JPH02150441A - Moldable resin composition - Google Patents
Moldable resin compositionInfo
- Publication number
- JPH02150441A JPH02150441A JP30518588A JP30518588A JPH02150441A JP H02150441 A JPH02150441 A JP H02150441A JP 30518588 A JP30518588 A JP 30518588A JP 30518588 A JP30518588 A JP 30518588A JP H02150441 A JPH02150441 A JP H02150441A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- formula
- present
- silicone
- ethylene
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 239000000203 mixture Substances 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- -1 polysiloxane Polymers 0.000 description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- QQIMUPFCBBIKKN-SOFGYWHQSA-N (11E)-tetradeca-1,11-diene Chemical compound CC\C=C\CCCCCCCCC=C QQIMUPFCBBIKKN-SOFGYWHQSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- YHHHHJCAVQSFMJ-FNORWQNLSA-N (3e)-deca-1,3-diene Chemical compound CCCCCC\C=C\C=C YHHHHJCAVQSFMJ-FNORWQNLSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- HITROERJXNWVOI-SOFGYWHQSA-N (5e)-octa-1,5-diene Chemical compound CC\C=C\CCC=C HITROERJXNWVOI-SOFGYWHQSA-N 0.000 description 1
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- VOSLXTGMYNYCPW-UHFFFAOYSA-N 1,10-Undecadiene Chemical compound C=CCCCCCCCC=C VOSLXTGMYNYCPW-UHFFFAOYSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920002943 EPDM rubber Polymers 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
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- IYPLTVKTLDQUGG-UHFFFAOYSA-N dodeca-1,11-diene Chemical compound C=CCCCCCCCCC=C IYPLTVKTLDQUGG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- JEJVUMPKJVMOEZ-UHFFFAOYSA-N hexadeca-1,15-diene Chemical compound C=CCCCCCCCCCCCCC=C JEJVUMPKJVMOEZ-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ZICBMHDDLLEGHU-UHFFFAOYSA-N nonadeca-1,18-diene Chemical compound C=CCCCCCCCCCCCCCCCC=C ZICBMHDDLLEGHU-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- CXFSMVPFLZVLLK-UHFFFAOYSA-N pentadeca-1,14-diene Chemical compound C=CCCCCCCCCCCCC=C CXFSMVPFLZVLLK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- ROEHNQZQCCPZCH-UHFFFAOYSA-N tert-butyl 2-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OC(C)(C)C ROEHNQZQCCPZCH-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
(・産業上の利用分野)
本発明は、フィルムやチューブに成形可能な樹脂組成物
に関する。更に詳しくは、本発明は、ポリエチレン系樹
脂ポリシロキサン系重合体、両末端に不飽和基を含有す
る化合物及び有機過酸化物からなる成形可能な樹脂組成
物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin composition that can be molded into a film or a tube. More specifically, the present invention relates to a moldable resin composition comprising a polyethylene resin polysiloxane polymer, a compound containing unsaturated groups at both ends, and an organic peroxide.
(従来の技術)
シリコーンは、その滑り性、離型性、易酸素透過性、は
っ水性、電気絶縁性等の優れた性質から、広く使用され
てきているが、機械的強度が低く、成膜が困難で、成型
性が劣るという欠点を有している。(Prior art) Silicone has been widely used due to its excellent properties such as slipperiness, mold releasability, easy oxygen permeability, water repellency, and electrical insulation, but it has low mechanical strength and It has the disadvantage that it is difficult to form a film and has poor moldability.
(発明が解決しようとする問題点)
本発明は、シリコーンが有している、低機械的強度、低
酸膜性、低成型性等の欠点の改良された樹脂を得ようと
するものである。(Problems to be Solved by the Invention) The present invention aims to obtain a resin that is improved from the disadvantages of silicone, such as low mechanical strength, low acid film resistance, and low moldability. .
(問題点を解決するための手段)
本発明者らは、シリコーンが有している、低機械的強度
、低成膜性、低成型性等の欠点の改良された樹脂を得る
ために鋭意研究の結果本発明を完成した。(Means for Solving the Problems) The present inventors have conducted extensive research in order to obtain a resin that has improved disadvantages of silicone, such as low mechanical strength, low film-forming properties, and low moldability. As a result, the present invention was completed.
即ち、本発明は、エチレン系ポリマー100重量部に対
し、
(A1式で表わされるオルガノポリシロキサン0.01
〜300重量部、
R’、 R”ゎSIO<−a−b (A
l(式中R′は脂肪族不飽和基、R2は脂肪族不飽和基
を含まない非置換または置換1価炭化水素基、O<a<
1,0.5<b<3.l<alb〈3)
(B1式で表わされる炭化水素化合物0.01〜30部
、
CH2”CH(CHa)CCH:CH2(al(式中、
Cは1〜30の整数)、
及び、有機過酸化物0.001〜3部からなる成形可能
な樹脂組成物である。That is, in the present invention, 0.01 parts of organopolysiloxane represented by formula A1 is added to 100 parts by weight of the ethylene polymer.
~300 parts by weight, R', R"ゎSIO<-a-b (A
l (in the formula, R' is an aliphatic unsaturated group, R2 is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated group, O<a<
1, 0.5<b<3. l<alb<3) (0.01 to 30 parts of a hydrocarbon compound represented by the formula B1, CH2''CH(CHa)CCH:CH2(al (in the formula,
C is an integer of 1 to 30), and 0.001 to 3 parts of an organic peroxide.
本発明の樹脂組成物は、フィルムやチューブ等に成形可
能であり、これよりエチレン系ポリマーと有機シリコー
ン化合物とが、マクロな分散不良な状態ではなく均一に
混合した成形物を得ることができる。The resin composition of the present invention can be molded into films, tubes, etc., and from this it is possible to obtain a molded product in which the ethylene polymer and the organic silicone compound are uniformly mixed without macroscopically poor dispersion.
エチレン系ポリマーと (A1式で表わされるオルガノ
ポリシロキサンとを、たとえば、バンバリーミキサ−で
混練しようとしても、スリップが起こり、混練しにくく
、混線できても、反応が起こりにくい、しかし、有機過
酸化物を系に添加すると短時間でトルクが上昇し、反応
が始まり、エチレン系ポリマーとオルガノポリシロキサ
ン化合物とが結合する。しかし、この系では、シリコー
ン架橋体の集合した塊状物が多く発生し、均一な樹脂に
はなりにくい。Even if an ethylene polymer and an organopolysiloxane represented by the formula A1 are kneaded in a Banbury mixer, for example, slipping occurs and kneading is difficult, and even if mixing occurs, reaction is difficult to occur. When a compound is added to the system, the torque increases in a short period of time, a reaction begins, and the ethylene polymer and organopolysiloxane compound bond together.However, in this system, many lumps of silicone crosslinked products are generated, It is difficult to form a uniform resin.
そこで、本発明者らは鋭意検討を続けた結果、この系に
、 (B1式で表わされる炭化水素化合物を添加するこ
とにより、シリコーン架橋体の集合した塊状物がほとん
ど発生しない、均一な樹脂を得ることができることを見
出した。Therefore, as a result of intensive studies, the present inventors found that by adding a hydrocarbon compound represented by the formula B1 to this system, a uniform resin in which almost no lumps of silicone crosslinks are generated is created. I found out what I can get.
本発明の組成物により得られる樹脂は、ポリエチレンな
どの一般の成型機でフィルムやチューブに加工できる。The resin obtained from the composition of the present invention can be processed into films and tubes using general molding machines such as polyethylene.
また、フィルムやチューブは、シリコーン架橋体の集合
した塊状物がほとんど無い、均一な成形物となる。Further, the film or tube becomes a uniform molded product with almost no lumps of silicone crosslinked material.
本発明の組成物により得られる樹脂は、他の樹脂、たと
えば、ポリスチレン、ナイロン、ポリエステル、ポリカ
ーボネートなどに混合することにより、その加工性や耐
衝撃性を改善することができる。The processability and impact resistance of the resin obtained from the composition of the present invention can be improved by mixing it with other resins such as polystyrene, nylon, polyester, polycarbonate, etc.
本発明において使用されるエチレン系ポリマーとは、エ
チレンを主成分とする重合体であり、高圧法ポリエチレ
ン、線状低密度ポリエチレン(LLDPEI 、エチレ
ン−αオレフィン共重合体、エチレン−酢酸ビニル共重
合体、エチレン−アクリル酸共重合体、エチレン−メタ
クリル酸共重合体、エチレン−アクリル酸メチル共重合
体、エチレン−メタクリル酸メチル共重合体、エチレン
−アクリル酸エチル共重合体、エチレン−メタクリル酸
エチル共重合体、エチレン−ビニルアルコール共重合体
、あるいは、エチレン−プロピレン−ジエン三元共重合
体その他が挙げられる。The ethylene polymer used in the present invention is a polymer whose main component is ethylene, such as high-pressure polyethylene, linear low-density polyethylene (LLDPEI), ethylene-α olefin copolymer, ethylene-vinyl acetate copolymer, etc. , ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl methacrylate copolymer Examples include polymers, ethylene-vinyl alcohol copolymers, ethylene-propylene-diene terpolymers, and others.
本発明で使用される fAj式で表わされるオルガノポ
リシロキサンにおいて、R’基としては、ビニル基、ア
リル基、アクリル基、メタクリル基等が例示され、R2
基としては、メチル基、エチル基、プロピル基、などの
アルキル基、フェニル基、トリル基などのアリール基、
シクロヘキシル基、シクロブチル基などのシクロアルキ
ル基およびこれら炭化水素基の炭素原子に結合した水素
基を部分的にハロゲン原子、シアン基、メルカプト基な
どで置換した基などが例示されるが、これらはその同種
または異種の組合せでもよい。In the organopolysiloxane represented by the formula fAj used in the present invention, examples of the R' group include a vinyl group, an allyl group, an acrylic group, a methacryl group, and R2
Examples of groups include alkyl groups such as methyl, ethyl, and propyl; aryl groups such as phenyl and tolyl;
Examples include cycloalkyl groups such as cyclohexyl and cyclobutyl groups, and groups in which the hydrogen group bonded to the carbon atom of these hydrocarbon groups is partially substituted with a halogen atom, cyan group, mercapto group, etc. It may be a combination of the same or different types.
又、aは0以上、1以下であり、0であるとエチレン系
ポリマーや (B)式で表わされる炭化水素化合物と反
応がおこらず望ましくなく、1以上であると、本発明の
組成物でつくった成形品が硬くなりすぎ望ましくない。Further, a is 0 or more and 1 or less; if it is 0, it will not react with the ethylene polymer or the hydrocarbon compound represented by formula (B), which is undesirable; if it is 1 or more, the composition of the present invention will not react. The molded product made becomes too hard, which is undesirable.
aは好適には0.0004〜0.06である。bは0.
5以上、3以下であり、0.5以下であると本発明の組
成物の混線がむつ゛かしく、加工性が劣り、3以上であ
ると本発明の組成物でつくった成形品が硬くなりすぎ望
ましくない、bは好適には1〜2である。a is preferably 0.0004 to 0.06. b is 0.
If it is 5 or more and 3 or less, and if it is 0.5 or less, the cross-wire of the composition of the present invention will be difficult and the processability will be poor, and if it is 3 or more, the molded product made from the composition of the present invention will be hard. Too undesirable, b is preferably 1-2.
本発明のオルガノポリシロキサンの分子構造は、 (A
)式の範囲に入っておれば、鎖状、分45゜41状、環
状、網状、立体網状等のい、ずれのものであってもよい
。The molecular structure of the organopolysiloxane of the present invention is (A
) may be in the form of a chain, a 45°41 shape, a ring shape, a net shape, a three-dimensional network shape, or any other shape.
本発明のオルガノポリシロキサンの重合度は、特に限定
しないが1本発明に使用するエチレン系ポリマーとの混
線に支障がない適度の重合度が必要であり、250以上
が望ましい。Although the degree of polymerization of the organopolysiloxane of the present invention is not particularly limited, it is necessary to have an appropriate degree of polymerization that does not interfere with crosstalk with the ethylene polymer used in the present invention, and is preferably 250 or more.
本発明で使用される、 (B1式で表わされる炭化水素
化合物の例として、 1.4−ペンタジェン、1,5−
へキサジエン、 1.6−へブタジェン、 1.7−オ
クタジエン、 1.8−ノナジェン、1.9−デカジエ
ン、l、 10−ウンデカジエン、1、11−ドデカジ
エン、1.12−トリデカジエン、1.13−テトラデ
カジエン、l、14−ペンタデカジエン、1,15−へ
キサデカジエン、1.16−’へブタデカジエン、l、
17−オクタデカジエン、1.18−ノナデカジエンそ
の他が挙げられる。Examples of the hydrocarbon compound represented by the formula B1 used in the present invention include 1,4-pentadiene, 1,5-
Hexadiene, 1.6-hebutadiene, 1.7-octadiene, 1.8-nonadiene, 1.9-decadiene, 1, 10-undecadiene, 1,11-dodecadiene, 1.12-tridecadiene, 1.13- Tetradecadiene, 1, 14-pentadecadiene, 1,15-hexadecadiene, 1.16-'hebutadecadiene, 1,
Examples include 17-octadecadiene, 1,18-nonadecadiene, and others.
本発明において使用される有機過酸化物は、分解温度が
半減期10分間で100〜220℃のものであり、次の
ものが例として挙げられる。ただし、括弧内は、分解温
度(°C)である。The organic peroxide used in the present invention has a decomposition temperature of 100 to 220° C. with a half-life of 10 minutes, and examples thereof include the following. However, the value in parentheses is the decomposition temperature (°C).
コハク酸ペルオキシド(1101、ベンゾイルペルオキ
シド(1101、t−ブチルペルオキシ−2−エチルヘ
キサノエート(113) p−クロロベンゾイルペル
オキシド(1151、t−ブチルペルオキシイソブチレ
ート(115) 、 t−ブチルペルオキシイソプロ
ビルカーボネート(1351、t −ブチルペルオキシ
ラウレートf140)、2,5−ジメチル−2,5−ジ
(ベンゾイルペルオキシ)ヘキサン(1401、t−ブ
チルペルオキシアセテート(140) 、ジ−t−ブチ
ルペルオキシフタレート(140) 、 t−ブチル
ペルオキシマレイン酸+1401 シクロヘキサノン
ペルオキシド(145) 、 t−ブチルペルオキシ
ベンゾエート(145)、シクミルヘルオキシド(15
0) 2,5−ジメチル−2,5−ジ(t−ブチル
ペルオキシ)ヘキサン(1551t−ブチルクミルペル
オキシド(1551、t−ブチルヒドロペルオキシド(
1581、ジーt−プチルヘルオキシド(160)2.
5−ジメチル−2,5−ジ(t−ブチルペルオキシ)ヘ
キシン3 (1701、ジ−イソプロピルベンゼンヒド
ロベルオキシド(170) 、 p−メンタンヒドロペ
ルオキシド(180)、 2,5−ジメチルヘキサン−
2,5−ジヒドロペルオキシド本発明において使用され
る、 (A)式で表わされるオルガノポリシロキサンは
、エチレン系ポリマー100重量部に対し、0.01部
以上必要であり、好ましくは0.05〜300部必要で
ある。 0.01部より少ないと、シリコーンの特性が
現われに(い、また、300部より多いと、成膜等が困
難になることがある。Succinic acid peroxide (1101, benzoyl peroxide (1101, t-butylperoxy-2-ethylhexanoate (113)) p-chlorobenzoyl peroxide (1151, t-butylperoxyisobutyrate (115), t-butylperoxyisopropyl carbonate (1351, t-butylperoxylaurate f140), 2,5-dimethyl-2,5-di(benzoylperoxy)hexane (1401, t-butylperoxyacetate (140), di-t-butylperoxyphthalate (140) ), t-butylperoxymaleic acid + 1401 cyclohexanone peroxide (145), t-butylperoxybenzoate (145), cycumylheroxide (15)
0) 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (1551 t-butylcumyl peroxide (1551, t-butyl hydroperoxide (
1581, di-t-butylheroxide (160)2.
5-dimethyl-2,5-di(t-butylperoxy)hexyne 3 (1701, di-isopropylbenzene hydroperoxide (170), p-menthane hydroperoxide (180), 2,5-dimethylhexane-
2,5-dihydroperoxide The organopolysiloxane represented by formula (A) used in the present invention is required in an amount of 0.01 part or more, preferably 0.05 to 300 parts by weight, per 100 parts by weight of the ethylene polymer. Part is necessary. If the amount is less than 0.01 part, the characteristics of silicone will not be exhibited (and if it is more than 300 parts, film formation etc. may become difficult).
本発明において使用される、 (B1式で表わされる炭
化水素化合物の量は、0.01部以上必要である。 0
.01部より少ないと、成形物に、シリコーン架橋体の
集合した塊状物が多く発生してしまう。The amount of the hydrocarbon compound represented by the formula B1 used in the present invention is required to be 0.01 part or more. 0
.. If the amount is less than 0.01 parts, many lumps of silicone crosslinked products will be formed in the molded product.
本発明において使用される有機過酸化物は、エチレン系
ポリマー100重量部に対し、0.001〜3部、好ま
しくは0.01〜0.05部必要である。The organic peroxide used in the present invention is required in an amount of 0.001 to 3 parts, preferably 0.01 to 0.05 parts, per 100 parts by weight of the ethylene polymer.
o、ooi部より少ないと反応が殆ど進行せず、3部よ
り多いと、樹脂の成形性を損なうことがある。If the amount is less than o or ooi parts, the reaction will hardly proceed, and if it is more than 3 parts, the moldability of the resin may be impaired.
本発明において組成物には必要により、酸化安定剤、紫
外線安定剤、無機充填剤、顔料、難燃剤、ゴム類などを
配合することができる。In the present invention, the composition may contain oxidation stabilizers, ultraviolet stabilizers, inorganic fillers, pigments, flame retardants, rubbers, etc., if necessary.
本発明の組成物を加熱混練することにより、均一化し、
押し出し成形等が可能になる。加熱混線は、バンバリー
ミキサ−12軸押出機その他、通常の混線装置で行なう
ことができる。加熱温度は、100℃〜300℃程度が
望ましい。By heating and kneading the composition of the present invention, it is homogenized,
Extrusion molding becomes possible. The heating and mixing can be carried out using a Banbury mixer, a 12-screw extruder, and other conventional mixing devices. The heating temperature is preferably about 100°C to 300°C.
(実施例)
実施例1
メルトインデックス(190℃、 2160g12.5
g/10111in +酢酸ビニル含量18wt%のエ
チレン−酢酸ビニル共重合体(日本ユニカー製)100
部、23℃における粘度が300.0OOC3で、メチ
ルビニルシリコーン含量1.0%のシリコーンガムスト
ック(日本ユニカー製)100部、 1.9デ力ジエン
1部、ジクミルペルオキシド0.05部、及びイルガノ
ックス1010 (チバガイギー製酸化防止剤)0.1
部をブーラベンダープラストグラフで、100℃で10
分間混線後、200℃で10分間混練した後、圧縮成形
法で厚さ1mmのシートにした。(Example) Example 1 Melt index (190°C, 2160g12.5
g/10111in + ethylene-vinyl acetate copolymer with a vinyl acetate content of 18 wt% (manufactured by Nippon Unicar) 100
100 parts of silicone gum stock (manufactured by Nippon Unicar) with a viscosity of 300.0 OOC3 at 23°C and a methyl vinyl silicone content of 1.0%, 1 part of 1.9 depot diene, 0.05 part of dicumyl peroxide, and Irganox 1010 (antioxidant manufactured by Ciba Geigy) 0.1
10% at 100°C using a Boulavender plastograph.
After mixing for a minute, the mixture was kneaded at 200° C. for 10 minutes, and then compressed into a sheet with a thickness of 1 mm.
このシートは、不均一な部分がなかった。この混線物の
メルトインデックスは0.5g710m1nであり、ま
た、引張強さ60kg/crn’、伸びが300%の表
面にシリコーンのにじみだしのないシートであった。こ
のシートをペレット化したものは、ブラベンダープラス
トグラフの押し出し装置で、160℃でテープに押し出
すことができた。This sheet had no non-uniform areas. The melt index of this mixed wire was 0.5 g, 710 m1n, and the sheet had a tensile strength of 60 kg/crn', an elongation of 300%, and no silicone bleeding on the surface. A pelletized version of this sheet could be extruded into a tape at 160° C. using a Brabender Plastograph extruder.
比較例1
実施例1と同様にして、ジクミルペルオキシドを添加せ
ずシート化し、ペレット化した。得られたシートは、に
じみたしが多く、ペレットは押し出しが困難であった。Comparative Example 1 In the same manner as in Example 1, it was formed into a sheet and pelletized without adding dicumyl peroxide. The resulting sheet had a lot of smudges and the pellets were difficult to extrude.
比較例2
実施例1と同様にして、 1.9デカジエンを添加せず
、混練したところ、シリコーン架橋物が、プラストグラ
フの内面に膜を形成してしまい、反応後、混線物を取り
出す時、内容物を完全には取り出せなかった。混線物を
シート化したものは、直径0.1〜0.5mm程度の、
有機シリコーン化合物の架橋体が集合した箇所が見られ
、均一なシートが得られなかった。Comparative Example 2 When kneading was carried out in the same manner as in Example 1 without adding 1.9 decadiene, the silicone crosslinked product formed a film on the inner surface of the plastograph, and when the mixed material was taken out after the reaction, The contents could not be completely removed. The mixed material is made into a sheet with a diameter of about 0.1 to 0.5 mm.
There were areas where crosslinked organic silicone compounds aggregated, and a uniform sheet could not be obtained.
実施例2
メルトインデックス1.5g710m1n 、酢酸ビニ
ル含量15wt%のエチレン−酢酸ビニル共重合体(日
本ユニカー製)100部、23℃における粘度が300
.0OOC3で、メチルビニルシリコーン含量5.0%
のシリコーンガムストック(日本ユニカー製)100部
、 1,9デ力ジエン2部、ジクミルペルオキシド0.
03部、及びイルガノックス1010 (チバガイギー
製酸化防止剤)0.1部をプラベンダープラストグラフ
で、 100℃で10分間混線後、200℃で10分間
混練した後、圧縮成形法で厚さ1mmのシートにした。Example 2 100 parts of ethylene-vinyl acetate copolymer (manufactured by Nippon Unicar) with a melt index of 1.5 g, 710 m1n and a vinyl acetate content of 15 wt%, and a viscosity of 300 at 23°C.
.. 0OOC3, methylvinyl silicone content 5.0%
100 parts of silicone gum stock (manufactured by Nippon Unicar), 2 parts of 1,9-diene, 0.0 parts of dicumyl peroxide.
03 parts and 0.1 part of Irganox 1010 (antioxidant manufactured by Ciba Geigy) were mixed in a Prabender Plastograph at 100°C for 10 minutes, then kneaded at 200°C for 10 minutes, and then compression molded into 1mm thick pieces. I made it into a sheet.
このシートは、不均一な部分がなかった。この混線物の
メルトインデックスは0.2g/10m1nであり、ま
た、引張強さ70kg/err?、伸びが300%の表
面に殆どシリコーンのにじみだしのないシートであった
。This sheet had no non-uniform areas. The melt index of this mixed wire is 0.2 g/10 m1n, and the tensile strength is 70 kg/err? The sheet had an elongation of 300% and had almost no silicone bleeding on its surface.
このシートをペレット化したものは、ブラベンダーブラ
ストグラフの押し出し装置で、 160℃でテープに押
し出すことができた。This sheet was pelletized and could be extruded into tape at 160°C using a Brabender Blastgraph extruder.
二オンカーバイド製)100部、23℃における粘度が
300.0OOC3で、メチルビニルシリコーン含量5
,0%のシリコーンガムストック(日本ユニカー製)1
00部、 1.9デ力ジエン2部、ジクミルペルオキシ
ド0.03部、及びイルガノックス1O1O(チバガイ
ギー製酸°化防止剤)0.1部をブラベンダープラスト
グラフで、 100℃で10分間混線後、 200℃で
10分間混練した後、圧縮成形法で厚さ1mmのシート
にした。この混練物のメルトインデックスは0.4g7
10m1nであり、また、引張強さ90kg/Ctrl
’、伸びが600%の表面に殆どシリコーンのにじみだ
しのないシートであった。このシートをペレット化した
ものは、ブラベンダープラストグラフの押し出し装置で
、160℃でテープに押し出すことができた。(manufactured by Nion Carbide) 100 parts, viscosity at 23°C is 300.0OOC3, methylvinyl silicone content 5
, 0% silicone gum stock (manufactured by Nippon Unicar) 1
00 parts, 2 parts of 1.9 DEG diene, 0.03 parts of dicumyl peroxide, and 0.1 part of Irganox 1O1O (oxidation inhibitor manufactured by Ciba Geigy) were mixed in a Brabender Plastograph at 100°C for 10 minutes. After that, the mixture was kneaded at 200°C for 10 minutes, and then compressed into a sheet with a thickness of 1 mm. The melt index of this kneaded product is 0.4g7
10m1n, and tensile strength 90kg/Ctrl
'The sheet had an elongation of 600% and had almost no silicone bleeding on its surface. A pelletized version of this sheet could be extruded into a tape at 160° C. using a Brabender Plastograph extruder.
実施例3
メルトインデックス4.7g710m1n 、密度0.
900の、エチレン−ブテン−1共重合体(ユ実施例4
メルトフローインデックス(200℃、5.000g1
10、0g/10m1nで、アイゾツト衝撃強さ(ノッ
チ付き) 1.3kg −am7cmのポリスチレン1
00部に対して、実施例1で得たペレットlo部をブラ
ベンダープラストグラフで、200℃で10分間混線後
、取り出してシート化し、アイゾツト衝撃強さを測定し
たところ、3.3kg −cm/amであった。Example 3 Melt index 4.7g710m1n, density 0.
900, ethylene-butene-1 copolymer (U Example 4 Melt flow index (200°C, 5.000 g
10.0g/10m1n, Izot impact strength (notched) 1.3kg -am7cm polystyrene 1
00 parts, the lo part of the pellet obtained in Example 1 was mixed with a Brabender plastograph at 200°C for 10 minutes, taken out and formed into a sheet, and the Izot impact strength was measured, and it was found to be 3.3 kg - cm / It was am.
(発明の効果)
本発明の組成物は、フィルム、シート、チューブその他
に成形可能なため、シリコーンの性質を保持した成型物
が得られ、医療用部品、工業用部品、電気材料部品その
他に適用され、また、エンジニアリングプラスチックス
の加工性、耐衝撃性の改良材として適用できる。(Effects of the Invention) Since the composition of the present invention can be molded into films, sheets, tubes, etc., molded products that retain the properties of silicone can be obtained, and can be applied to medical parts, industrial parts, electrical material parts, etc. It can also be used as a material to improve the processability and impact resistance of engineering plastics.
特許出願人 日本ユニカー株式会社 (ばか2名)Patent applicant: Nippon Unicar Co., Ltd. (2 idiots)
Claims (2)
式で表わされるオルガノポリシロキサン0.01〜30
0重量部、 R^1_aR^2_bSiO_4_−_a_−_b_/
_2(A)(式中R^1は脂肪族不飽和基、R^2は脂
肪族不飽和基を含まない非置換または置換1価炭化水素
基、0<a<1、0.5<b<3、1<a+b<3) (B)式で表わされる炭化水素化合物0.01〜30部
、 CH_2=CH(CH_2)cCH=CH_2(B)(
式中、cは1〜30の整数)、 及び、有機過酸化物0.001〜3部からなる成形可能
な樹脂組成物。(1) For 100 parts by weight of ethylene polymer, (A)
Organopolysiloxane represented by the formula 0.01-30
0 parts by weight, R^1_aR^2_bSiO_4_-_a_-_b_/
_2(A) (in the formula, R^1 is an aliphatic unsaturated group, R^2 is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated group, 0<a<1, 0.5<b <3, 1<a+b<3) (B) 0.01 to 30 parts of a hydrocarbon compound represented by the formula, CH_2=CH(CH_2)cCH=CH_2(B)(
(where c is an integer of 1 to 30); and 0.001 to 3 parts of an organic peroxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30518588A JP2704649B2 (en) | 1988-12-02 | 1988-12-02 | Moldable resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30518588A JP2704649B2 (en) | 1988-12-02 | 1988-12-02 | Moldable resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02150441A true JPH02150441A (en) | 1990-06-08 |
JP2704649B2 JP2704649B2 (en) | 1998-01-26 |
Family
ID=17942077
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30518588A Expired - Lifetime JP2704649B2 (en) | 1988-12-02 | 1988-12-02 | Moldable resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2704649B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0404004A2 (en) * | 1989-06-19 | 1990-12-27 | Nippon Unicar Company Limited | A shape memory elastic body |
EP0405278A2 (en) * | 1989-06-19 | 1991-01-02 | Nippon Unicar Company Limited | A coating agent and coated material thereof |
JP2010518197A (en) * | 2007-02-05 | 2010-05-27 | ダウ グローバル テクノロジーズ インコーポレイティド | Crosslinkable polyethylene composition, process for producing the same and article produced therefrom |
-
1988
- 1988-12-02 JP JP30518588A patent/JP2704649B2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0404004A2 (en) * | 1989-06-19 | 1990-12-27 | Nippon Unicar Company Limited | A shape memory elastic body |
EP0405278A2 (en) * | 1989-06-19 | 1991-01-02 | Nippon Unicar Company Limited | A coating agent and coated material thereof |
JP2010518197A (en) * | 2007-02-05 | 2010-05-27 | ダウ グローバル テクノロジーズ インコーポレイティド | Crosslinkable polyethylene composition, process for producing the same and article produced therefrom |
Also Published As
Publication number | Publication date |
---|---|
JP2704649B2 (en) | 1998-01-26 |
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