JPH0379648A - Polyolefin resin composition - Google Patents
Polyolefin resin compositionInfo
- Publication number
- JPH0379648A JPH0379648A JP21672189A JP21672189A JPH0379648A JP H0379648 A JPH0379648 A JP H0379648A JP 21672189 A JP21672189 A JP 21672189A JP 21672189 A JP21672189 A JP 21672189A JP H0379648 A JPH0379648 A JP H0379648A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin resin
- sulfur
- compound
- pts
- 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.)
- Pending
Links
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 28
- 239000011342 resin composition Substances 0.000 title claims description 14
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 15
- 150000002989 phenols Chemical class 0.000 claims abstract description 9
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 229920001155 polypropylene Polymers 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 239000006096 absorbing agent Substances 0.000 abstract description 3
- 230000003078 antioxidant effect Effects 0.000 abstract description 3
- 239000004611 light stabiliser Substances 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 2
- 238000005453 pelletization Methods 0.000 abstract 1
- -1 polyethylene Polymers 0.000 description 17
- 238000012360 testing method Methods 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- DOTYDHBOKPPXRB-UHFFFAOYSA-N 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioic acid Chemical compound CCCCC(C(O)=O)(C(O)=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DOTYDHBOKPPXRB-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- HBYRZSMDBQVSHO-UHFFFAOYSA-N tris(2-tert-butyl-4-methylphenyl) phosphite Chemical compound CC(C)(C)C1=CC(C)=CC=C1OP(OC=1C(=CC(C)=CC=1)C(C)(C)C)OC1=CC=C(C)C=C1C(C)(C)C HBYRZSMDBQVSHO-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の背景〕
〈産業上の利用分野〉
本発明のポリオレフィン樹脂組成物は、耐熱老化性に優
れ、自動車の外装材、中空容器、シート成形品などの素
材として有用なものである。[Detailed Description of the Invention] [Background of the Invention] [Industrial Field of Application] The polyolefin resin composition of the present invention has excellent heat aging resistance and is useful as a material for automobile exterior materials, hollow containers, sheet molded products, etc. It is something.
〈従来の技術〉
ポリオレフィン樹脂は優れた物理的、化学的、電気的性
質を有しているため、押出成形、射出成形あるいは吹込
成形等の方法により成形品、パイプ、シート、フィルム
、繊維などに加工され、広範囲の分野で使用されている
。<Prior art> Polyolefin resin has excellent physical, chemical, and electrical properties, so it can be made into molded products, pipes, sheets, films, fibers, etc. by extrusion molding, injection molding, blow molding, etc. It is processed and used in a wide range of fields.
しかしながら、ポリエチレン、ポリプロピレン、またそ
の共重合体などのポリオレフィン樹脂は、それを単独で
用いた場合、加工時又は、使用１’７において、酸素の
存在下、熱、光の作用によって比較的容易に酸化劣化を
受けて、軟化、脆化又は変色などの現象を作ってその物
性が著しく低下するので、各種使用に耐えられなくなる
ことが知られている。However, when polyolefin resins such as polyethylene, polypropylene, and their copolymers are used alone, they are relatively easily affected by heat and light in the presence of oxygen during processing or use. It is known that due to oxidative deterioration, phenomena such as softening, embrittlement, and discoloration occur, resulting in a significant decrease in physical properties, making it impossible to withstand various uses.
このような老化現象を防止するために、従来より種々の
酸化防止剤または二種以上の酸化防止剤の組み合わせに
よる改良技術が開発されている。In order to prevent such aging phenomena, improved techniques using various antioxidants or a combination of two or more antioxidants have been developed.
例えば、２．６−ジーｔ−ブチル−４−メチルフェノー
ル、ｎ−オクタデシル−β−（３，５−ジ−ｔ−ブチル
−４−ヒドロキシフェニル）プロピオネート、テトラキ
ス［メチレン−３−（３゜５−ジ−ｔ−ブチル−４−ヒ
ドロキシフェニル）プロピオネートコメタン、３．５−
トリメチル−２，４，６−）リス（３，５，−ジ−ｔ−
ブチル−４−ヒドロキシベンジル）ベンゼン、１，１゜
３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブ
チルフェニル）ブタンなどの酸化防１１．剤を使用した
り、これらの酸化防止剤とジラウリルチオジプロピオネ
ート、ジステアリルチオジプロピオネートまたは、ペン
タエリスリトール−テトラキス（β−ドデシルチオプロ
ピオネート）との組み合わせなどを使用する改良方法が
知られている。For example, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, tetrakis[methylene-3-(3°5 -di-t-butyl-4-hydroxyphenyl)propionate comethane, 3.5-
Trimethyl-2,4,6-)lis(3,5,-di-t-
Antioxidants such as butyl-4-hydroxybenzyl)benzene and 1,1°3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane 11. There are improvement methods that use antioxidants or combinations of these antioxidants with dilaurylthiodipropionate, distearylthiodipropionate, or pentaerythritol-tetrakis (β-dodecylthiopropionate). Are known.
一方、トリス（３−メチル−５−ｔ−ブチル−４−ヒド
ロキシベンジル）イソシアヌレートをポリオレフィン樹
脂中に配合して老化を防止させることは、本化合物が特
公昭４６−３５０４１号公報記載の発明の一般式に包含
されていることから公知であるが、該発明の明細書中に
は上記化合物の具体的例示もなされていないし、しがち
、その明細書中で構造的に対称型のトリス−（３，５ジ
ーｔ−アルキル−４−ヒドロキシベンジル）イソシアヌ
レート誘導体が好ましい化合物である旨記載されている
ことから、上記発明中に形式的に包含されているが、前
記非対称型の化合物が対称型の化合物より効果が劣るこ
とを示唆しているので、その効果にあまり期待を寄せる
ことはできなかった。On the other hand, incorporating tris(3-methyl-5-t-butyl-4-hydroxybenzyl) isocyanurate into a polyolefin resin to prevent aging is the invention of the present invention described in Japanese Patent Publication No. 46-35041. Although it is known from the fact that it is included in the general formula, there is no specific example of the above compound in the specification of the invention, and it tends to be the case that the structurally symmetric tris-( Since the 3,5 di-t-alkyl-4-hydroxybenzyl) isocyanurate derivative is described as a preferred compound, it is formally included in the above invention; This suggests that it is less effective than the other compound, so we could not have much hope for its effectiveness.
〈発明が解決しようとする課題〉
しかしながら、前記酸化防止剤同志の組み合わせによる
改良技術においても十分に満足するものを得ることは困
難であったし、また、前記非対称型の化合物を単独で用
いるだけでは、上記明細書に記載されている通り優れた
効果を発揮することはできなく、実用に供することは困
難であった。<Problems to be Solved by the Invention> However, it has been difficult to obtain a fully satisfactory result even with the improvement technique using a combination of the above-mentioned antioxidants, and it has been difficult to obtain a sufficiently satisfactory result by using the above-mentioned asymmetric compound alone. However, as described in the above specification, it was not possible to exhibit the excellent effects, and it was difficult to put it into practical use.
く要 旨〉
本発明者らは、上記課題に鑑みて鋭意研究を重ねた結果
、特定のフェノール系化合物と特定の硫黄系化合物とを
ポリオレフィン樹脂に配合することにより、今までの酸
化防止剤同志の組み合わせ技術からは到底予測し難い極
めて優れた熱及び酸化安定性を有する驚くべき相乗効果
が得られるポリオレフィン樹脂組成物が得られることを
見い出し、本発明を完成するに至った。Summary> As a result of extensive research in view of the above issues, the present inventors have found that by blending a specific phenol compound and a specific sulfur compound into a polyolefin resin, the present inventors have succeeded in improving the effectiveness of conventional antioxidants. The present inventors have discovered that a polyolefin resin composition can be obtained that exhibits a surprising synergistic effect with extremely excellent thermal and oxidative stability that would be difficult to predict from a combination technique, and has completed the present invention.
すなわち、本発明のポリオレフィン樹脂組成物は、ポリ
オレフィン樹脂１００重量部、下記式（Ｉ）で表される
フェノール系化合物０．０１〜３重量部及び２個以上の
硫黄原子を有する硫黄系化合物０１０１〜３重量部から
なること、を特徴とするものである。That is, the polyolefin resin composition of the present invention comprises 100 parts by weight of a polyolefin resin, 0.01 to 3 parts by weight of a phenolic compound represented by the following formula (I), and 0101 to 0101 of a sulfur compound having two or more sulfur atoms. 3 parts by weight.
（Ｉ）
く効 果〉
本発明の特定なフェノール系化合物と２個以上の硫黄原
子を有する硫黄化合物とを配合したポリオレフィン樹脂
組成物は、酸化劣化を受は易い高温時の老化において優
れているので、高温度に加熱されるときがある自動車の
外装材、中空容器、シート成形品などの素材として有用
である。(I) Effect> The polyolefin resin composition containing the specific phenolic compound of the present invention and a sulfur compound having two or more sulfur atoms is excellent in aging at high temperatures, which is susceptible to oxidative deterioration. Therefore, it is useful as a material for automobile exterior materials, hollow containers, sheet molded products, etc., which are sometimes heated to high temperatures.
〔Ｉ〕構成成分
（Ｉ）ポリオレフィン樹脂成分
本発明のポリオレフィン樹脂組成物において用いられる
ポリオレフィン樹脂は、低密度ポリエチレン、中密度ポ
リエチレン、リニアー低密度ポリエチン、ポリプロピレ
ン、ポリブテン−１などのポリα−オレフィン、エチレ
ン・プロピレンランダムまたはブロック共重合体、エチ
レン・ブテン１ランダム共重合体などのポリα−オレフ
ィン共重合体、無水マレイン酸変性ポリプロピレンなど
のポリα−オレフィンとじニルモノマーの共重合体及び
これらの混合物などを挙げることができるが、これらの
中でプロピレン重合体に対して特に有効である。[I] Constituent Component (I) Polyolefin Resin Component The polyolefin resin used in the polyolefin resin composition of the present invention includes poly-α-olefins such as low-density polyethylene, medium-density polyethylene, linear low-density polyethine, polypropylene, and polybutene-1; Polyα-olefin copolymers such as ethylene/propylene random or block copolymers, ethylene/butene 1 random copolymers, polyα-olefin copolymers such as maleic anhydride-modified polypropylene, and mixtures thereof, etc. Among these, it is particularly effective for propylene polymers.
（２）フェノール系化合物
本発明のポリオレフィン樹脂組成物において用いられる
フェノール系化合物は、下記式（Ｉ）で表されるもので
ある。(2) Phenol Compound The phenol compound used in the polyolefin resin composition of the present invention is represented by the following formula (I).
（Ｉ）
（３）硫黄系化合物成分
本発明のポリオレフィン樹脂組成物において用いられる
硫黄系化合物は、分子中に２個以上、好ましくは３個以
上の硫黄原子を持つ硫黄系化合物である。そのような硫
黄化合物を一般式で表わされる化学式で示せば次に示す
ものがある。(I) (3) Sulfur-based compound component The sulfur-based compound used in the polyolefin resin composition of the present invention is a sulfur-based compound having two or more, preferably three or more, sulfur atoms in the molecule. Such sulfur compounds have the following chemical formulas:
１
（Ｒ−Ｓ−ＣＨ２ＣＨ２Ｃ−） ａＺ
（ＩＩ）
（、ＩＩＩ）
（ただし、
式中のａは、
２〜１２、好ましくは３
〜６の整数を表わし、
１
Ｒは、−Ｃｎ中２ｏ＋１ｌ−ＣＨ２ＣＨ２ＣＯＣｏＨ２
ｎ＋１（ｎは、８〜２０１好ましくは１０〜１８の整数
）
を表わし、
Ｚは、
ＣＨ２Ｏ−
−Ｏ−ＣＨ２−Ｃ
ＣｍＨ２ＩＩ＋１
（ｍは１〜５の整数）、
Ｈ２Ｏ−
Ｈ２Ｏ−
−０−ＣＨ２−Ｃ−ＣＨ２−ＯＨ
Ｈ２Ｏ−
Ｈ２Ｏ−
−０−ＣＨ２−Ｃ−ＣＨ２−０−
ＣＨ２Ｏ−
ＣＨ２Ｏ−
ＣＨ２０
次に、
これら化合物の具体例を示すと、
Ｎｏ。1 (R-S-CH2CH2C-) aZ (II) (, III) (However, a in the formula represents an integer of 2 to 12, preferably 3 to 6, and 1 R is 2o+1l-CH2CH2COCoH2 in -Cn
n+1 (n is an integer of 8 to 201, preferably 10 to 18), Z is CH2O- -O-CH2-C CmH2II+1 (m is an integer of 1 to 5), H2O- H2O- -0-CH2- C-CH2-OH H2O- H2O- -0-CH2-C-CH2-0- CH2O- CH2O- CH20 Next, specific examples of these compounds are shown below.
１： （Ｈ２５Ｃ１２−８−Ｃ Ｎｏ。1: (H25C12-8-C No.
５： （Ｈ２Ｓｅ、２−３−Ｃ ：Ｈ２ＣＨ２Ｃ０ＣＨ２−）４Ｃ １ Ｈ２−８−ＣＨ２ＣＨ２ＣＯＣＨ２−）４Ｃ１ Ｈ−８−ＣＨ２ＣＨ２ＣＯＣＨ２−）３Ｃ−Ｃ２Ｈ５１ ：Ｈ２ＣＨ２Ｃ０ＣＨ２−） Ｃ−ＣＨＯＨ ３２ Ｎｏ。5: (H2Se, 2-3-C :H2CH2C0CH2-)4C 1 H2-8-CH2CH2COCH2-)4C1 H-8-CH2CH2COCH2-)3C-C2H51 :H2CH2C0CH2-) C-CHOH 32 No.
１１：Ｈ２５Ｃ１２０ＣＣＨ２ＣＨ２−３−ＣＨ２Ｃ１
Ｈ２５Ｃ１２０ＣＣＨ２ＣＨ２−８−ＣＨ２５Ｃ１２０
ＣＣＨ２ＣＨ２−８−Ｃ月１
【
等を、挙げることができる。11: H25C120CCH2CH2-3-CH2C1 H25C120CCH2CH2-8-CH25C120
CCH2CH2-8-Cmonth1 [ etc. can be mentioned.
（４〉その他の配合剤成分
本発明のポリオレフィン樹脂組成物には上記（Ｉ）〜（
３）の必須成分の他に添加剤、例えば紫外線吸収剤、光
安定剤、燐系安定剤、酸化防止剤、金属不活性剤、金属
石鹸類、造核剤、滑剤、帯電防止剤、難燃剤、顔料、顔
料分散剤及び充坑剤などを本発明の効果を著しく損なわ
ない範囲で含有させてもよい。(4> Other compounding agent components The polyolefin resin composition of the present invention includes the above (I) to (
In addition to the essential components 3), additives such as ultraviolet absorbers, light stabilizers, phosphorus stabilizers, antioxidants, metal deactivators, metal soaps, nucleating agents, lubricants, antistatic agents, and flame retardants. , pigments, pigment dispersants, fillers, etc., may be included within the range that does not significantly impair the effects of the present invention.
とりわけ紫外線吸収剤、ヒンダードアミン系光安定剤な
ど、例えば２−ヒドロキシ−４−メトキシベンゾフェノ
ン、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノ
ン、２ （２’ −ヒドロキシ−５′ −メチルフェ
ニル）ベンゾトリアゾール、２（２′ −ヒドロキシ−
３′ −ｔ−ブチル−５′−メチルフェニル）−５−ク
ロロ−ベンゾトリアゾール、２（２′ −ヒドロキシ−
３′ ５′ −ジ−ｔ−ブチルフェニル）−５−クロ
ロ−ベンゾトリアゾール、２（２′ −ヒドロキシ−３
′ ５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾ
ール、［２，２’ −チオビス（４−ｔ−オクチルフ
ェノラート）］ブチルアミンＮｉ塩、２．２，６，６−
テトラメチル−４−ピペリジルベンゾエート、ビス（２
，２，６，６−テトラメチル−４−ピペリジル）セバケ
ート、２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシ
ベンジル）−２−ｎ−ブチル−マロン酸ビス（Ｉ，２，
２，６，６−ベンタメチルー４−ピペリジル）、１−
［２−＋３−（３，５−ジ−ｔ−ブチル−４−ヒドロ
キシフェニル）プロピオニルオキシ）エチル］−４−［
’４− （３，５−ジ−ｔ−ブチル−４−ヒドロキシフ
ェニル）プロピオニルオキシ］ −２，２，６，６−
テトラメチルビベリジン、コハク酸ジメチル・１− （
２−ヒドロキシエチル）−４−ヒドロキシ−２，２，６
，６−テトラメチルビペリジン重縮合物、トリス（Ｉ，
２，２，６，６−ベンタメチルー４−ピペリジル）ホス
ファイト、ポリ［〔６（Ｉ，１，３，３，−テトラメチ
ルブチルイミノ）−１，３，５−トリアジン−２，４−
ジイル〕（（２，２，６，６−テトラメチル−４−ピペ
リジル）イミノ〕へキサメチレン（（２，２，６ローテ
トラメチルー４−ピペリジル）イミノ〕］、ポリ〔〔６
−モルホリノ−１，３，５−トリアジン−２，４−ジイ
ル）（（２，２，６，６−テドラメチルー４−ピペリジ
ル）イミノ〕ヘキサメチレンＣ（２，２，６，６−テト
ラメチル−４−ピペリジル）イミノ〕］、テトラキス（
２，２，６゜６−テトラメチル−４−ピペリジル）−１
２３，４−ブタンテトラカルボキシレートなどを添加す
ることによってその耐光性を改善することができる。In particular, ultraviolet absorbers, hindered amine light stabilizers, etc., such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2(2'-hydroxy-5'-methylphenyl)benzotriazole, 2(2'-hydroxy-
3'-t-butyl-5'-methylphenyl)-5-chloro-benzotriazole, 2(2'-hydroxy-
3'5' -di-t-butylphenyl)-5-chloro-benzotriazole, 2(2' -hydroxy-3
'5'-di-t-amylphenyl)benzotriazole, [2,2'-thiobis(4-t-octylphenolate)]butylamine Ni salt, 2.2,6,6-
Tetramethyl-4-piperidylbenzoate, bis(2
, 2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl-malonate bis(I,2,
2,6,6-bentamethyl-4-piperidyl), 1-
[2-+3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-4-[
'4- (3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy] -2,2,6,6-
Tetramethyl biveridine, dimethyl succinate 1- (
2-hydroxyethyl)-4-hydroxy-2,2,6
, 6-tetramethylbiperidine polycondensate, tris(I,
2,2,6,6-bentamethyl-4-piperidyl)phosphite, poly[[6(I,1,3,3,-tetramethylbutylimino)-1,3,5-triazine-2,4-
diyl]((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6-tetramethyl-4-piperidyl)imino)], poly[[6
-morpholino-1,3,5-triazine-2,4-diyl)((2,2,6,6-tedramethyl-4-piperidyl)imino]hexamethylene C(2,2,6,6-tetramethyl-4 -piperidyl)imino]], tetrakis(
2,2,6゜6-tetramethyl-4-piperidyl)-1
Its light resistance can be improved by adding 23,4-butanetetracarboxylate or the like.
また、本発明のポリオレフィン樹脂組成物に、燐系酸化
防止剤を添加することによって、その色相、耐熱老化性
及び、耐候性を改善することができる。これら燐系酸化
防止剤としては、例えば、ジステアリルペンタエリスリ
トールジホスファイト、トリス（２，４−ジ−ｔ−ブチ
ルフェニル）ホスファイト、トリス（２−ｔ−ブチル−
４−メチルフェニル）ホスファイト、ビス（２，４−ジ
−ｔ−ブチルフェニル）ペンタエリスリトールジホスフ
ァイト、テラトキス（２，４−ジ−ｔ−ブチルフェニル
）−４，４’ −ビフェニレンジホスホナイト、テト
ラトリデシル−４，４′ −ブチリデンビス−（３−メ
チル−６−ｔ−ブチルフェノール）−ジホスファイト、
ビス−（２，６−ジｔ−ブチル−４−メチルフェニル）
ペンタエリスリトールジホスフイトなどを卒げることか
できる。Further, by adding a phosphorus antioxidant to the polyolefin resin composition of the present invention, its hue, heat aging resistance, and weather resistance can be improved. Examples of these phosphorus antioxidants include distearylpentaerythritol diphosphite, tris(2,4-di-t-butylphenyl)phosphite, and tris(2-t-butyl-
4-methylphenyl) phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, teratokis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite , tetratridecyl-4,4'-butylidenebis-(3-methyl-6-t-butylphenol)-diphosphite,
Bis-(2,6-di-t-butyl-4-methylphenyl)
It is possible to avoid drugs such as pentaerythritol diphosphite.
（ｎ）配合
（Ｉ） ｆｆｉ比
本発明のポリオレフィン樹脂組成物における、フェノー
ル系化合物及び硫黄系化合物の総添加瓜は、ポリオレフ
ィン樹脂１００重量部に対してフェノール系化合物を０
．０１〜３重量部、好ましくは０．０５〜１重量部で、
硫黄系化合物を０．０１〜３重量部、好ましくは０．０
５〜１重量部である。また、上記フェノール系化合物に
対する硫黄系化合物の併用における重量比は、フェノー
ル系化合物１に対して０．５〜２０．特に０．５〜６の
範囲内であることが好ましい。(n) Formulation (I) ffi ratio The total addition of phenolic compounds and sulfur compounds in the polyolefin resin composition of the present invention is such that the amount of phenolic compounds added is 0 to 100 parts by weight of the polyolefin resin.
．． 01 to 3 parts by weight, preferably 0.05 to 1 part by weight,
0.01 to 3 parts by weight of a sulfur compound, preferably 0.0
It is 5 to 1 part by weight. In addition, the weight ratio of the sulfur compound to the phenol compound in combination is 0.5 to 20. In particular, it is preferably within the range of 0.5 to 6.
（２）配合
本発明のポリオレフィン樹脂組成物は、上記化合物をロ
ール、ヘンシェルミキサー、スーパーミキサー、■ブレ
ンダー、タンブラ−ミキサー、リボンブレンダー、バン
バリーミキサ−、ニーダーブレンダ−又は押出機のごと
き混合機を用いて所定時間混合した後、通常の押出機に
てペレット状にすることが好ましい。(2) Compounding The polyolefin resin composition of the present invention is prepared by mixing the above-mentioned compounds using a mixer such as a roll, Henschel mixer, super mixer, ■ blender, tumbler mixer, ribbon blender, Banbury mixer, kneader blender, or extruder. After mixing for a predetermined period of time, it is preferable to form the mixture into pellets using an ordinary extruder.
また、上記混合混線において組成物成分の配合割合は、
各成分の目的量を配合しておく以外に、フェノール系化
合物成分及び硫黄系化合物成る）を目的とする組成物の
配合成分より多量にポリオレフィン樹脂成分配合して高
濃度の配合物とした後、これを成形直前にポリオレフィ
ン樹脂により希釈混合して使用する、いわゆるマスター
バッチとしても良い。In addition, the blending ratio of the composition components in the above mixed crosstalk is as follows:
In addition to blending the desired amounts of each component, a polyolefin resin component is blended in a larger amount than the target composition (consisting of a phenolic compound component and a sulfur compound) to form a highly concentrated blend. This may be used as a so-called masterbatch, which is diluted and mixed with a polyolefin resin immediately before molding.
（ｍ）応用
以上、本発明に関して、ポリオレフィン樹脂組成物につ
き具体的に説明してきたが、上記ポリオレフィン樹脂に
代えて以下に示す合成高分子にも使用可能であり、これ
らの合成高分子としては、ポリ塩化ビニル、メタクリル
樹脂、ポリスチレン、耐衝撃性ポリスチレン、ＡＢＳ樹
脂、ＡＥＳ樹脂等ノスチレン系樹脂、ポリエチレンテレ
フタレート、ポリブチレンテレフタレート等のポリエス
テル、ポリアミド、ポリカーボネート、ポリアセタール
、ポリエチレンオキシド、ポリフェニレンエーテル、ポ
リスルフォン、ポリウレタン、不飽和ポリエステル樹脂
などがあげられる。(m) Application In the above, the polyolefin resin composition has been specifically explained in relation to the present invention, but instead of the above polyolefin resin, the following synthetic polymers can also be used, and these synthetic polymers include: Polyvinyl chloride, methacrylic resin, polystyrene, high-impact polystyrene, ABS resin, AES resin and other nostyrene resins, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamide, polycarbonate, polyacetal, polyethylene oxide, polyphenylene ether, polysulfone, polyurethane , unsaturated polyester resin, etc.
また、セルロース、ゴム、蛋白質、あるいは酢酸セルロ
ース等やそれらの誘導体などの天然重合体や鉱油、動植
物油、ロウなどの天然有機化合物にも用いることができ
る。Furthermore, natural polymers such as cellulose, rubber, protein, cellulose acetate, and derivatives thereof, and natural organic compounds such as mineral oil, animal and vegetable oils, and wax can also be used.
下記に実施例及び比較例を挙げて本発明をさらに具体的
に説明する。The present invention will be explained in more detail with reference to Examples and Comparative Examples below.
実施例１〜１０および比較例１〜１４
１３５℃テトラリン中で測定した極限粘度が１．９でア
イソタクチックなものが９８％のポリプロピレン粉末１
００重量部に、第１表に示す各添加剤を配合して、ミキ
サーで充分混合した。Examples 1 to 10 and Comparative Examples 1 to 14 Polypropylene powder 1 with an intrinsic viscosity of 1.9 measured in tetralin at 135°C and 98% isotactic
Each additive shown in Table 1 was added to 0.00 parts by weight and thoroughly mixed with a mixer.
そしてシリンダー温度２６０℃、Ｌ／Ｄ−２０゜２０ｍ
ｍ径の押出機によってこの溶融混練して這粒した。こう
して得られたペレットを２３０℃で厚さ０．５ｍｍのシ
ートに圧縮成型して試験片とした。And cylinder temperature 260℃, L/D-20゜20m
The mixture was melt-kneaded and granulated using an m-diameter extruder. The pellets thus obtained were compression molded at 230° C. into a sheet with a thickness of 0.5 mm to obtain a test piece.
耐熱老化性は、１５０℃の循環式空気炉中で試験片を加
熱して試験片が酸化劣化によって褐突脆化する迄の所要
時間を測定した。Heat aging resistance was determined by heating a test piece in a circulating air oven at 150°C and measuring the time required until the test piece became brittle due to oxidative deterioration.
耐候性は、アトラス社製６５／ＸＷ−ＷＲ型キセノンウ
エザオメーターを用い、ブラックパネル温度８０℃で試
験片に光照射し、試験片を１８０度に折り曲げたとき、
試験片が脆化してクラックを発生するまでの′所要時間
を測定した。Weather resistance was determined using an Atlas 65/XW-WR xenon weather meter, when the test piece was irradiated with light at a black panel temperature of 80°C and the test piece was bent at 180 degrees.
The time required for the test piece to become brittle and crack was measured.
結果は、第１表に示す通りであった。The results were as shown in Table 1.
なお、第１表中の略号は次の通りである。The abbreviations in Table 1 are as follows.
化合物（Ｉ）
本文中記載のフェノール系化合物
Ｎｏ、１〜１２
本文中記載の硫黄系化合物
（硫黄系酸化防止剤）
ＤＭＴ Ｐ チオジプロピオン酸シミリスチル（フェ
ノール系酸化防止剤）
−１
トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベン
ジル）イソシアヌレート
（商品名： Ｇｏｏｄ Ｒｌｔｅ ３１１４）−２
トリス（３，５−ジメチル−４−ヒドロキシベンジル）
イソシアヌレート
−３
テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒド
ロキシフェニル）プロピオニルオキシメチルコメタン
（商品名： ｌｒｇａｎｏｘ １０１０）−４
３，９−［ビス１，１−ジ−メチル−２（β−（３−ｔ
−ブチル−４−ヒドロキシ−５−メチルフェニル）プロ
ピオニルオキシ）エチル］−２．４．８，１．０−テト
ラオキサスピロ［５，５コウンデカン
（商品名；ＭＡ■ＡＯ−８０）Compound (I) Phenolic compound Nos. 1 to 12 described in the text Sulfur-based compounds (sulfur-based antioxidant) described in the text DMT P Similistyl thiodipropionate (phenolic antioxidant) -1 Tris (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate (trade name: Good Rlte 3114)-2 tris(3,5-dimethyl-4-hydroxybenzyl)
Isocyanurate-3 Tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethylcomethane (trade name: lrganox 1010)-4 3,9-[bis1,1-di- Methyl-2(β-(3-t
-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl]-2.4.8,1.0-tetraoxaspiro[5,5-oundecane (trade name; MA■AO-80)
Claims (1)
で表されるフェノール系化合物０．０１〜３重量部及び
２個以上の硫黄原子を有する硫黄系化合物０．０１〜３
重量部からなることを特徴とする、ポリオレフィン樹脂
組成物。 ▲数式、化学式、表等があります▼[Claims] 1. 100 parts by weight of polyolefin resin, the following formula (I)
0.01 to 3 parts by weight of a phenolic compound represented by and 0.01 to 3 parts by weight of a sulfur compound having 2 or more sulfur atoms
A polyolefin resin composition comprising parts by weight. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21672189A JPH0379648A (en) | 1989-08-23 | 1989-08-23 | Polyolefin resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21672189A JPH0379648A (en) | 1989-08-23 | 1989-08-23 | Polyolefin resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0379648A true JPH0379648A (en) | 1991-04-04 |
Family
ID=16692883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21672189A Pending JPH0379648A (en) | 1989-08-23 | 1989-08-23 | Polyolefin resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0379648A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001064252A (en) * | 1999-08-27 | 2001-03-13 | Nippon Shokubai Co Ltd | Organic sulfide compound, use of the same, polymerization method and polymer using the same |
| US8389608B2 (en) | 2010-09-09 | 2013-03-05 | Chevron Phillips Chemical Company Lp | Aminoplast-polythiol compositions and articles produced therefrom |
-
1989
- 1989-08-23 JP JP21672189A patent/JPH0379648A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001064252A (en) * | 1999-08-27 | 2001-03-13 | Nippon Shokubai Co Ltd | Organic sulfide compound, use of the same, polymerization method and polymer using the same |
| US8389608B2 (en) | 2010-09-09 | 2013-03-05 | Chevron Phillips Chemical Company Lp | Aminoplast-polythiol compositions and articles produced therefrom |
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