン―２，３無水ジカルボン酸、エンド―ビ
―シクロ―〔２，２，１〕―５―ヘプテン―２，
３無水ジカルボン酸、シス―４―シクロヘキセン
―１，２無水ジカルボン酸、アクリル酸メチル、
メタクリル酸メチル、アクリル酸エチル、メタク
リル酸エチル、アクリル酸ブチル、メタクリル酸
ブチル、マレイン酸エステル（モノエステル、ジ
エステル）等があげられる。これら不飽和カルボ
ン酸またはその誘導体の中では、エンド―ビ―シ
クロ―〔２，２，１〕―５―ヘプテン―２，３無
水ジカルボン酸または無水マレイン酸を使用する
のが好ましい。
該ポリオレフインまたはエチレン―α―オレフ
イン共重合体ゴムを変性するには公知の種々の方
法を採用することができる。例えば、ポリオレフ
インと不飽和カルボン酸またはその誘導体を溶媒
の存在下、または不存在下で反応開始剤を添加し
てまたは添加せずに加熱することによつて製造で
きる。
ここで、ポリオレフインに付加する不飽和カル
ボン酸またはその誘導体の付加量は0.01〜３重量
％が好ましい。
本発明に用いられる充填剤のタルクは、平均粒
子径が0.5〜15μでアスペクト比が３〜10、マイカ
はマスコバイト系、フロゴパイト系、スゾライト
系等があるが、いれでもよく平均粒子径が１〜
200μでアスペクト比が10〜100、繊維結晶性ケイ
酸カルシウムは平均粒子径が１〜100μでアスペ
クト比が３〜30のものがあげられる。これらのう
ちでもアスペクト比の高いものの配合が好まし
く、特にアスペクト比３以上のものの配合が好ま
しい。このアスペクト比の高い充填剤の配合は、
エチレン―α―オレフイン共重合体ゴムの配合に
よる剛性の低下を防止するために有効である。な
お、これら充填剤は、シランあるいはチタンカツ
プリング剤等で表面処理をしてもしなくてもよい
が、表面処理を行つた方がよい結果を与える。
また、これらの各充填剤の配合による組成物の
特徴は、耐衝撃性を改善すると共に、タルクの場
合は塗膜剥離強度、マイカの場合は曲げ弾性率、
成形時の寸法精度、塗膜剥離強度、繊維結晶性ケ
酸カルシウムの場合は塗膜剥離強度、ウエルド強
度等の改善に特に優れるものである。
本発明の組成物中に含まれる特に好ましい各成
分の配合割合は、結晶性エチレン―プロピレンブ
ロツクまたはランダム共重合体７〜87重量％、エ
チレン―α―オレフイン共重合体ゴム５〜50重量
％、変性ポリオレフイン３〜50重量％、充填剤５
〜40重量％からなるものである。
上記の含有量において、エチレン―α―オレフ
イン共重合体ゴムが５重量％未満では耐衝撃強
度、可飾性が改善されず、一方50重量％を越える
場合は樹脂軟化温度の低下による成形性が悪く、
また剛性が低下する。次に、変性ポリオレフイン
が３重量％未満の場合は剛性、耐衝撃性、可飾性
及び成形時の寸法精度をさらに向上させる効果が
なく、一方50重量％を越える場合は助長効果がな
く、逆に曲げ弾性率の低下などがあり好ましくな
い。また、充填剤が５重量％未満の場合は成形収
縮率、ソリ等の成形時の寸法精度及び剛性が改善
されず、一方40重量％を越える場合は成形加工性
が悪くなる。
本発明の組成物を製造する方法としては、結晶
性エチレン―プロピレンブロツクまたはランダム
共重合体、変性ポリオレフイン、エチレン―α―
オレフイン共重合体ゴム及び無機充填剤の各成分
を、例えばヘンシエルミキサー、高速ミキサー等
で予備混合し、この混合物をバンバリーミキサ
ー、ロール、二軸押出機等の混練機を用いて加熱
溶融状態で混練する等があげられるが必ずしもこ
の方法には限定されない。なお、各成分の配合混
練に際し、酸化防止剤、紫外線吸収剤等の安定
剤、滑剤、帯電防止剤、顔料等の各添加剤を配合
することができる。
以上、本発明のポリオレフイン組成物は、射出
成形において成形加工性に優れ金型からの離型も
よく、押出成形あるいはブロー成形も可能であ
る。そして、得られる成形品は低温耐衝撃性、可
飾性能（塗装、メツキ等）、寸法安定性に優れ、
ソリ、ヒケが少く種々の分野に用いることができ
るが、特に自動車のバンパーとして好適である。
以下に本発明を実施例でさらに具体的に説明す
る。なお、実施例における各成分の％は重量を示
し、試験法は次のとおりである。
(1) MI ASTM Ｄ―1238
(2) 曲げ弾性率 ASTM Ｄ―790
(3) アイゾツト衝撃強度 ASTM Ｄ―256
3.2mm厚試験片、 ノツチ付
(4) 成形収縮率
350×100×３mmのシートを成形後24時間20℃
恒温室に放置し測定する。
(5) 塗膜剥離強度
70×120×３mmのシートを成形して脱脂し、
ポリプロピレン用のプライマー、ウレタントツ
プペイントを用い常法で塗装焼付し得られた塗
装プレートの塗膜をインストローン万能試験機
を用いた、10mm巾にて180゜剥離させ、得られた
強度を剥離強度とした。
(6) ソ リ
直径150mm、厚み1.5mmの円板をセンターダイ
レクトゲートにて成形し、24時間放置後に平板
上におき、平板よりの変形高さをソリとした。
(7) ウエルド強度保持率
ASTMD―638の１号引張試験片をその長手
方向両端よりサイドゲートにて射出成形する。
得られた試験片をASTM Ｄ―638により引張
試験し、得られた強度をウエルド強度とした。
実施例 １
ポリプロピレンホモポリマー（MI＝1.0）また
はエチレン―プロピレンブロツク共重合体（MI
＝1.0、エチレン含有量＝7.0％）100重量部にエ
ンド―ビ―シクロ―〔２，２，１〕―５―ヘプテ
ン―２，３―ジカルボン酸無水物（以下無水ハイ
ミツク酸）１重量部及び２，５―ジメチル―２，
５―ジ―（タ―シヤリ―ブチルペルオキシ）ヘキ
シン―３を0.5重量部を加え常温で予備混合し、
混合物を押出機に供給し230℃で溶融混練して押
出し変性ポリプロピレン（以下変性PP―Ｉ）ま
たは変性エチレン―プロピレンブロツク共重合体
（以下変性PP―）を得た。ハイミツク酸の含有
量は各1.0重量％であつた。
結晶性エチレン―プロピレンブロツク共重合体
（）（MI＝15、エチレン含有量＝７％）、結晶性
エチレン―プロピレンランダム共重合体（MI＝
９、エチレン含有量２％）、上記の無水ハイミツ
ク酸変性PP、HDPE（MI＝0.3、密度0.960）、
LDPE（MI＝９、密度＝0.912）、EPR（エチレン
含有量＝75％、ムーニー粘度＝70）、EPDM（エ
チレン含有量＝50％、第三成分＝エチリデンノル
ボルネン、ムーニー粘度＝105）及びタルク（平
均粒子径10μ、アスペクト比３〜10）を表―１に
示す各実験番号の組合せで配合して高速ミキサー
で混合し、得られた混合物を２軸混練機を用いて
シリンダー温度200〜250℃で溶融混練機ペレツト
を得た。得られたペレツトん温度230℃、圧力900
Kg／cm2の射出成形条件で各試験片を成形した。得
られた各試験片について曲げ弾性率、アイゾツト
衝撃強度、成形収縮率、塗膜剥離強度、ソリ及び
ウエルド強度保持率を測定し、その結果を表―１
に示した（実験番号１〜７）。
比較のために上記において、変性PPを配合し
ないもの、平均粒子径10μ、アスペクト比３未満
のタルクを配合した場合及びEPR又はEPDMを
配合しない場合についての各物性について表―１
に併記した。（実験番号８〜13）。
The present invention relates to improvements in the rigidity, low-temperature impact resistance, decorative properties, and molding dimensional accuracy of crystalline polyolefins. More specifically, crystalline polyolefin, ethylene-α-olefin copolymer rubber, talc,
The present invention relates to a polyolefin composition comprising mica or fibrous crystalline calcium silicate and a modified polyolefin. Conventionally, polyolefins, such as polyethylene,
Polypropylene and the like are widely used in general to industrial fields as molded products, films, fibers, and the like having various excellent physical and mechanical properties. However, such polyolefins have drawbacks due to the substance itself, and its use as it is may be limited depending on the field of use.
For example, when polypropylene is used in industrial fields such as automobile parts, good dimensional accuracy and high rigidity and impact strength are required, so propylene-ethylene block copolymers or inorganic filler-reinforced polypropylene are used. It is used. However, although the propylene-ethylene block copolymer improves its impact resistance near room temperature, it does not improve its impact resistance at low temperatures.
Decorative properties such as plating and adhesion, molding shrinkage rate, and dimensional accuracy during molding such as warping are also low. Further, when an inorganic filler is added to polypropylene, the rigidity and dimensional accuracy are improved, but there is a drawback that the low-temperature impact resistance is significantly reduced and the material becomes brittle. Therefore, proposals have been made for compositions in which impact strength modifiers are blended with polyolefins. For example, a thermoplastic resin composition consisting of 89 to 20% by weight of polyolefin, 1 to 20% by weight of synthetic rubber or natural rubber, and 10 to 60% by weight of powdered talc filler (Japanese Patent Application Laid-Open No. 136735/1989), ethylene Content 20% by weight or less, melt flow index (hereinafter referred to as MI)
50 to 90% by weight of a crystalline ethylene-propylene block copolymer with an MI of 0.5 to 10, 5 to 20% by weight of an amorphous ethylene-α-olefin copolymer with an MI of 0.2 to 10, and 5 to 40% by weight of talc. Impact resin compositions (JP-A-53-64257) and the like are known. However, although impact resistance has been improved in these prior art techniques, rigidity, low-temperature impact resistance, paintability, dimensional accuracy during molding, weld strength, etc. are not necessarily sufficient. The present inventors have conducted various studies on methods for modifying polyolefin in order to further improve such properties, and as a result, we have developed crystalline polyolefin, ethylene-α-olefin copolymer rubber, talc,
By blending a polyolefin modified with an unsaturated carboxylic acid or its derivative into a composition consisting of mica and a fiber crystalline calcium silicate filler, impact resistance and decorative properties are achieved without reducing mechanical strength. It was discovered that dimensional accuracy during molding, weld strength, etc. can be further improved. That is, the present invention has (1) an ethylene content of 20% by weight;
7 to 87% by weight of the following crystalline ethylene-propylene block or random copolymers; (2) 5 to 50% by weight of ethylene-α-olefin copolymer rubber with an ethylene content of 20 to 90% and a Mooney viscosity of 10 to 120; %, (3) 3 to 50% by weight of a modified polyolefin obtained by modifying a crystalline polyolefin and/or ethylene-α-olefin copolymer rubber with an unsaturated carboxylic acid or its derivative, and (4) average particle size.
Talc with an aspect ratio of 3 to 10 with an average particle size of 0.5 to 15 μ, mica with an average particle size of 1 to 200 μ and an aspect ratio of 10 to 100, or 5 to 40% by weight of fibrous crystalline calcium silicate with an average particle size of 1 to 100 μ and an aspect ratio of 3 to 30. The present invention provides a polyolefin composition comprising: The ethylene content used in the present invention is 20
Crystalline ethylene-propylene block or random copolymer with weight percent or less has an MI of 0.5 to 50 g/10
It is preferable to use low density polyethylene (hereinafter referred to as LDPE), linear low density polyethylene (hereinafter referred to as L-LDPE), medium density polyethylene (hereinafter referred to as MDPE) or high density polyethylene (hereinafter referred to as HDPE), etc. as necessary. may contain a small amount of polyethylene. The ethylene-α-olefin copolymer rubber used in the present invention is a copolymer rubber of ethylene and α-olefin, such as propylene, 1-butene, 1-hexene, etc., or a rubber based on an ethylene-propylene system. non-conjugated dienes as three components,
For example, terpolymer rubber (hereinafter referred to as
EPDM) etc. Among these,
Ethylene-propylene copolymer rubber (hereinafter referred to as
EPR) or EPDM is preferred. These ethylene-α-olefin copolymer rubbers have an ethylene content of 20 to 90% by weight and a Mooney viscosity (JIS K-6300 M'L1+4 100℃ or less) of 10 to 90%.
120 are used. In the present invention, the polyolefin modified with an unsaturated carboxylic acid or a derivative thereof is a crystalline polyolefin or an ethylene-α-olefin copolymer rubber, and examples of the crystalline polyolefin include LDPE, L-LDPE, MDPE, HDPE, and polypropylene. , poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene block or random copolymer, ethylene-1-butene copolymer, propylene-1-butene copolymer,
Ethylene-vinyl acetate copolymers and mixtures thereof are used, and the ethylene-α-olefin copolymer rubbers mentioned above are used. Preferred examples of these crystalline polyolefins or ethylene-α-olefin copolymer rubbers include:
Examples include LDPE, HDPE, polypropylene, ethylene-propylene block or random copolymers with an ethylene content of 20% by weight or less, EPR EPDM, and ethylene-1-butene copolymer rubber. Crystalline polyolefin or ethylene-α-
Examples of unsaturated carboxylic acids used for modifying olefin copolymer rubber include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, endo-bicyclo[2,2,
1]-1,4,5,6,7,7-hexachloro-
5-heptene-2,3 dicarboxylic acid, endo-bicyclo-[2,2,1]-5-heptene-2,
3-dicarboxylic acid, cis-4-cyclohexene
Examples include 1,2-dicarboxylic acid. In addition, examples of derivatives of unsaturated carboxylic acids include acid anhydrides and esters, such as maleic anhydride, citraconic anhydride, endobicyclo[2,2,1]
-1,4,5,6,7,7-hexachloro-5-
heptene-2,3 dicarboxylic anhydride, endo-bicyclo-[2,2,1]-5-heptene-2,
3 dicarboxylic anhydride, cis-4-cyclohexene-1,2 dicarboxylic anhydride, methyl acrylate,
Examples include methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, maleate ester (monoester, diester), and the like. Among these unsaturated carboxylic acids or derivatives thereof, it is preferable to use endo-bicyclo-[2,2,1]-5-heptene-2,3 dicarboxylic anhydride or maleic anhydride. Various known methods can be employed to modify the polyolefin or ethylene-α-olefin copolymer rubber. For example, it can be produced by heating a polyolefin and an unsaturated carboxylic acid or a derivative thereof in the presence or absence of a solvent, with or without the addition of a reaction initiator. Here, the amount of the unsaturated carboxylic acid or its derivative added to the polyolefin is preferably 0.01 to 3% by weight. Talc, the filler used in the present invention, has an average particle size of 0.5 to 15μ and an aspect ratio of 3 to 10, and mica includes muscovite, phlogopite, and szolite types, but any of them may be used. ~
200μ and an aspect ratio of 10 to 100, and fibrous crystalline calcium silicate has an average particle size of 1 to 100μ and an aspect ratio of 3 to 30. Among these, those with a high aspect ratio are preferred, and those with an aspect ratio of 3 or more are particularly preferred. This high aspect ratio filler formulation is
This is effective in preventing a decrease in rigidity due to the combination of ethylene-α-olefin copolymer rubber. Note that these fillers may or may not be surface-treated with silane or titanium coupling agents, but better results will be obtained if surface-treated. In addition, the characteristics of compositions created by blending each of these fillers are that they improve impact resistance, as well as film peel strength in the case of talc, flexural modulus in the case of mica,
It is particularly excellent in improving dimensional accuracy during molding, coating peel strength, and in the case of fibrous crystalline calcium silicate, coating peel strength, weld strength, etc. Particularly preferred blending ratios of each component contained in the composition of the present invention are: 7 to 87% by weight of crystalline ethylene-propylene block or random copolymer, 5 to 50% by weight of ethylene-α-olefin copolymer rubber, Modified polyolefin 3-50% by weight, filler 5
~40% by weight. In the above content, if the ethylene-α-olefin copolymer rubber is less than 5% by weight, impact strength and decorative properties will not be improved, while if it exceeds 50% by weight, moldability will decrease due to a decrease in resin softening temperature. Bad,
Moreover, rigidity decreases. Next, if the modified polyolefin content is less than 3% by weight, it will not have the effect of further improving rigidity, impact resistance, decoration, and dimensional accuracy during molding, while if it exceeds 50% by weight, there will be no promoting effect, and vice versa. This is undesirable because it causes a decrease in flexural modulus. Furthermore, if the filler content is less than 5% by weight, the molding shrinkage rate, dimensional accuracy such as warping, and rigidity during molding will not be improved, while if it exceeds 40% by weight, moldability will deteriorate. The method for producing the composition of the present invention includes crystalline ethylene-propylene block or random copolymer, modified polyolefin, ethylene-α-
The olefin copolymer rubber and inorganic filler components are premixed using a Henschel mixer, high-speed mixer, etc., and this mixture is heated and melted using a kneading machine such as a Banbury mixer, roll, or twin-screw extruder. Examples include kneading, but are not necessarily limited to this method. In addition, when blending and kneading each component, various additives such as antioxidants, stabilizers such as ultraviolet absorbers, lubricants, antistatic agents, pigments, etc. can be blended. As described above, the polyolefin composition of the present invention has excellent molding processability in injection molding, and can be easily released from a mold, and can also be extruded or blow molded. The resulting molded product has excellent low-temperature impact resistance, decorative performance (painting, plating, etc.), and dimensional stability.
It has few warps and sink marks and can be used in various fields, but is particularly suitable for automobile bumpers. The present invention will be explained in more detail below using Examples. In addition, the percentage of each component in the examples indicates the weight, and the test method is as follows. (1) MI ASTM D-1238 (2) Flexural modulus ASTM D-790 (3) Izot impact strength ASTM D-256 3.2mm thick test piece, with notch (4) Molding shrinkage rate 350 x 100 x 3 mm sheet 20℃ for 24 hours after molding
Leave it in a constant temperature room and measure it. (5) Paint peel strength: Form a sheet of 70 x 120 x 3 mm, degrease it,
Using a primer for polypropylene and urethane top paint, the paint film of the painted plate obtained by baking is peeled off at 180° in a 10 mm width using an Instron universal testing machine, and the strength obtained is calculated as the peel strength. And so. (6) Sled A disk with a diameter of 150 mm and a thickness of 1.5 mm was formed using a center direct gate, and after being left for 24 hours, it was placed on a flat plate and the deformed height above the flat plate was warped. (7) Weld strength retention rate A No. 1 tensile test piece of ASTMD-638 is injection molded from both longitudinal ends using side gates.
The obtained test piece was subjected to a tensile test according to ASTM D-638, and the obtained strength was defined as the weld strength. Example 1 Polypropylene homopolymer (MI=1.0) or ethylene-propylene block copolymer (MI
= 1.0, ethylene content = 7.0%) to 100 parts by weight of endo-bicyclo-[2,2,1]-5-heptene-2,3-dicarboxylic acid anhydride (hereinafter referred to as hymic anhydride) and 2,5-dimethyl-2,
Add 0.5 parts by weight of 5-di-(tertiary-butylperoxy)hexyne-3 and premix at room temperature.
The mixture was fed into an extruder and melt-kneaded at 230°C to obtain an extrusion-modified polypropylene (hereinafter referred to as modified PP-I) or a modified ethylene-propylene block copolymer (hereinafter referred to as modified PP-). The content of hemic acid was 1.0% by weight each. Crystalline ethylene-propylene block copolymer () (MI = 15, ethylene content = 7%), crystalline ethylene-propylene random copolymer (MI =
9. Ethylene content 2%), the above-mentioned highmic acid anhydride modified PP, HDPE (MI = 0.3, density 0.960),
LDPE (MI = 9, density = 0.912), EPR (ethylene content = 75%, Mooney viscosity = 70), EPDM (ethylene content = 50%, third component = ethylidene norbornene, Mooney viscosity = 105) and talc ( (average particle diameter 10μ, aspect ratio 3-10) are blended in the combinations of each experiment number shown in Table 1 and mixed in a high-speed mixer, and the resulting mixture is heated at a cylinder temperature of 200-250℃ using a twin-screw kneader. Melt-kneader pellets were obtained. Obtained pellet temperature 230℃, pressure 900
Each test piece was molded under injection molding conditions of Kg/cm 2 . The flexural modulus, isot impact strength, mold shrinkage rate, coating peel strength, warp and weld strength retention rate of each test piece obtained were measured, and the results are shown in Table 1.
(Experiment numbers 1 to 7). For comparison, Table 1 shows the physical properties of the cases in which modified PP is not blended, talc with an average particle diameter of 10μ and aspect ratio of less than 3 is blended, and EPR or EPDM is not blended.
Also listed. (Experiment numbers 8-13).
【表】
実施例 ２
結晶性エチレン―プロピレンブロツク共重合体
として、共重合体（）もしくは共重合体（）
（MI＝9.0、エチレン含有量＝7.0％）、及びタルク
に代りマイカ（平均粒子径100μ、アスペクト比
10〜100）を用いた以外は実施例１と同じものを
用いて表―２に示す実験番号の組合せで配合し、
実施例１と同様の方法で試験片を成形して各物性
を測定し、その結果を表―２に示した（実験番号
14―19）。
比較のために上記において、変性PPを配合し
ないもの、平均粒子径100μ、アスペクト比３未
満のマイカを配合した場合及びEPR又はEPDM
を配合しない場合についての各物性について表―
２に併記した（実験番号20〜24）。[Table] Example 2 As a crystalline ethylene-propylene block copolymer, copolymer () or copolymer ()
(MI = 9.0, ethylene content = 7.0%), and mica (average particle size 100μ, aspect ratio
10 to 100) was used, except that the same materials as in Example 1 were used, and the combinations of experiment numbers shown in Table 2 were used.
Test pieces were molded in the same manner as in Example 1 and their physical properties were measured, and the results are shown in Table 2 (Experiment No.
14-19). For comparison, in the above cases, one does not contain modified PP, one contains mica with an average particle size of 100μ and an aspect ratio of less than 3, and EPR or EPDM.
Table for each physical property when not blended with
2 (experiment numbers 20 to 24).
【表】
実施例 ３
実施例２において、マイカの代り平均粒子径
9μ、アスペクト比３〜30の繊維結晶性ケイ酸カ
ルシウム（商品名；ウオラストナイト）を用いた
以外は同じものを用いて表―３に示す実験番号の
組合せで配合し、実施例１と同様の方法で試験片
を成形して各物性を測定し、その結果を表―３に
示した（実験番号25〜30）。
比較のために上記において、変性PPを配合し
ないもの、平均粒子径9μ、アスペクト比３未満
の繊維結晶性ケイ酸カルシウムを配合した場合及
びEPR又はEPDMを配合しない場合についての
各物性について表―３に併記した（実験番号31〜
35）。[Table] Example 3 In Example 2, instead of mica, average particle diameter
Same as Example 1 except that fibrous crystalline calcium silicate (trade name: Wollastonite) of 9μ and aspect ratio of 3 to 30 was used, and the same materials were used and the combinations of experiment numbers shown in Table 3 were used. Test pieces were molded using the method described above, and their physical properties were measured, and the results are shown in Table 3 (experiment numbers 25 to 30). For comparison, Table 3 shows the physical properties of the cases in which modified PP is not blended, fibrous crystalline calcium silicate with an average particle size of 9μ and aspect ratio of less than 3 is blended, and EPR or EPDM is not blended. (Experiment number 31~
35).
【表】
実施例 ４
実施例１におけるEPRを用いて、実施例１と
同様に無水ハイミツク酸変性EPR（酸含有量0.5
％）を得た。
実施例１における結晶性エチレン―プロピレン
ブロツク共重合体（）、EPDM、変性PP―、
タルク、実施例２のマイカ、実施例３のウオラス
トナイト及び上記の変性EPRを用いて表―４に
示す実験番号の組合せで配合し、実施例１と同様
の方法で試験片を成形して各物性を測定し、その
結果を表―４に示した。（実験番号36〜39）。[Table] Example 4 Using the EPR in Example 1, in the same manner as in Example 1, EPR modified with Himicic anhydride (acid content 0.5
%) was obtained. Crystalline ethylene-propylene block copolymer (), EPDM, modified PP in Example 1,
Using talc, the mica of Example 2, the wollastonite of Example 3, and the modified EPR described above, the mixtures were mixed according to the experiment numbers shown in Table 4, and test pieces were molded in the same manner as in Example 1. Each physical property was measured and the results are shown in Table 4. (Experiment numbers 36-39).
Claims (1)
ン―プロピレンブロツクまたはランダム共重合体
７〜87重量％、(2)エチレン含有量20〜90重量％で
ムーニー粘度10〜120のエチレン―α―オレフイ
ン共重合体ゴム５〜50重量％、(3)結晶性ポリオレ
フインおよび／またはエチレン―α―オレフイン
共重合体ゴムを不飽和カルボン酸またはその誘導
体で変性してなる変性ポリオレフイン３〜50重量
％、および(4)平均粒子径0.5〜15μでアスペクト比
３〜10のタルク、平均粒子１〜200μでアスペク
ト比10〜100のマイカまたは平均粒子径１〜100μ
でアスペクト比３〜30の繊維結晶性ケイ酸カルシ
ウム５〜40重量％とからなるポリオレフイン組成
物。1. Crystalline ethylene-propylene block or random copolymer with an ethylene content of 20% by weight or less or 7-87% by weight, (2) Ethylene-α-olefin copolymer with an ethylene content of 20-90% by weight and a Mooney viscosity of 10-120. 5 to 50% by weight of polymer rubber, (3) 3 to 50% by weight of modified polyolefin obtained by modifying crystalline polyolefin and/or ethylene-α-olefin copolymer rubber with an unsaturated carboxylic acid or a derivative thereof, and ( 4) Talc with an average particle size of 0.5 to 15μ and an aspect ratio of 3 to 10, mica with an average particle size of 1 to 200μ and an aspect ratio of 10 to 100, or an average particle size of 1 to 100μ
and 5 to 40% by weight of fibrous crystalline calcium silicate having an aspect ratio of 3 to 30.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11297881A JPS5815544A (en) | 1981-07-21 | 1981-07-21 | Polyolefin composition |
| CA000407596A CA1218179A (en) | 1981-07-21 | 1982-07-20 | Polyolefin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11297881A JPS5815544A (en) | 1981-07-21 | 1981-07-21 | Polyolefin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5815544A JPS5815544A (en) | 1983-01-28 |
| JPS6342930B2 true JPS6342930B2 (en) | 1988-08-26 |
Family
ID=14600326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11297881A Granted JPS5815544A (en) | 1981-07-21 | 1981-07-21 | Polyolefin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5815544A (en) |
| CA (1) | CA1218179A (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58213043A (en) * | 1982-06-04 | 1983-12-10 | Mitsui Toatsu Chem Inc | Polypropylene resin composition |
| JPS5964647A (en) * | 1982-10-06 | 1984-04-12 | Idemitsu Petrochem Co Ltd | Polypropylene resin composition |
| JPS59206446A (en) * | 1983-04-04 | 1984-11-22 | Idemitsu Petrochem Co Ltd | Propylene resin composition |
| JPS59206447A (en) * | 1983-04-07 | 1984-11-22 | Idemitsu Petrochem Co Ltd | Propylene resin composition |
| JPS6015446A (en) * | 1983-07-07 | 1985-01-26 | Idemitsu Kosan Co Ltd | Polyethylene resin composition and its laminate |
| JPS6082683A (en) * | 1983-10-06 | 1985-05-10 | Japan Storage Battery Co Ltd | Manufacture of electrochemical apparatus using ion- exchange membrane |
| JPS6081241A (en) * | 1983-10-12 | 1985-05-09 | Idemitsu Petrochem Co Ltd | Propylene-ethylene block copolymer composition |
| JPS6162544A (en) * | 1984-09-03 | 1986-03-31 | Mitsubishi Chem Ind Ltd | Resin composition |
| JPS6189235A (en) * | 1984-10-09 | 1986-05-07 | Sumitomo Chem Co Ltd | Coating of olefin resin molded article |
| JPH0749499B2 (en) * | 1985-09-26 | 1995-05-31 | 住友化学工業株式会社 | Polypropylene resin composition |
| US5145892A (en) * | 1985-12-19 | 1992-09-08 | Chisso Corporation | Polypropylene resin composition |
| CA1275523C (en) * | 1985-12-19 | 1990-10-23 | Hiroyoshi Asakuno | Polypropylene resin composition |
| JPS62151437A (en) * | 1985-12-26 | 1987-07-06 | Toyoda Gosei Co Ltd | Polypropylene resin composition |
| KR100241274B1 (en) * | 1997-08-27 | 2000-02-01 | 정몽규 | A polyolefin resin composition for motor's outer layer |
| KR100399834B1 (en) * | 2000-12-19 | 2003-09-29 | 삼성종합화학주식회사 | Polyolefine resin composition having low specific density and high heat-resistance |
| JP2005206639A (en) * | 2004-01-20 | 2005-08-04 | Riken Technos Corp | Resin composition containing organic filler |
| KR100638183B1 (en) * | 2005-03-29 | 2006-10-26 | 삼성토탈 주식회사 | The polyolefin composition with improved metal-gloss and a product manufactured using the same |
| TWI619754B (en) * | 2016-11-01 | 2018-04-01 | Chen Jin Fu | Environmental protection materials and curtain blades made from the environmental protection materials |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51136735A (en) * | 1975-05-22 | 1976-11-26 | Mitsui Toatsu Chem Inc | Thermoplastic resin com position |
| JPS5364257A (en) * | 1976-11-22 | 1978-06-08 | Toyoda Gosei Co Ltd | Impact-resistant resin composition |
| JPS5521494A (en) * | 1978-07-31 | 1980-02-15 | Bethlehem Steel Corp | Olefin composition having high antiishock and high temperature flow resistance and metal plastic laminate obtained therefrom |
| JPS55112248A (en) * | 1979-02-22 | 1980-08-29 | Furukawa Electric Co Ltd:The | Polyolefinic resin composition highly filled with inorganic material |
| JPS55131031A (en) * | 1979-03-31 | 1980-10-11 | Idemitsu Petrochem Co Ltd | Polypropylene resin composition |
-
1981
- 1981-07-21 JP JP11297881A patent/JPS5815544A/en active Granted
-
1982
- 1982-07-20 CA CA000407596A patent/CA1218179A/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51136735A (en) * | 1975-05-22 | 1976-11-26 | Mitsui Toatsu Chem Inc | Thermoplastic resin com position |
| JPS5364257A (en) * | 1976-11-22 | 1978-06-08 | Toyoda Gosei Co Ltd | Impact-resistant resin composition |
| JPS5521494A (en) * | 1978-07-31 | 1980-02-15 | Bethlehem Steel Corp | Olefin composition having high antiishock and high temperature flow resistance and metal plastic laminate obtained therefrom |
| JPS55112248A (en) * | 1979-02-22 | 1980-08-29 | Furukawa Electric Co Ltd:The | Polyolefinic resin composition highly filled with inorganic material |
| JPS55131031A (en) * | 1979-03-31 | 1980-10-11 | Idemitsu Petrochem Co Ltd | Polypropylene resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5815544A (en) | 1983-01-28 |
| CA1218179A (en) | 1987-02-17 |
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