JPH0420551A - Resin composition - Google Patents
Resin compositionInfo
- Publication number
- JPH0420551A JPH0420551A JP12434490A JP12434490A JPH0420551A JP H0420551 A JPH0420551 A JP H0420551A JP 12434490 A JP12434490 A JP 12434490A JP 12434490 A JP12434490 A JP 12434490A JP H0420551 A JPH0420551 A JP H0420551A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- graft copolymer
- meth
- silicone
- resin
- 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
- 239000011342 resin composition Substances 0.000 title claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000005977 Ethylene Substances 0.000 claims abstract description 42
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 abstract description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012986 chain transfer agent Substances 0.000 abstract description 3
- 150000008282 halocarbons Chemical group 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 239000005871 repellent Substances 0.000 abstract 1
- 229940117958 vinyl acetate Drugs 0.000 abstract 1
- -1 polyethylene Polymers 0.000 description 37
- 239000004698 Polyethylene Substances 0.000 description 18
- 229920000573 polyethylene Polymers 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 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
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 102100040440 Adenylate kinase isoenzyme 5 Human genes 0.000 description 2
- 101710168711 Adenylate kinase isoenzyme 5 Proteins 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-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
- 238000002715 modification method Methods 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 239000005053 propyltrichlorosilane Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- KWDQAHIRKOXFAV-UHFFFAOYSA-N trichloro(pentyl)silane Chemical compound CCCCC[Si](Cl)(Cl)Cl KWDQAHIRKOXFAV-UHFFFAOYSA-N 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- HILHCDFHSDUYNX-UHFFFAOYSA-N trimethoxy(pentyl)silane Chemical compound CCCCC[Si](OC)(OC)OC HILHCDFHSDUYNX-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N vinyl ethyl ether Natural products CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）発明の目的
〔産業上の利用分野〕
本発明は、高圧法ポリエチレン、中・低圧法ポリエチレ
ンまたはエチレン−アクリル酸エステル共重合体等のエ
チレン系樹脂の改質に関するものである。Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention is directed to the modification of ethylene resins such as high-pressure polyethylene, medium- and low-pressure polyethylene, or ethylene-acrylic acid ester copolymers. It is related to.
近年、高圧法あるいは中・低圧法で製造されるポリエチ
レンに対して、例えば、耐ブロッキング性、耐汚染性、
潤滑性、撥水・撥油性などのような、元来ポリエチレン
に備わっていない特性が望まれており、ポリエチレンに
それらの特性をも付与させるべく各種改質方法が検討さ
れている。In recent years, polyethylene produced by high pressure or medium/low pressure methods has improved, for example, blocking resistance, stain resistance,
Characteristics that polyethylene does not originally have, such as lubricity, water repellency, and oil repellency, are desired, and various modification methods are being investigated to impart these characteristics to polyethylene.
例えば、高圧法ポリエチレンはフィルムとして大量に使
用されているが、押出機等で成形されたフィルムを巻き
取ると、フィルム同士がくっつく現象すなわちブロッキ
ング現象が起こる。さらに、ブロッキングし易いフィル
ムは開口性、包装適性が劣るという問題もある。従って
、ブロッキングの防止の目的で、ポリエチレンに、ケイ
ソウ土、カオリン、タルク等の無機物の微粉末を添加す
るか、または上記無機物の微粉末と共に、オレイン酸ア
ミド、エルシン酸アミドなどの不飽和樹脂酸アミドから
なる滑剤を併用するという解決手段が採用されていた。For example, high-pressure polyethylene is used in large quantities as a film, but when a film formed using an extruder or the like is wound up, a phenomenon in which the films stick together, that is, a blocking phenomenon occurs. Furthermore, there is also the problem that films that are easily blocked have poor opening properties and packaging suitability. Therefore, for the purpose of preventing blocking, fine inorganic powders such as diatomaceous earth, kaolin, and talc are added to polyethylene, or unsaturated resin acids such as oleic acid amide and erucic acid amide are added together with the above inorganic fine powders. A solution was adopted in which a lubricant consisting of an amide was used in combination.
しかしながら、上記方法では一時的にブロッキング防止
効果は有るが、長期保存あるいは使用にあってはブロッ
キング防止剤がポリエチレンから剥落してしまい、耐久
性に問題があった。However, although the above method temporarily has an anti-blocking effect, the anti-blocking agent peels off from the polyethylene during long-term storage or use, posing a problem in durability.
高圧法ポリエチレンのブロッキングに対する、他の解決
策として、エチレンと共にスチレンあるいは酢酸ビニル
等を共重合しポリエチレン系共重合体とすることにより
、ブロッキング性を抑制する方法も検討されているが、
この方法ではポリエチレン本来の物性が多少とも損われ
るため、用途的に制約があった。As another solution to the blocking of high-pressure polyethylene, a method of suppressing the blocking property by copolymerizing styrene, vinyl acetate, etc. with ethylene to form a polyethylene copolymer is also being considered.
In this method, the physical properties inherent in polyethylene are impaired to some extent, so there are limitations in terms of its use.
一方、中・低圧法ポリエチレンは、融点が高く、機械的
強度に優れているため、ロープ、漁網および縫糸等に成
形されて、包装用、漁業、農業用、船舶用等の用途に使
用されているが、剛性、潤滑性、耐汚染性等において不
十分な場合があった。On the other hand, medium/low pressure polyethylene has a high melting point and excellent mechanical strength, so it is formed into ropes, fishing nets, sewing threads, etc. and used for packaging, fishing, agriculture, ships, etc. However, there were cases where the rigidity, lubricity, stain resistance, etc. were insufficient.
すなわち、例えば中・低圧法ポリエチレン製の漁網等に
おいては、通常フッ素系化合物等を用いる汚染防止のた
めの表面処理が施されているとおりである。しかし、フ
ッ素系化合物は一般にポリエチレンとの親和性に劣るた
めに、汚染防止が長期的に持続しないという問題はなお
未解決のままであった。That is, for example, fishing nets made of medium- and low-pressure polyethylene are usually subjected to surface treatment using a fluorine compound or the like to prevent contamination. However, since fluorine-based compounds generally have poor affinity with polyethylene, the problem that pollution prevention does not last long has remained unsolved.
本発明は、エチレン系樹脂を成形して得られる成形品の
表面に、耐ブロンキング性、耐汚染性、潤滑性、撥水・
撥油性を発現させることができ、かつその効果を長期的
に持続できる樹脂組成物を提供しようとするものである
。The present invention provides the surface of molded products obtained by molding ethylene resin with bronking resistance, stain resistance, lubricity, water repellency,
The object of the present invention is to provide a resin composition that can exhibit oil repellency and maintain its effect over a long period of time.
（ロ）発明の構成
〔課題を解決するための手段〕
本発明者らは、前記課題を解決するために鋭意検討した
結果、高圧下に、エチレンとシリコーンの片末端に（メ
タ）アクリロイル基が結合してなるシリコーン系マクロ
モノマーとをラジカル重合して得られる新規なグラフト
共重合体が、ポリエチレン単位を主成分とするエチレン
系樹脂と相溶性が良く、−旦該エチレン系樹脂と混練り
されると長期に亘り分離せず、安定でかつ品質が改善さ
れた樹脂組成物となることを見出し、本発明を完成する
に至った。(B) Structure of the Invention [Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors discovered that a (meth)acryloyl group was formed at one end of ethylene and silicone under high pressure. A new graft copolymer obtained by radical polymerization with a silicone-based macromonomer that is bonded has good compatibility with an ethylene-based resin whose main component is polyethylene units, and is kneaded with the ethylene-based resin once it is kneaded with the ethylene-based resin. The present inventors have discovered that the resin composition does not separate over a long period of time, is stable, and has improved quality, and has completed the present invention.
すなわち、本発明は、数平均分子量が２．０００〜５０
，０００のシリコーン分子の片末端に（メタ）アクリロ
イル基を有するマクロ千ツマー０．０５〜２０重量％、
エチレン８０〜９９．９５重量％およびその他のラジカ
ル重合性単量体０−１９．９５重量％を、高圧下でラジ
カル共重合して得られるグラフト共重合体とエチレン系
樹脂からなる樹脂組成物である。That is, in the present invention, the number average molecular weight is 2.000 to 50.
,000 silicone molecules having a (meth)acryloyl group at one end, 0.05 to 20% by weight;
A resin composition consisting of a graft copolymer obtained by radical copolymerization of 80 to 99.95% by weight of ethylene and 0 to 19.95% by weight of other radically polymerizable monomers under high pressure and an ethylene resin. be.
以下、本発明について更に詳しく説明する。The present invention will be explained in more detail below.
本発明においてエチレン系樹脂に配合されるシリコーン
系マクロモノマーは、
（式中、ｎは整数であり、またＲ８、Ｒ２は、炭素数１
〜１０の１価の飽和脂肪族炭化水素基、フェニル基また
は１価のハロゲン化炭化水素基である）
で示されるシリコーン骨格からなり、かつ該シリコーン
分子の片末端に（メタ）アクリロイル基を有する、数平
均分子量が２，０００〜５０，０００のマクロモノマー
であり、その製造方法としては以下の方法が挙げられる
。The silicone macromonomer blended into the ethylene resin in the present invention is as follows:
~10 monovalent saturated aliphatic hydrocarbon groups, phenyl groups, or monovalent halogenated hydrocarbon groups), and has a (meth)acryloyl group at one end of the silicone molecule. , is a macromonomer having a number average molecular weight of 2,000 to 50,000, and its manufacturing method includes the following method.
すなわち、ヘキサメチルシクロトリシロキサンまたはオ
クタメチルシクロトリシロキサン等の環状シロキサンを
アニオン重合させた後、ｒ−メタクリルオキシプロピル
ジメチルクロルシラン等のラジカル重合性基を有するア
ニオン重合停止剤によって重合停止させることにより、
ラジカル重合性のメタクリロイル基を有するシリコーン
系マクロモノマーを製造することができる（特開昭５８
１５４７６６号公報）。That is, after anionically polymerizing a cyclic siloxane such as hexamethylcyclotrisiloxane or octamethylcyclotrisiloxane, the polymerization is terminated with an anionic polymerization terminator having a radically polymerizable group such as r-methacryloxypropyldimethylchlorosilane. ,
A silicone-based macromonomer having a radically polymerizable methacryloyl group can be produced (Japanese Patent Application Laid-open No. 1986
154766).
（式中、ｎは正数であり、Ｒ１およびＲ２は炭素数１〜
工０の１価の飽和脂肪族炭化水素基またはフェニル基な
どである）で示されるα、ω−ジヒドロキシシリコーン
と、（メタ）アクリロイルオキシプロピルトリメトキシ
シラン、ｒ−（メタ）アクリロイルオキシプロピルトリ
クロロシラン、３−（１−（メタ）アクリロイルオキシ
エトキシ）プロピルトリメトキシシラン、３− （２−
（メタ）アクリロイルオキシエトキシ）プロピルトリク
ロロシラン、５−（（メタ）アクリロイルオキシ）ペン
チルトリメトキシシラン、５−（（メタ）アクリロイル
オキシ）ペンチルトリクロロシラン等とを縮合させても
得られる（特開昭６１−１５１２７２号公報等）。(In the formula, n is a positive number, and R1 and R2 have 1 to 1 carbon atoms.
(meth)acryloyloxypropyltrimethoxysilane, r-(meth)acryloyloxypropyltrichlorosilane , 3-(1-(meth)acryloyloxyethoxy)propyltrimethoxysilane, 3-(2-
It can also be obtained by condensing (meth)acryloyloxyethoxy)propyltrichlorosilane, 5-((meth)acryloyloxy)pentyltrimethoxysilane, 5-((meth)acryloyloxy)pentyltrichlorosilane, etc. 61-151272, etc.).
さらに、例えば東亜合成化学工業蛛製シリコーン系マク
ロモノマーＡＫ−５（末端メタクリロイル基型、数平均
分子量；５，０００）およびＡＫ−３０（末端メタクリ
ロイル基型、数平均分子量； ３０．０００） 、チッ
ソ■製サイロブレンＦＭＯ７２１（末端メタクリロイル
基型、平均分子量；５，０００）、同型ＦＭＯ７２５（
末端メタクリロイル基型、平均分子量ｉ１０，０００）
等の市販のシリコーン系マクロモノマーを用いてもよい
。Furthermore, for example, silicone macromonomers AK-5 (terminal methacryloyl group type, number average molecular weight; 5,000) and AK-30 (terminal methacryloyl group type, number average molecular weight; 30,000) manufactured by Toagosei Kagaku Kogyo Himi, Nisso. ■ Silobrene FMO721 (terminal methacryloyl group type, average molecular weight: 5,000), same type FMO725 (
Terminal methacryloyl group type, average molecular weight i10,000)
Commercially available silicone macromonomers such as the following may also be used.
マクロモノマーの数平均分子量が２，０００未満である
と、得られるグラフト共重合体をエチレン系樹脂に添加
しても、該樹脂にシリコーンの持つ特性である撥水・撥
油性、潤滑性などの物性を十分付与できず、一方５０，
０００を超えると、マクロモノマーとエチレンとの共重
合性が低下する。If the number average molecular weight of the macromonomer is less than 2,000, even if the resulting graft copolymer is added to an ethylene resin, the resin will not have the characteristics of silicone, such as water repellency, oil repellency, and lubricity. On the other hand, 50,
If it exceeds 000, the copolymerizability of the macromonomer and ethylene will decrease.
より好ましい数平均分子量は３，０００〜３０．０００
である。More preferable number average molecular weight is 3,000 to 30,000
It is.
グラフト共重合体の製造に用いる単量体混合物中におけ
るマクロモノマーの量は、０．０５〜２０重量％であり
、より好ましくは０．１〜１０重量％である。２０重量
％を超えると、得られるグラフト共重合体中に未重合の
シリコーン系マクロモノマーが多く残り、エチレン系樹
脂に添加した際、それが分離してエチレン系樹脂の表面
に浸出する。The amount of macromonomer in the monomer mixture used to produce the graft copolymer is from 0.05 to 20% by weight, more preferably from 0.1 to 10% by weight. If it exceeds 20% by weight, a large amount of unpolymerized silicone macromonomer remains in the resulting graft copolymer, and when added to the ethylene resin, it separates and leaches onto the surface of the ethylene resin.
一方、０．０５重量％未満であると、グラフト共重合体
中のシリコーン量が不足して、シリコーンの特性が具備
されない。On the other hand, if it is less than 0.05% by weight, the amount of silicone in the graft copolymer will be insufficient and will not have the characteristics of silicone.
上記シリコーン系マクロモノマーと共重合させるエチレ
ンの量は、単量体混合物全体を基準にして８０〜９９．
９５重量％である。単量体混合物におけるエチレンの量
が、８０重量％未満であると、グラフト共重合体におけ
るポリエチレン単位の量が過少となり、得られるグラフ
ト共重合体のエチレン系樹脂への相溶性が劣る。The amount of ethylene to be copolymerized with the silicone macromonomer is 80-99% based on the entire monomer mixture.
It is 95% by weight. If the amount of ethylene in the monomer mixture is less than 80% by weight, the amount of polyethylene units in the graft copolymer will be too small, and the resulting graft copolymer will have poor compatibility with the ethylene resin.
本発明において採用される高圧ラジカル重合におけるエ
チレンの重合転換率は、通常４０％以下であり、エチレ
ンの仕込み量が上記８０〜９９．９５重量％である本発
明におけるグラフト共重合体中のエチレン単量体単位の
量は、６０重量％以上である。The polymerization conversion rate of ethylene in the high-pressure radical polymerization employed in the present invention is usually 40% or less, and the ethylene monomer in the graft copolymer in the present invention in which the amount of ethylene charged is 80 to 99.95% by weight. The amount of mer units is 60% by weight or more.
本発明においては、上記必須成分以外に他のラジカル重
合性単量体を０〜１９．９５重量％の割合で共重合させ
ることができ、かかるラジカル重合性単量体としては、
酢酸ビニル、プロピオン酸ビニル、ビニルベンゾエート
等のビニルエステル；アクリル酸、メタクリル酸〔以下
これらを（メタ）アクリル酸と総称する］、マレイン酸
、マレイン酸無水物、イタコン酸、フマル酸等の不飽和
カルボン酸； （メタ）アクリル酸メチル、（メタ）ア
クリル酸エチル、（メタ）アクリル酸プロピル、（メタ
）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチ
ル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）ア
クリル酸ｎ−ヘキシル、（メタ）アクリル酸ｎ−ヘプチ
ル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリ
ル酸２−エチルヘキシルおよび（メタ）アクリル酸ｎ−
デシル等の（メタ）アクリル酸アルキル；スチレンまた
はその誘導体、ビニルピリジン、ビニルナフタレン等の
ビニル芳香族化合物；Ｎ−ビニルピロリドン、Ｎ−ビニ
ルカプロラクタム等のＮ−ビニル化合物；ビニルメチル
エーテル、ビニルエチルエーテル等のビニルエーテル；
（メタ）アクリル酸グリシジル、（メタ）アクリル酸
アミド、マレイン酸モノエステルおよびジエステル、（
メタ）アクリロニトリル、塩化ビニルおよび一酸化炭素
等が挙げられる。これらの単量体は、単独または２種以
上組み合わせて使用することができる。In the present invention, in addition to the above-mentioned essential components, other radically polymerizable monomers can be copolymerized in a proportion of 0 to 19.95% by weight, and such radically polymerizable monomers include:
Vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate; unsaturated compounds such as acrylic acid, methacrylic acid [hereinafter collectively referred to as (meth)acrylic acid], maleic acid, maleic anhydride, itaconic acid, and fumaric acid Carboxylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, ( n-hexyl meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-(meth)acrylate
Alkyl (meth)acrylates such as decyl; Vinyl aromatic compounds such as styrene or its derivatives, vinylpyridine and vinylnaphthalene; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; Vinyl methyl ether, vinyl ethyl ether vinyl ethers such as;
Glycidyl (meth)acrylate, (meth)acrylic acid amide, maleic acid monoester and diester, (
Examples include meth)acrylonitrile, vinyl chloride, and carbon monoxide. These monomers can be used alone or in combination of two or more.
本発明においてグラフト共重合体は、高圧ラジカル重合
によって製造され、具体的には以下に示す重合条件が採
用できる。In the present invention, the graft copolymer is produced by high-pressure radical polymerization, and specifically, the following polymerization conditions can be employed.
すなわち、マクロモノマ−、エチレンおよびその他のラ
ジカル重合性単量体の総重量に基づき、０．００１〜１
重量％のラジカル重合開始剤を使用して、圧力５００〜
４，０００ｋｇ／ｃｉａ好ましくは１゜０００〜３．５
００ｋｇ／ｃｉｉ、反応温度５０〜４００°Ｃ好ましく
は１００〜３５０°Ｃの条件下で、連鎖移動剤および必
要に応じ助剤の存在下に、槽型および／または前型反応
器内で重合することができる。That is, based on the total weight of macromonomer, ethylene and other radically polymerizable monomers, 0.001 to 1
Using wt% radical polymerization initiator, pressure 500 ~
4,000kg/cia preferably 1°000~3.5
00 kg/cii, reaction temperature 50-400°C, preferably 100-350°C, in the presence of a chain transfer agent and optionally auxiliary agents, in a tank-type and/or front-type reactor. be able to.
ラジカル重合開始剤としては、ペルオキシド、ヒドロペ
ルオキシド、アゾ化合物、アミンオキシド化合物および
酸素等が挙げられる。Examples of the radical polymerization initiator include peroxides, hydroperoxides, azo compounds, amine oxide compounds, and oxygen.
連鎖移動剤としては、水素、プロピレン、ブテン−１、
Ｃ８〜Ｃ０またはそれ以上の飽和脂肪族度化水素および
ハロゲン置換炭化水素、例えばメタン、エタン、プロパ
ン、ブタン、ｉｓｏ −７’タン、ｎ−ヘキサン、ｎ−
へブタン、シクロパラフィン類、二酸化炭素、アセトン
およびメチルエチルケトンならびに芳香族炭化水素例え
ばトルエン、ジエチルベンゼンおよびキシレン等が挙げ
られる。Chain transfer agents include hydrogen, propylene, butene-1,
Saturated aliphatic and halogenated hydrocarbons of C8 to C0 or higher, such as methane, ethane, propane, butane, iso-7'thane, n-hexane, n-
Mention may be made of hebutane, cycloparaffins, carbon dioxide, acetone and methyl ethyl ketone and aromatic hydrocarbons such as toluene, diethylbenzene and xylene.
上記重合により、ポリエチレン単位を主体とする重合体
からなる幹成分およびシリコーンを枝成分とするグラフ
ト共重合体が得られる。かかる構造のシリコーン系グラ
フト共重合体をエチレン系樹脂に添加すると、前記幹成
分がエチレン系樹脂と親和性があるため、グラフト共重
合体とエチレン系樹脂は相分離し難く、さらに枝成分は
グラフト共重合体とエチレン系樹脂との樹脂組成物から
なる成形品の表面に配向し、該表面にシリコーンの特異
的な物性を発現する。By the above polymerization, a graft copolymer having a main component consisting of a polymer mainly composed of polyethylene units and a branch component composed of silicone is obtained. When a silicone-based graft copolymer with such a structure is added to an ethylene-based resin, the graft copolymer and the ethylene-based resin are difficult to phase separate because the main component has an affinity for the ethylene-based resin, and furthermore, the branch components are grafted. It is oriented on the surface of a molded article made of a resin composition of a copolymer and an ethylene resin, and exhibits the specific physical properties of silicone on the surface.
本発明の上記グラフト共重合体が配合される樹脂は、エ
チレン系樹脂であり、具体的には、高圧ラジカル重合法
による低密度ポリエチレン（ＬＤＰＥ）、チーグラー系
触媒またはフィリップス触媒等によるイオン重合で得ら
れる線状および分岐状ノ低密度ポリエチレン（ＬＬＤＰ
Ｅ）および超低密度ポリエチレン（ＶＬＤＰＥ）等のポ
リエチレン類およびエチレン単位を主体とする共重合体
が挙げられ、かかる共重合体としては、エチレンと（メ
タ）アクリル酸、無水マレイン酸、（メタ）アクリル酸
グリシジル等の共重合体、エチレンとアクリル酸メチル
やアクリル酸ブチルなどのアクリル酸エステルとの共重
合体、エチレン−酢酸ビニル共重合体、エチレン−スチ
レン共重合体、エチレン−プロピレン共重合体、エチレ
ン−プロピレン−ジエンモノマー共重合体、およびエチ
レン−プロピレン共重合体またはエチレン−プロピレン
−ジエンモノマー共重合体に（メタ）アクリル酸、無水
マレイン酸または（メタ）アクリル酸グリシジル等をグ
ラフト重合させた共重合体、ならびに一般的にアイオノ
マー樹脂と称されるエチレン系共重合体等がある。The resin to which the graft copolymer of the present invention is blended is an ethylene resin, and specifically, low density polyethylene (LDPE) obtained by high-pressure radical polymerization, ionic polymerization using a Ziegler catalyst or a Phillips catalyst, etc. Linear and branched low density polyethylene (LLDP)
E) and copolymers mainly composed of polyethylenes and ethylene units such as very low density polyethylene (VLDPE); such copolymers include ethylene and (meth)acrylic acid, maleic anhydride, (meth) Copolymers such as glycidyl acrylate, copolymers of ethylene and acrylic esters such as methyl acrylate and butyl acrylate, ethylene-vinyl acetate copolymers, ethylene-styrene copolymers, ethylene-propylene copolymers , ethylene-propylene-diene monomer copolymer, and ethylene-propylene copolymer or ethylene-propylene-diene monomer copolymer graft-polymerized with (meth)acrylic acid, maleic anhydride, glycidyl (meth)acrylate, etc. ionomer resins, and ethylene-based copolymers, which are generally called ionomer resins.
グラフト共重合体のエチレン系樹脂への配合割合は、エ
チレン系樹脂９９．９〜７０重量％およびグラフト共重
合体０．１〜３０重量％となる割合が好ましい、グラフ
ト共重合体の割合が０．１重量％未満の樹脂組成物では
、本発明が目的とする水準の耐ブロッキング性、耐汚染
性、潤滑性、耐水・耐湿性が得られず、また３０重量％
以上であると、エチレン系樹脂本来の物性が消失し易い
。グラフト共重合体のより好ましい量は、組成物全体を
基準にして０．５〜２０重量％である。The ratio of the graft copolymer to the ethylene resin is preferably 99.9 to 70% by weight of the ethylene resin and 0.1 to 30% by weight of the graft copolymer, and the ratio of the graft copolymer is 0. If the resin composition is less than .1% by weight, the level of blocking resistance, stain resistance, lubricity, water/moisture resistance that is the objective of the present invention cannot be obtained;
If it is more than that, the original physical properties of the ethylene resin are likely to be lost. A more preferred amount of graft copolymer is 0.5-20% by weight based on the total composition.
エチレン系樹脂にグラフト共重合体を添加して得られる
本発明の樹脂組成物には、必要に応じて安定剤、顔料、
充填剤、架橋剤、発泡剤、帯電防止剤、難燃剤およびそ
の他一般的にポリエチレンに使用される添加剤を使用し
ても良い。The resin composition of the present invention obtained by adding a graft copolymer to an ethylene resin may contain stabilizers, pigments,
Fillers, crosslinkers, blowing agents, antistatic agents, flame retardants and other additives commonly used in polyethylene may also be used.
〔実施例］
以下実施例および比較例を挙げて、本発明を更に具体的
に説明する。[Example] The present invention will be explained in more detail below with reference to Examples and Comparative Examples.
参考例（グラフト共重合体の製造）
内容積３．８１の撹拌機付き金属製オートクレーブ型反
応器内を、窒素およびエチレンで置換した後、以下の割
合でマクロモノマー（末端メタクリロイルポリジメチル
シロキサン、数平均分子量５０００ ；東亜合成化学工
業■製ＡＫ−５，）ルエン溶液）、連鎖移動剤（ｎ−ヘ
キサン）および重合開始剤（ジ−ｔ−ブチルバーオキシ
ド）を仕込み、以下の２種のグラフト共重合体； ＧＰ
−１およびＣＰ−２を合成した。Reference Example (Production of Graft Copolymer) After purging the inside of a metal autoclave type reactor with an internal volume of 3.81 mm with a stirrer with nitrogen and ethylene, macromonomers (terminated methacryloyl polydimethylsiloxane, several Average molecular weight 5000; AK-5 manufactured by Toagosei Kagaku Kogyo ■) A toluene solution), a chain transfer agent (n-hexane), and a polymerization initiator (di-t-butyl peroxide) were prepared, and the following two types of graft compounds were prepared. Polymer; GP
-1 and CP-2 were synthesized.
ＣＰ−Ｉ ＣＰ−２
エチレン （ｇ） １７００ １７
００マクロモノマー（ｇ） ３
５０トルエン（ｇ） ５０
１６５ｎ−ヘキサン軸＞ ３００
３００なお、重合圧力１６００ｋｇ／ｃｉｉ、温度１
７０°Ｃで１時間重合させた。CP-I CP-2 Ethylene (g) 1700 17
00 macromonomer (g) 3
50 Toluene (g) 50
165n-hexane axis > 300
300, polymerization pressure 1600 kg/cii, temperature 1
Polymerization was carried out at 70°C for 1 hour.
得られたグラフト共重合体を加熱した四塩化炭素に溶解
したのち、この溶液を多量のメチルエチルケトン中に投
入し再沈させ精製した。After the obtained graft copolymer was dissolved in heated carbon tetrachloride, this solution was poured into a large amount of methyl ethyl ketone and reprecipitated to purify it.
精製されたグラフト共重合体について赤外線吸収スペク
トル、元素分析およびＮＭＲスペクトルを測定した結果
、ＣＰ−１およびＣＰ−２は次の組成（重量％）を有す
ることが分かった。As a result of measuring the infrared absorption spectrum, elemental analysis, and NMR spectrum of the purified graft copolymer, it was found that CP-1 and CP-2 had the following composition (% by weight).
ＣＰ−Ｉ ＣＰ−２
エチレン単量体単位 ９８．５ ７５．７マクロ
モノマ一単位 １．５ ２４．３実施例１〜３
および比較例
日本石油化学■製低密度ポリエチレン（８石しクスロン
Ｍ１５）に、参考例で得られたＣＰ−１およびＣＰ−２
を表１に示した割合で添加し、温度１５０°Ｃで２軸押
出機で溶融混合した。CP-I CP-2 Ethylene monomer unit 98.5 75.7 Macromonomer unit 1.5 24.3 Examples 1 to 3
and Comparative Example CP-1 and CP-2 obtained in the Reference Example were added to low-density polyethylene (8 stone Xuron M15) manufactured by Nippon Petrochemical ■.
were added in the proportions shown in Table 1, and melt-mixed using a twin-screw extruder at a temperature of 150°C.
得られたベレットをプレス成形して試験片を作成し、そ
の表面物性を測定した。結果は表１に記載のとおりであ
る。The obtained pellet was press-molded to prepare a test piece, and its surface properties were measured. The results are shown in Table 1.
なお、上記ポリエチレンのみからなる試験片に関する具
体例を比較例とした。In addition, the specific example regarding the test piece made only of the said polyethylene was made into the comparative example.
実施例４
実施例２の試験片について、７０°Ｃのオーブンに７２
時間放置させた後、表面物性を測定した。Example 4 The specimen of Example 2 was placed in an oven at 70°C for 72 hours.
After being allowed to stand for a period of time, surface properties were measured.
その結果は、動摩擦係数０．１５８９、接触角９１゜で
あり、上記加温によりシリコーンを樹脂組成物から分離
促進させたが、グラフト共重合体はポリエチレンと分離
せず、従って試験片は加温前と同様な表面物性を維持し
ていた。The results showed that the coefficient of dynamic friction was 0.1589 and the contact angle was 91°. Although the heating described above promoted the separation of the silicone from the resin composition, the graft copolymer did not separate from the polyethylene, so the test piece was heated. The same surface properties as before were maintained.
（ハ）発明の効果
本発明の樹脂組成物から得られる成形品においては、グ
ラフト共重合体の枝成分として存在するシリコーンが、
成形品の表面に濃縮される。(c) Effects of the invention In the molded article obtained from the resin composition of the invention, the silicone present as a branch component of the graft copolymer is
It is concentrated on the surface of the molded product.
その結果、前記成形品の表面には、シリコーンの特性で
ある耐ブロッキング性、耐汚染性、潤滑性および撥水性
が付与される。しかも、グラフト共重合体は、幹成分と
してポリエチレン単位を主体とする重合体を有しており
、幹成分がエチレン系樹脂に対しアンカー作用を示すた
め、グラフト共重合体がエチレン系樹脂から分離し難い
ので、表面改質は長期に亘り持続する。As a result, the surface of the molded article is provided with blocking resistance, stain resistance, lubricity, and water repellency, which are characteristics of silicone. Moreover, the graft copolymer has a polymer mainly composed of polyethylene units as a backbone component, and since the backbone component exhibits an anchoring effect on the ethylene resin, the graft copolymer does not separate from the ethylene resin. Since the surface modification is difficult, the surface modification lasts for a long time.
Claims (1)
ーン分子の片末端に（メタ）アクリロイル基を有するマ
クロモノマー０．０５〜２０重量％、エチレン８０〜９
９．９５重量％およびその他のラジカル重合性単量体０
〜１９．９５重量％を、高圧下でラジカル共重合して得
られるグラフト共重合体とエチレン系樹脂からなる樹脂
組成物。1. 0.05-20% by weight of a macromonomer having a (meth)acryloyl group at one end of a silicone molecule with a number average molecular weight of 2,000-50,000, ethylene 80-9
9.95% by weight and 0 other radically polymerizable monomers
A resin composition comprising a graft copolymer obtained by radical copolymerization of ~19.95% by weight under high pressure and an ethylene resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12434490A JPH0420551A (en) | 1990-05-15 | 1990-05-15 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12434490A JPH0420551A (en) | 1990-05-15 | 1990-05-15 | Resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0420551A true JPH0420551A (en) | 1992-01-24 |
Family
ID=14883039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12434490A Pending JPH0420551A (en) | 1990-05-15 | 1990-05-15 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0420551A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6292162B1 (en) | 1996-06-07 | 2001-09-18 | Nec Corporation | Driving circuit capable of making a liquid crystal display panel display and expanded picture without special signal processor |
-
1990
- 1990-05-15 JP JP12434490A patent/JPH0420551A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6292162B1 (en) | 1996-06-07 | 2001-09-18 | Nec Corporation | Driving circuit capable of making a liquid crystal display panel display and expanded picture without special signal processor |
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