JPH0362811A - Modified elastomer - Google Patents
Modified elastomerInfo
- Publication number
- JPH0362811A JPH0362811A JP6403690A JP6403690A JPH0362811A JP H0362811 A JPH0362811 A JP H0362811A JP 6403690 A JP6403690 A JP 6403690A JP 6403690 A JP6403690 A JP 6403690A JP H0362811 A JPH0362811 A JP H0362811A
- Authority
- JP
- Japan
- Prior art keywords
- elastomer
- weight
- modified
- parts
- copolymer
- 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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 69
- 239000000806 elastomer Substances 0.000 title claims abstract description 67
- 229920000098 polyolefin Polymers 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 20
- -1 composed of the same Substances 0.000 abstract description 9
- 230000035939 shock Effects 0.000 abstract description 9
- 238000010030 laminating Methods 0.000 abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 3
- 239000011780 sodium chloride Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-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
- 229910001369 Brass Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- MUBKMWFYVHYZAI-UHFFFAOYSA-N [Al].[Cu].[Zn] Chemical compound [Al].[Cu].[Zn] MUBKMWFYVHYZAI-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- NRIMHVFWRMABGJ-UHFFFAOYSA-N bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylic acid Chemical compound C1C2C(C(=O)O)=C(C(O)=O)C1C=C2 NRIMHVFWRMABGJ-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- DHZBEENLJMYSHQ-XCVPVQRUSA-N cantharidin Chemical compound C([C@@H]1O2)C[C@@H]2[C@]2(C)[C@@]1(C)C(=O)OC2=O DHZBEENLJMYSHQ-XCVPVQRUSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 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
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、変性エラストマー、さらに詳しくは、金属、
ポリオレフィン、ポリアミド、ポリエステル、ポリ塩化
ビニルまたはポリビニルアルコールに対して高接着性を
有し持つ変性エラストマーに関し、特にこのエラストマ
ーは耐温水性、耐塩水性、耐サーマルショック性に優れ
た積層物を与える。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to modified elastomers, more specifically metals,
The present invention relates to modified elastomers having high adhesion to polyolefins, polyamides, polyesters, polyvinyl chloride or polyvinyl alcohol; in particular, these elastomers provide laminates with excellent hot water resistance, salt water resistance and thermal shock resistance.
従来、金属の耐食性や外観の改善のために、金属管の内
外面、金属板、ワイヤーなどに種々の合成樹脂を被覆し
たり、あるいは各種合金樹脂のもつ欠点を改善するため
の他種の樹脂との貼り合せによる積層物が提案されてい
る。このような合成樹脂の素材としては、低価格で種々
の物理的、化学的特性に優れたポリオレフィンが金属や
他の合成樹脂との積層物として注目されているが、本来
、ポリオレフィンは無極性であることから金属や各種合
成樹脂との親和性は少く、接着が簡単にできないという
欠点があり、このような欠点を改善するために、種々の
方法が提案されている。Conventionally, in order to improve the corrosion resistance and appearance of metals, various synthetic resins have been coated on the inner and outer surfaces of metal tubes, metal plates, wires, etc., or other types of resins have been coated to improve the drawbacks of various alloy resins. A laminate has been proposed by bonding with. As a material for such synthetic resins, polyolefins are attracting attention due to their low cost and excellent physical and chemical properties as laminates with metals and other synthetic resins, but polyolefins are originally non-polar. For this reason, it has a drawback that it has little affinity with metals and various synthetic resins, and cannot be easily bonded. Various methods have been proposed to improve these drawbacks.
例えば、無水マレイン酸のような不飽和カルボン酸をグ
ラフト重合させた変性ポリオレフィンを介する金属とポ
リオレフィンとからなる積層物（特公昭４２−”１０７
５７号公報）、不飽和カルボン酸またはその無水物によ
り変性したポリオレフィンとナイロンを共押出しして複
層シートを得る方法（特公昭５１−４３０５５号公報）
、さらにはこれらの接着力を改善する方法として、結晶
性ポリオレフィンにゴム化合物１〜２０重量％を添して
不飽和カルボン酸またはその無水物で変性する方法（特
開昭５２−８０３５号公報）、結晶性ポリオレフィン７
０〜９８重量％と無水マレイン酸をグラフト重合させた
変性エチレンとα−オレフィンとの共重合体３０〜２重
量％とからなる組成物、または結晶性ポリオレフィン７
０〜９８重量％とエチレンとα−オレフィンとの共重合
体３０〜２重量％との混合物を不飽和カルボン酸または
その無水物を反応させた変性ポリオレフィンをポリアミ
ド、ポリエステル、エチレン−酢酸ビニル共重合体ケン
化物に積層する方法（特開昭５４８２号、同５４−８３
号公報）、実質的に飽和のエチレン−α−オレフィン共
重合体ゴムに不飽和カルボン酸またはその無水物をグラ
フトさせる熱可塑性エラストマーの製造方法（特開昭５
２−４５６８９号公報）などである。For example, a laminate consisting of a metal and a polyolefin via a modified polyolefin obtained by graft polymerization of an unsaturated carboxylic acid such as maleic anhydride (Japanese Patent Publication No. 42-107)
57), a method for obtaining a multilayer sheet by coextruding polyolefin modified with an unsaturated carboxylic acid or its anhydride and nylon (Japanese Patent Publication No. 51-43055)
Furthermore, as a method for improving these adhesive forces, there is a method of adding 1 to 20% by weight of a rubber compound to crystalline polyolefin and modifying it with an unsaturated carboxylic acid or its anhydride (Japanese Patent Laid-Open No. 8035/1983). , crystalline polyolefin 7
A composition consisting of 0 to 98% by weight and 30 to 2% by weight of a copolymer of modified ethylene and α-olefin obtained by graft polymerization of maleic anhydride, or crystalline polyolefin 7
A modified polyolefin obtained by reacting a mixture of 0 to 98% by weight and 30 to 2% by weight of a copolymer of ethylene and α-olefin with an unsaturated carboxylic acid or its anhydride is used as polyamide, polyester, or ethylene-vinyl acetate copolymer. Method of laminating on a combined saponified product (JP-A No. 5482, No. 54-83)
(Japanese Unexamined Patent Application Publication No. 1989-1993), a method for producing a thermoplastic elastomer by grafting an unsaturated carboxylic acid or its anhydride onto a substantially saturated ethylene-α-olefin copolymer rubber
2-45689).
しかしながら、これらの方法により接着強度を向上させ
た変性ポリオレフィンも海水、食塩水などの電解質含有
水への接触、加熱液体への接触、あるいは温度変化に対
して接着強度が短時間のうちに低下し、接着面から剥離
するという現象がある。また、より高接着性を要求され
る共押出しブロー形成への応用にはまだ充分とはいえな
い。さらに、変性ポリオレフィンの接着性を発現させる
ためには、加工工程において通常２００℃程度の高温が
必要であり、多大なエネルギーコストを消費するため、
加工温度の低下が望まれている。However, even with modified polyolefins whose adhesive strength has been improved by these methods, the adhesive strength decreases in a short period of time due to contact with electrolyte-containing water such as seawater or saline water, contact with heated liquids, or temperature changes. , there is a phenomenon of peeling off from the adhesive surface. Furthermore, it is still not sufficient for application to coextrusion blow molding, which requires higher adhesion. Furthermore, in order to develop the adhesive properties of modified polyolefin, a high temperature of about 200°C is usually required in the processing process, which consumes a large amount of energy cost.
It is desired to lower the processing temperature.
本発明者らは、以上のような問題点を改善するために種
々の検討を重ねた結果、エラストマーとしてエチレン−
ブテン−１共重合体もしくはそれを主成分とする混合エ
ラストマー１００重量部に対し０．０５〜０．８重量部
のエンド−ビシクロＣ２，２，１３−５−へブテン−２
，３ジカルボン酸またはその無水物を加えて変性したも
のが、極めて高強度の接着性を示すことを見出し、本発
明を完成したものである。As a result of various studies in order to improve the above problems, the present inventors have developed an ethylene-based elastomer.
0.05 to 0.8 parts by weight of endo-bicycloC2,2,13-5-hebutene-2 per 100 parts by weight of butene-1 copolymer or mixed elastomer containing it as a main component.
, 3 dicarboxylic acid or its anhydride exhibits extremely high adhesive strength, and the present invention was completed based on this finding.
すなわち、本発明はエチレン−ブテン−１共重合体もし
くはそれを主成分とする混合エラストマー１００重量部
または該エラストマーに結晶性ポリオレフィン５０重量
部以下を加えた混合物１００重量部に０．０５〜０．８
重量部のエンド−ビシクロ［２，２，１，１−５−ヘプ
テン２．３−ジカルボン酸またはその無水物を添加し、
付加してなる変性エラストマーであり、特に該変性エラ
ストマーまたは該変性エラストマーに結晶性ポリオレフ
ィンまたは充填材を加えた組成物は金属、ポリアミド、
ポリエステル、ポリ塩化ビニルおよびポリビニルアルコ
ールの群より選ばれたものとの積層物とするのに適する
。That is, the present invention provides 100 parts by weight of an ethylene-butene-1 copolymer or a mixed elastomer containing the same as a main component, or a mixture of 50 parts by weight or less of crystalline polyolefin added to the elastomer in an amount of 0.05 to 0. 8
adding parts by weight of endo-bicyclo[2,2,1,1-5-heptene 2,3-dicarboxylic acid or anhydride thereof;
It is a modified elastomer obtained by adding a crystalline polyolefin or a filler to the modified elastomer or a composition in which a crystalline polyolefin or a filler is added to the modified elastomer or the modified elastomer.
Suitable for laminates with those selected from the group of polyester, polyvinyl chloride and polyvinyl alcohol.
本発明で用いられるエラストマーは、エチレン−ブテン
−１共重合体もしくはそれを主成分とする混合物である
が、その引張強度が６０ｋｇ／ ｃｕｔ以上、特に１０
０ｋｇ／ｃｆｆ１以上であることが望ましい。また、こ
れらエラストマー自体の９張強度が低い場合には適宜結
晶性ポリオレフィン、たとえばポリエチレン、ポリプロ
ピレン、ポリブテン−ｌまたはそれらの混合物を添加し
てエラストマーの引張強度を向上させることが望ましい
。エチレン−ブテン−１共重合体としては、エチレンの
含有量が１０〜９０重量％、特に好ましくは７０〜８５
重量％、ムニー粘度（＾ＳＴＭＤ９２７−５７Ｔ以下同
じ）が１００℃で以下−２００のものが好ましい。The elastomer used in the present invention is an ethylene-butene-1 copolymer or a mixture containing it as a main component, and its tensile strength is 60 kg/cut or more, particularly 10
It is desirable that it is 0 kg/cff1 or more. In addition, when the tensile strength of these elastomers themselves is low, it is desirable to improve the tensile strength of the elastomer by appropriately adding a crystalline polyolefin such as polyethylene, polypropylene, polybutene-1, or a mixture thereof. The ethylene-butene-1 copolymer has an ethylene content of 10 to 90% by weight, particularly preferably 70 to 85% by weight.
It is preferable that the weight percent and Muny viscosity (the same applies below STMD927-57T) are -200 or below at 100°C.
本発明で用いられる結晶性ポリオレフィンは、たとえば
高密度ポリエチレン、中密度ポリエチレン、低密度ポリ
エチレン、結晶性エチレン−プロピレン共重合体、結晶
性エチレン−ブテン１共重合体、ポリプロピレン、結晶
性プロピレン−エチレン共重合体、ポリブテン−１、ポ
リ４−メチルペンテン−ｌなどオレフィン類の単独重合
体または異種のオレフィン類との共重合体があげられ、
これらは２種以上の混合物として用いることができる。Examples of the crystalline polyolefin used in the present invention include high density polyethylene, medium density polyethylene, low density polyethylene, crystalline ethylene-propylene copolymer, crystalline ethylene-butene 1 copolymer, polypropylene, and crystalline propylene-ethylene copolymer. Polymers, homopolymers of olefins such as polybutene-1, poly-4-methylpentene-1, or copolymers with different types of olefins,
These can be used as a mixture of two or more.
そしてこれらの中では、高密度ポリエチレン、低密度ポ
リエチレンまたはポリプロピレンが特に好ましい。Among these, high density polyethylene, low density polyethylene and polypropylene are particularly preferred.
本発明で用いる変性用の不飽和カルボン酸またはその無
水物はエンド−ビシクロ−〔２，２Ｉ’１ｌ−５−−ヘ
プテン−２，３−ジカルボン酸およびエンド−ビシクロ
−［２２，１］−５へブテン−２，３−無水ジカルボン
酸である。The unsaturated carboxylic acids or anhydrides thereof for modification used in the present invention are endo-bicyclo-[2,2I'11-5-heptene-2,3-dicarboxylic acid and endo-bicyclo-[22,1]-5 Hebutene-2,3-dicarboxylic anhydride.
そしてこれらの中では、エンド−ビシクロ［：２，２．
Ｎ−５−ヘプテン−２，３−無水ジカルボン酸を用いる
のが特に好ましい。And among these, endo-bicyclo[:2,2.
Particular preference is given to using N-5-heptene-2,3-dicarboxylic anhydride.
上記不飽和カルボン酸またはその無水物の量は、エチレ
ン−ブテン−１共重合体もしくはそれを主成分とする混
合エラストマーまたはそれらと結晶性ポリオレフィンと
の混合物１００重量部に対し０．０５〜０．８重量部、
好ましくは０．２〜０．７重量部を加えることが必要で
あり、０．０５重量部未満では接着強度が十分でなく、
０、８重量部を越えると剥離強度が落ち、また本発明の
ように不飽和カルボン酸の添加量を低くすることによっ
てゲル状物、発色等の増大を抑えることができる。The amount of the unsaturated carboxylic acid or its anhydride is 0.05 to 0.05 parts by weight per 100 parts by weight of the ethylene-butene-1 copolymer, the mixed elastomer containing the same as a main component, or the mixture thereof with the crystalline polyolefin. 8 parts by weight,
Preferably, it is necessary to add 0.2 to 0.7 parts by weight, and if it is less than 0.05 parts by weight, the adhesive strength will not be sufficient.
When the amount exceeds 0.8 parts by weight, the peel strength decreases, and by reducing the amount of unsaturated carboxylic acid added as in the present invention, it is possible to suppress the increase in gel-like substances and color development.
本発明の変性エラストマーは、前記のエヂｌノンーブテ
ンー１共重合体もしくはそれを主成分とする混合エラス
トマーまたはそれらと結晶性ポリオレフィンとの混合物
に不飽和カルボン酸またはその無水物を添加して公知の
種々の変性方法を適用して製造することができる。たと
えば、上記のエチレン−ブテン−↓共重合体もしくはそ
れを主成分とする混合エラストマーまたは該エラストマ
ーに結晶性ポリオレフィンを加えた混合物に不飽和カル
ボン酸またはその無水物とラジカル発生剤、たとえばジ
ターシャリ−ブチルパーオキサイド、ジクミルパーオキ
サイド、ベンゾイルパーオキサイドなどの有機過酸化物
を添加し、または添加せず、ヘンシェルミキサー リボ
ンブレンダー、Ｖ字ブレンダーまたはタンブラ−などの
混合機で混合し、この混合物をバンバリーミキサ−１車
軸また・は多軸の押出機で、１２０〜３００℃好ましく
は１８０〜２５０℃で溶融混練する。または、前記共重
合体基材と不飽和カルボン酸またはその無水物を水中ま
たは有機溶媒中に分散し、上記ラジカル発生剤または水
溶性の過酸化物の存在下で加熱することによっても得ら
れる。The modified elastomer of the present invention can be obtained by adding an unsaturated carboxylic acid or its anhydride to the above-mentioned non-butene-1 copolymer, a mixed elastomer containing the same as a main component, or a mixture of these and a crystalline polyolefin. It can be manufactured by applying the following modification method. For example, the above-mentioned ethylene-butene-↓ copolymer or a mixed elastomer containing the copolymer as a main component, or a mixture of the elastomer and a crystalline polyolefin, combined with an unsaturated carboxylic acid or its anhydride and a radical generator, such as ditertiary-butyl Mix with or without the addition of organic peroxides such as peroxide, dicumyl peroxide, benzoyl peroxide, etc. in a mixer such as a Henschel mixer, ribbon blender, V-shaped blender, or tumbler, and then mix this mixture in a Banbury mixer. - Melt-kneading is carried out at 120 to 300°C, preferably 180 to 250°C, using a single-axle or multi-axle extruder. Alternatively, it can also be obtained by dispersing the copolymer base material and the unsaturated carboxylic acid or its anhydride in water or an organic solvent, and heating in the presence of the radical generator or water-soluble peroxide.
ここで、前記のエチｌノンーブテンー１共重合体もしく
はそれを主成分とする混合エラストマーと結晶性ポリオ
レフィンその混合割合は、前者が５０重量部以上で特に
好ましくは７０重量部以上、後者が５０重量部以下で特
に好ましくは３０重量部以下である。エチレン−ブテン
１共重合体もしくはそれを主成分とする混合エラストマ
ーの５０重量部に対して結晶性ポリオレフィンが５０重
量部を超えると変性エラストマーの特性が失われ、接着
性の改良効果が充分でなく特に耐温水性、耐塩水性、耐
サーマルショック性などが劣るために好ましくない。ま
た、有機過酸化物の添加量は、エチレン−ブテンＩ共重
合体もしくはそれを主成分とする混合エラストマーおよ
び該エラストマーと結晶性ポリオレフィンとの混合物１
００重量部に対して０、１重量部９下で好ましくは０．
００１〜０１０８重量部である。Here, the mixing ratio of the above-mentioned ethyl non-butene-1 copolymer or a mixed elastomer containing the same as a main component and the crystalline polyolefin is such that the former is 50 parts by weight or more, preferably 70 parts by weight or more, and the latter is 50 parts by weight. Particularly preferably 30 parts by weight or less. If the amount of crystalline polyolefin exceeds 50 parts by weight with respect to 50 parts by weight of the ethylene-butene 1 copolymer or mixed elastomer containing it as a main component, the properties of the modified elastomer will be lost and the effect of improving adhesion will not be sufficient. In particular, it is unfavorable because it has poor hot water resistance, salt water resistance, thermal shock resistance, etc. In addition, the amount of organic peroxide added is 1:1 for ethylene-butene I copolymer or a mixed elastomer containing it as a main component, and a mixture of the elastomer and crystalline polyolefin.
0 to 00 parts by weight, preferably 0.0 to 1 part by weight.
001 to 0108 parts by weight.
このようにして得られた変性エラストマーは単独で使用
するのが望ましいが、これらに未変性エラストマーある
いは結晶性ポリオレフィンまたはそれらとの混合物を添
加して使用することができる。たとえば、エチＬ／ンー
ブテンー１共重合体もしくはそれを主成分とする混合エ
ラストマーまたは該エラストマーに結晶性ポリオレフィ
ンを加えた混合物の１００重量部に対して不飽和カルボ
ン酸またはその無水物を０．０５〜０．８重量部、特に
好ましくは０．１〜０．７重量部、有機過酸化物を０．
１重量部以下、好ましくは０．００↓〜０．０８重量部
とを混合し、温度１２０〜３００℃、好ましくは１８０
〜２５０℃で溶融混練して得られた変性エラストマーと
未変性エラストマーまたは結晶性ポリオレフィンとをリ
ボンブレンダー、Ｖ字ブレンダー、タンブラ−またはヘ
ンシェルミキサーなどの混合機で混合し、この混合物を
混練機、たとえばバンバリーミキサ−１車軸または多軸
の押出機で１２０〜２５０℃で溶融混練することによっ
て０
製造できる。ここで、変性エラストマーと未変性エラス
トマーまたは結晶性ポリオレフィンからなる変性エラス
トマー組成物の混合割合は、その使用目的により任意に
選択できるものではあるが未変性エラストマーまたは結
晶性ポリオレフィンの添加量が多くなると変性エラスト
マーの性質が失なわれて接着性の改良が充分でなく、特
に耐温水性、耐塩水性、耐サーマルショック性が劣るた
めに好ましくない。変性エラストマー１００重量部に対
する未変性エラストマーまたは結晶性ポリオレフィンの
添加量は１００重量部以下で、好ましくは４３重量部以
下であるが、変性エラストマー中に結晶性ポリオレフィ
ンを含有する場合は、結晶性ポリオレフィンの添加量を
減少し、変性エラストマー組成物１００重量部中に含有
する結晶性ポリオレフィンの全体量が５０重量部以下と
なるように添加することが好ましい。さらに、上記の変
性エラストマーまたはエラストマー組成物には、必要に
応じて炭酸カルシウム、ホワイトカーボン、カーボンブ
ラック、タルク、クレイ、硫酸バリウムなどの各種充填
材あるいは酸化防止剤、紫外線吸収剤、各種安定剤、帯
電防止剤、離型剤、滑剤、顔料などを適宜配合すること
ができる。Although it is desirable to use the modified elastomer thus obtained alone, it is also possible to add an unmodified elastomer, a crystalline polyolefin, or a mixture thereof to the modified elastomer. For example, 0.05 to 100 parts by weight of an unsaturated carboxylic acid or its anhydride is added to 100 parts by weight of an ethyl-L/butene-1 copolymer, a mixed elastomer containing the same as a main component, or a mixture of the elastomer and a crystalline polyolefin. 0.8 parts by weight, particularly preferably 0.1 to 0.7 parts by weight, and 0.8 parts by weight of organic peroxide.
1 part by weight or less, preferably 0.00↓ to 0.08 parts by weight, at a temperature of 120 to 300°C, preferably 180°C.
The modified elastomer obtained by melt-kneading at ~250°C and the unmodified elastomer or crystalline polyolefin are mixed in a mixer such as a ribbon blender, V-shaped blender, tumbler or Henschel mixer, and this mixture is mixed in a kneader, e.g. It can be produced by melt-kneading at 120 to 250°C using a Banbury mixer, a single-axle extruder, or a multi-screw extruder. Here, the mixing ratio of the modified elastomer composition consisting of the modified elastomer and the unmodified elastomer or the crystalline polyolefin can be arbitrarily selected depending on the intended use, but if the amount of the unmodified elastomer or the crystalline polyolefin added is large, the This is not preferred because the properties of the elastomer are lost and the adhesion is not sufficiently improved, and in particular, the hot water resistance, salt water resistance, and thermal shock resistance are poor. The amount of unmodified elastomer or crystalline polyolefin added to 100 parts by weight of the modified elastomer is 100 parts by weight or less, preferably 43 parts by weight or less, but when the modified elastomer contains crystalline polyolefin, the amount of crystalline polyolefin It is preferable to reduce the amount added so that the total amount of crystalline polyolefin contained in 100 parts by weight of the modified elastomer composition is 50 parts by weight or less. Furthermore, the above-mentioned modified elastomer or elastomer composition may optionally contain various fillers such as calcium carbonate, white carbon, carbon black, talc, clay, barium sulfate, antioxidants, ultraviolet absorbers, various stabilizers, etc. Antistatic agents, mold release agents, lubricants, pigments, etc. can be appropriately blended.
次に、本発明の変性ニジストマーを用いるのに適する積
層物（以下該積層物という）における金属は、アルミニ
ウム、銅、亜鉛、ニッケル、鉄、錫、ステンレス、真ち
ゅう、ブリキまたはトタンなどがあげられる。ポリアミ
ドは、ラクタム開環重合、アミノカルボン酸の重縮合あ
るいはジアミンと二塩基酸の重縮合などにより得られる
酸アミド（〜Ｃ０ＮＨ−）をくり返し単位にもつ高分子
で一般にナイロンという商品名で呼ばれている。Next, examples of metals in a laminate (hereinafter referred to as the laminate) suitable for using the modified nidistomer of the present invention include aluminum, copper, zinc, nickel, iron, tin, stainless steel, brass, tinplate, and galvanized iron. Polyamide is a polymer with repeating units of acid amide (~C0NH-) obtained by ring-opening polymerization of lactams, polycondensation of aminocarboxylic acids, or polycondensation of diamines and dibasic acids, and is generally referred to by the trade name nylon. ing.
たとえばナイロン６、ナイロン６−６、ナイロン１■、
ナイロン１２、ナイロン６−１０などがあげられる。ポ
リエステルは、分子の主鎖にエステル結合を有する高分
子化合物で、通常二塩基酸と二価アルコールの重縮合に
より得られる。たとえばポリエチレンテレフタレート、
２
ポリブチレンテレフタレートなどがあげられる。For example, nylon 6, nylon 6-6, nylon 1■,
Examples include nylon 12 and nylon 6-10. Polyester is a polymer compound having an ester bond in the main chain of the molecule, and is usually obtained by polycondensation of a dibasic acid and a dihydric alcohol. For example, polyethylene terephthalate,
2. Examples include polybutylene terephthalate.
ポリ塩化ビニルは、塩化ビニル単量体だけを重合した単
独重合体または酢酸ビニルなどのほかの単量体を共重合
させた共重合体などで、軟質、硬質、高衝撃など各品種
ものである。ポリビニルアルコールは、重合度１２００
〜２０００のポリ酢酸ビニルをケン化して得られる水溶
性樹脂で、この樹脂を原料とするものに商品名でビニロ
ンと呼ばれるものがあげられる。Polyvinyl chloride is a homopolymer made by polymerizing only vinyl chloride monomers or a copolymer made by copolymerizing other monomers such as vinyl acetate, and there are various types such as soft, hard, and high impact. . Polyvinyl alcohol has a polymerization degree of 1200
A water-soluble resin obtained by saponifying polyvinyl acetate of ~2000, and a product using this resin as a raw material is known as Vinylon.
該積層物は、前記の変性エラストマーまたは変性エラス
トマー組成物と、上記の金属、ポリアミド、ポリエステ
ル、ポリ塩化ビニル、ポリビニルアルコールまたはポリ
オレフィンから選択されるものとの溶融積層によって得
られる。The laminate is obtained by melt lamination of the above-mentioned modified elastomer or modified elastomer composition with one selected from the above-mentioned metals, polyamides, polyesters, polyvinyl chloride, polyvinyl alcohol or polyolefins.
積層する方法は特に限定されるものではなく、たとえば
それぞれをフィルム、シート状としておき熱圧着する方
法、グイ外部でラミネートする方法、グイ内部でラミネ
ートする方法あるいは押出しコーティングする方法など
の公知の方法を利用することができる。該積層物の構造
は、３
変性エラストマーまたは変性エラストマー組成物と前記
の金属、ポリオレフィン、ポリアミド、ポリエステル、
ポリ塩化ビニルまたはポリビニルアルコールから選択さ
れるものに積層する２層構造、さらに変性エラストマー
または変性エラストマー組成物をサンドイッチした３層
構造を基本とするものであるが、用途に応じて基構成要
素を含む範囲内で種々の組合せを用いることができる。The method of laminating is not particularly limited, and known methods such as forming each into a film or sheet and thermocompression bonding, laminating outside the gou, laminating inside the gou, or extrusion coating can be used. can be used. The structure of the laminate includes 3 modified elastomers or modified elastomer compositions and the above-mentioned metals, polyolefins, polyamides, polyesters,
It is basically a two-layer structure laminated on polyvinyl chloride or polyvinyl alcohol, and a three-layer structure sandwiching a modified elastomer or a modified elastomer composition, but may contain base components depending on the application. Various combinations within the range can be used.
以上、本発明による変性エラストマーまたは変性エラス
トマー組成物は、前記の金属または各種の樹脂と良好な
接着性を示し、接着強度の高い積層物を作ることができ
る。また、この積層物の接着面は、耐温水性、耐塩水性
、耐サーマルショック性が従来の変性ポリオレフィンを
中間層とする積層物に比べて著しく改善されるものであ
る。As described above, the modified elastomer or modified elastomer composition according to the present invention exhibits good adhesion to the above-mentioned metals or various resins, and can produce a laminate with high adhesive strength. Furthermore, the adhesive surface of this laminate has significantly improved hot water resistance, salt water resistance, and thermal shock resistance compared to conventional laminates having modified polyolefin as an intermediate layer.
本発明で得られる樹脂積層物は、ガス不透性、耐湿性、
耐油性などの利点を生かし、包装用のフィルム、シート
、ボルト、容器などに使用す４
ることかできる。また、針金、ケーブル、金属板、金属
管、その他の金属インサーｌ−物１Ｊど金属の被覆をす
る場合の中間層としても利用できる。この場合は、被覆
する金属に本発明の変性エラストマーまたはその組成物
を付着せしめるか、あるいはそのシーＩ・を巻きつけた
あと金型に設置してポリオレフィンを成形することによ
り接着強度の大きな金属を含む成形物が得られる。The resin laminate obtained by the present invention has gas impermeability, moisture resistance,
Taking advantage of its oil resistance and other advantages, it can be used in packaging films, sheets, bolts, containers, etc. It can also be used as an intermediate layer when covering metals such as wires, cables, metal plates, metal tubes, and other metal inserts. In this case, the modified elastomer of the present invention or its composition may be attached to the metal to be coated, or the metal with high adhesive strength may be coated by wrapping the sheet I and placing it in a mold to mold the polyolefin. A molded article containing the above is obtained.
実施例１〜４、比較例１
エチｌノン含有量７７重量％、１・−二−粘度（ＭＬ、
＋４１００℃）、メルトインデックス（ＡＳＴＭＬＩ−
１２３８Ｂ以下同じＭＩと略す）４０（１９０℃）、密
度０．８９であるエチレン−ブテン−１共重合体く以下
ｃ；−ｃ：Ｈ、と略ず）、エンド−ビシクロ−［２２，
１〕−５−ヘプテン−２，３−無水ジカルボン酸 （以
下無水ジカルボン酸−Ｈと略す）、ジターシャリーブチ
ルパーオキザイド（以下Ｄ Ｔ Ｂ Ｉ）と略す）をそ
れぞれ第１表に示す割合で、ヘンシェルミキサーにより
常温で混合し、混合物をベント付６５ｍｍφの押出機に
供給して、２３０℃で押出し円筒状ペレットを作成した
。Examples 1 to 4, Comparative Example 1 Ethylnon content 77% by weight, 1·-2-viscosity (ML,
+4100℃), melt index (ASTMLI-
1238B (hereinafter abbreviated as MI) 40 (190°C), density 0.89 ethylene-butene-1 copolymer (hereinafter abbreviated as c;-c:H), endo-bicyclo-[22,
1] -5-heptene-2,3-dicarboxylic anhydride (hereinafter abbreviated as dicarboxylic anhydride-H) and ditertiary butyl peroxide (hereinafter abbreviated as DTBI)) in the proportions shown in Table 1, respectively. The mixture was mixed at room temperature using a Henschel mixer, and the mixture was supplied to a vented 65 mmφ extruder and extruded at 230° C. to produce cylindrical pellets.
ここで得られた各変性エラストマーのペレットを熱ペレ
ス成形機により２００℃、４０ｋｇ／ｃｆｆｌの条件で
厚さ０．２ ｎｕ＋＋のシートに成形した。この名シー
トと厚さ０．１ ｍｍのアルミニウムシートを用いて、
アルミニウムシート／変性エラストマー／アルミニウム
シートの各３層積層物を、８０℃、１００℃、２００℃
の各予熱温度および接着温度、４０ｋｇ／ｃｎ！で２分
間融着の各条件で作成した。この３層積層物を２５ｍｍ
巾に切断し、インストロン万能引張試験機にて３層積層
物の９０’剥離強度を測定した。その結果を第１表に示
す。The pellets of each modified elastomer obtained here were molded into a sheet with a thickness of 0.2 nu++ at 200° C. and 40 kg/cffl using a hot pellet molding machine. Using this famous sheet and an aluminum sheet with a thickness of 0.1 mm,
Each three-layer laminate of aluminum sheet/modified elastomer/aluminum sheet was heated at 80°C, 100°C, and 200°C.
Each preheating temperature and bonding temperature of 40kg/cn! It was prepared under each condition of fusion bonding for 2 minutes. This 3 layer laminate is 25mm
The 90' peel strength of the three-layer laminate was measured using an Instron universal tensile tester. The results are shown in Table 1.
積層物の耐温水性試験、耐塩水性試験、耐サーマルシヨ
ツク性試験は、」二記の変性エラストマーとリン酸処理
した鉄板（ＪＩＳ Ｇ−３１，４１０，７ｍｍ＋Ｘ ７
０ｍｍＸ １２０ｍｍ）の２層積層物を、上記の層間剥
離強度測定用の積層物と同様の方法で作成して行った。The hot water resistance test, salt water resistance test, and thermal shock resistance test of the laminate were conducted using the modified elastomer and phosphoric acid-treated iron plate (JIS G-31, 410, 7 mm +
A two-layer laminate (0 mm x 120 mm) was prepared in the same manner as the laminate for interlayer peel strength measurements described above.
なお、変性エラストマー層の厚みは０゜１５ｍｍであっ
た。The thickness of the modified elastomer layer was 0.15 mm.
（１）耐温水性試験
２層積層物の変性エラストマー層に鋭利なナイフで金属
に到達する長さ６０ｍｍのクロスハツチをつけ、６０℃
の温水中に浸漬し、クロスハツチからのしみ込みが２１
１１［ｉｌに達した時間（日数）を耐久時間とした。(1) Hot water resistance test A crosshatch with a length of 60 mm reaching the metal was attached to the modified elastomer layer of the two-layer laminate using a sharp knife, and the temperature was increased to 60°C.
Soaked in warm water, the seepage from the crosshatch was 21
The time (days) when 11 [il was reached was defined as the durability time.
（２）耐塩水性試験
耐塩水性試験と同様のクロスハツチを入れた２層積層物
を、５０℃、３％食塩水中に浸漬し、クロスハツチから
のしみ込みが２ ｍｍに達した時間（日数）を耐久時間
とした。(2) Salt water resistance test A two-layer laminate with cross hatches similar to those in the salt water resistance test was immersed in 3% saline at 50°C, and the durability was measured for the time (number of days) until the seepage from the cross hatches reached 2 mm. It was time.
（３） 耐サーマルショック性試験
２層積層物に、室温（３０分）０５０℃（２時間）→室
温（３０分）＝３０℃（２時間）→室温の条件を与えて
、積層物の変性エラストマーがリン酸亜鉛処理鉄板から
剥離したときのサイクル数を耐サーマルシヨツク回数と
した。以上の結果を第１表に示す。(3) Thermal shock resistance test The two-layer laminate was subjected to the following conditions: room temperature (30 minutes), 050°C (2 hours) → room temperature (30 minutes) = 30°C (2 hours) → room temperature, and the laminate was denatured. The number of cycles at which the elastomer peeled off from the zinc phosphate treated iron plate was defined as the number of thermal shock resistance cycles. The above results are shown in Table 1.
７
比較例２〜３
ポリプロピレン［：ＭＩ＝１．０ （２３０℃）密度
０．９０以下ＰＰと略す〕、プロピレン−エチレン−ブ
ロック共重合体〔エチレン含有量７重量％、ＭＩ＝１．
０（２３０℃）密度０．９０以下Ｐ／Ｅブロツクと略す
〕をそれぞれ第２表に示す割合で、実施例１と同様の方
法で変性し、この各変性ポリオレフィンについて実施例
１と同様の方法で試験片を作成し、９０°剥離強度およ
び耐温水性、耐塩水性、耐サーマルショック性の接着耐
久性試験を行った。以上の結果を第２表に示す。7 Comparative Examples 2 to 3 Polypropylene [abbreviated as PP: MI=1.0 (230° C.) density 0.90 or less], propylene-ethylene-block copolymer [ethylene content 7% by weight, MI=1.
0 (230°C) density 0.90 or less (abbreviated as P/E block)] were modified in the same manner as in Example 1 at the ratios shown in Table 2, and each modified polyolefin was modified in the same manner as in Example 1. A test piece was prepared, and adhesive durability tests were conducted on 90° peel strength, hot water resistance, salt water resistance, and thermal shock resistance. The above results are shown in Table 2.
参考例１、比較参考例１
実施例１の変性エラストマー組成物、比較例２の変性ポ
リオレフィンを用いて、それぞれ第３表に示す各種の金
属との３層積層物を、実施例１と同様の方法で作成して
９０’剥離強度を測定した。結果を第３表に示す。Reference Example 1, Comparative Reference Example 1 Using the modified elastomer composition of Example 1 and the modified polyolefin of Comparative Example 2, three-layer laminates with various metals shown in Table 3 were prepared in the same manner as in Example 1. method, and the 90' peel strength was measured. The results are shown in Table 3.
第 表 ２No. table 2
Claims (1)
れを主成分とする混合エラストマー１００重量部または
該エラストマーに結晶性ポリオレフィン５０重量部以下
を加えた混合物１００重量部に０．０５〜０．８重量部
のエンド−ビシクロ〔２，２，１〕−５−ヘプテン−２
，３−ジカルボン酸もしくはその無水物を添加し、付加
してなる変性エラストマー。[Scope of Claims] 0.05 to 100 parts by weight of an ethylene-butene-1 copolymer elastomer or a mixed elastomer containing it as a main component, or a mixture of the elastomer and 50 parts by weight or less of crystalline polyolefin. 0.8 parts by weight of endo-bicyclo[2,2,1]-5-heptene-2
, 3-dicarboxylic acid or its anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6403690A JPH0362811A (en) | 1990-03-16 | 1990-03-16 | Modified elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6403690A JPH0362811A (en) | 1990-03-16 | 1990-03-16 | Modified elastomer |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13083579A Division JPS5655413A (en) | 1979-10-12 | 1979-10-12 | Modified elastomer and laminate thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0362811A true JPH0362811A (en) | 1991-03-18 |
| JPH0413393B2 JPH0413393B2 (en) | 1992-03-09 |
Family
ID=13246490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6403690A Granted JPH0362811A (en) | 1990-03-16 | 1990-03-16 | Modified elastomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0362811A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5245689A (en) * | 1975-10-09 | 1977-04-11 | Mitsui Petrochem Ind Ltd | Process for preparig thermoplastic elastomers |
| JPS5249289A (en) * | 1975-10-17 | 1977-04-20 | Mitsui Petrochem Ind Ltd | Rocess for preparing thermoplastic elastomers |
| JPS54130835A (en) * | 1978-03-31 | 1979-10-11 | Sanyo Electric Co Ltd | Noise reduction system of chrominance subcarrier |
| JPS5655413A (en) * | 1979-10-12 | 1981-05-16 | Toa Nenryo Kogyo Kk | Modified elastomer and laminate thereof |
| JPS6325006A (en) * | 1986-07-09 | 1988-02-02 | バイエル・アクチエンゲゼルシヤフト | Method and device for manufacturing foamed cushion, particularly, seat cushion for automobile, with fiber coating |
-
1990
- 1990-03-16 JP JP6403690A patent/JPH0362811A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5245689A (en) * | 1975-10-09 | 1977-04-11 | Mitsui Petrochem Ind Ltd | Process for preparig thermoplastic elastomers |
| JPS5249289A (en) * | 1975-10-17 | 1977-04-20 | Mitsui Petrochem Ind Ltd | Rocess for preparing thermoplastic elastomers |
| JPS54130835A (en) * | 1978-03-31 | 1979-10-11 | Sanyo Electric Co Ltd | Noise reduction system of chrominance subcarrier |
| JPS5655413A (en) * | 1979-10-12 | 1981-05-16 | Toa Nenryo Kogyo Kk | Modified elastomer and laminate thereof |
| JPS6325006A (en) * | 1986-07-09 | 1988-02-02 | バイエル・アクチエンゲゼルシヤフト | Method and device for manufacturing foamed cushion, particularly, seat cushion for automobile, with fiber coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0413393B2 (en) | 1992-03-09 |
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