JPH0326236B2 - - Google Patents
Info
- Publication number
- JPH0326236B2 JPH0326236B2 JP8881081A JP8881081A JPH0326236B2 JP H0326236 B2 JPH0326236 B2 JP H0326236B2 JP 8881081 A JP8881081 A JP 8881081A JP 8881081 A JP8881081 A JP 8881081A JP H0326236 B2 JPH0326236 B2 JP H0326236B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- modified
- copolymer
- ethylene
- hydrogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims description 18
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 17
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 16
- 239000004711 α-olefin Substances 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 239000004840 adhesive resin Substances 0.000 claims description 7
- 229920006223 adhesive resin Polymers 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 description 18
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 13
- 229920000098 polyolefin Polymers 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920001400 block copolymer Polymers 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000012360 testing method Methods 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 206010040844 Skin exfoliation Diseases 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 239000004744 fabric Substances 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
- 239000000155 melt Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical class CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- XKJMBINCVNINCA-UHFFFAOYSA-N Alfalone Chemical compound CON(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XKJMBINCVNINCA-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920003368 Kevlar® 29 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229920006266 Vinyl film Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical group C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- CCTKMNJLQSXENT-UHFFFAOYSA-L nickel(2+) octanoate triethylalumane Chemical compound [Ni++].CC[Al](CC)CC.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CCTKMNJLQSXENT-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Description
本発明は接着性に優れたポリオレフイン系重合
体組成物に関する。
ポリオレフインの接着性を改良する目的でポリ
オレフインに無水マレイン酸等の不飽和カルボン
酸またはその誘導体をグラフト変性することは公
知であり、無水マレイン酸グラフトポリエチレン
はポリアミドとポリエチレンの積層フイルムの接
着層や、大口径管のポリエチレン被覆の際の接着
層等の用途にすでに使用されている。また、接着
性の改良を目的とした変性ポリオレフイン組成物
についても数多くの提案がなされており、２種の
ポリオレフイン系重合体のブレンド（特公昭55−
18251号公報、特公昭55−19259号公報、特開昭55
−13718号公報等参照）、変性ポリオレフインとエ
ラストマーとのブレンド（特開昭52−80334号公
報、特開昭52−123443号公報、特開昭55−104373
号公報、特公昭56−9942号公報等参照）あるい
は、他の添加剤等とのブレンド（特開昭55−
66981号公報等参照）等がある。しかしながら、
これらの発明は特定の被着体に対する接着強さの
向上を目的としたものであつて、一般に接着が困
難とされているポリアクリロニトリル系樹脂やフ
ツ素系樹脂に対する接着性は不充分であり、特に
変性ポリエチレンや変性ポリプロピレンをベース
とした組成物に対してはほとんど接着できなかつ
た。
また、エチレン系共重合体の改質材としてモノ
ビニル置換芳香族化合物と共役ジエンとのブロツ
ク共重合体の変性物を用いることも提案されてい
るが（特開昭55−13719号公報、特開昭55−13727
号公報参照）、このブロツク共重合体は熱安定性
があまり良好ではなく、グラフト変性時にゲルを
生じ易いため不飽和カルボン酸等を多量にグラフ
ト付加することが困難であり、しかもブロツク共
重合体100重量部に対して１重量部以上グラフト
付加させると、かえつて接着性能が低下してしま
うものであつた。
本発明者は幅広い被着体によく接着するポリオ
レフイン系重合体を得る目的で、各種の変性ポリ
オレフインの探索を行なつた結果、エチレンとα
−オレフインとの共重合体の不飽和カルボン酸ま
たはその誘導体によるグラフト変性物（以下単に
変性ポリエチレン−α−オレフイン共重合体と呼
ぶ）が最も優れた接着性能を有することを見い出
した。しかしこの変性ポリエチレン−α−オレフ
イン共重合体単独では低温での接着性能が充分で
なく、積層品の接着層として用いた場合、０℃以
下では剥離する危険性がある。そこで本発明者は
更に変性ポリエチレン−α−オレフイン共重合体
の接着性能、特に低温接着性能を改良するため、
各種の配合剤について数多く検討を行なつた結
果、配合剤として、スチレン−ブタジエンブロツ
ク共重合体の水素添加物に不飽和カルボン酸また
はその誘導体をグラフトした変性物（以下、単に
変性スチレン−ブタジエンブロツク共重合体水添
物と呼ぶ）を選び、さらにグラフト付加量を従来
のの技術より多くすることにより、目的とする上
記低温接着性能を改良できるばかりでなく、接着
できる被着体の種類も増大し、極めて広範な用途
に使用できる接着性樹脂組成物が得られることを
見い出し本発明を完成した。
すなわち本発明に係る接着性樹脂組成物は、
Ａ ：エチレン−α−オレフイン共重合体100重
量部に不飽和カルボン酸またはその誘導体1.1
〜10重量部をグラフト付加した変性物と、
Ｂ ：水素添加されたスチレン−ブタジエンブロ
ツク共重合体100重量部に不飽和カルボン酸ま
たはその誘導体1.1〜10重量部をグラフト付加
した変性物
を含んで成り、前記成分Ａの割合が60〜90重量
％で成分Ｂの割合が40〜10重量％であることを
特徴とする。
本発明で用いられるエチレン−α−オレフイン
共重合体は、エチレン−プロピレン共重合体、エ
チレン−ブテン−１共重合体等で代表される軟質
共重合体であり、好ましくはエチレンを10〜90重
量％含むものであつて、密度が0.86〜0.91の範囲
にあり、メルトインデツクス（190℃、2.16Kg）
が0.1〜100程度のものである。このエチレン−α
−オレフイン共重合体にグラフトされる不飽和カ
ルボン酸またはその誘導体としては、例えばアク
リル酸、メタクリル酸、マレイン酸、フマル酸、
イタコン酸、クロトン酸およびこれらのカルボン
酸の酸無水物、エステル、酸アミド等の誘導体が
あげられるが、特にアクリル酸、メタクリル酸、
およびそのエステル類並びにマレイン酸、無水マ
レイン酸が接着力に優れていて好ましい。これら
の不飽和カルボン酸またはその誘導体は単独で用
いてもよく、また２種以上混合して用いることも
でき、そのグラフト反応による付加量はエチレン
−α−オレフイン共重合体100重量部に対して1.1
〜10重量部である。この範囲を越えるとグラフト
変性物の加工性が低下し、逆にこの範囲より少な
い場合は接着性に劣るものになる。
エチレン−α−オレフイン共重合体に不飽和カ
ルボン酸またはその誘導体をグラフト変性させる
方法としては、従来公知の任意の方法を用いるこ
とができ、例えば、ラジカル発生剤をさらに加え
て溶融混練中あるいは適当な溶媒中で加熱反応さ
せる方法があげられる。なおラジカル発生剤を用
いたグラフト反応の場合は、一般に未反応のモノ
マーがかなりの割合で残ることがあるが、本発明
においてはこの未反応物は真空乾燥等の方法によ
つて除去することが好ましく、除去後の実際のグ
ラフト量が前記した1.1〜10重量部の範囲内であ
ることが必要である。
本発明で用いられる水素添加されたスチレン−
ブタジエンブロツク共重合体は、スチレンブロツ
クとブタジエンブロツクをそれぞれ１つ以上有す
るブロツク共重合体のブタジエン部分を80％以上
水素添加したブロツク共重合体であり、好ましく
はスチレンを10〜60重量％含むものであつて、密
度が0.88〜0.94の範囲にあり、メルトインデツク
ス（200℃、５Kg）が10以下程度のものである。
このブロツク共重合体のブロツク構造は（Ｓ−
Ｂ）ｎ、（Ｓ−Ｂ）ｎ−Ｓ、（Ｓ−Ｂ）mX（但し、
Ｓはポリスチレンブロツク、Ｂはブタジエンブロ
ツク、ｎは１〜５の整数、ｍは２〜７の整数、Ｘ
はｍ個の重合体鎖が結合している多官能性化合物
を示す）のような直鎖構造または分枝構造のいず
れでもよく、またテーパー部分あるいは一部ラン
ダム部分を含んでいてもよい。この水素添加され
たスチレン−ブタジエンブロツク共重合体にグラ
フトされる不飽和カルボン酸またはその誘導体と
しては、前記変性エチレン−α−オレフイン共重
合体に用いたものがそのまま使用でき、本発明の
それぞれの組成物において、変性エチレン−α−
オレフイン共重合体と変性スチレン−ブタジエン
ブロツク共重合体水添物は同一の不飽和カルボン
酸またはその誘導体でグラフト変性されたもので
あることが好ましいが、異なるものでグラフト変
性されていても使用することができる。変性スチ
レン−ブタジエンブロツク共重合体水添物におけ
るグラフト反応による付加量は、変性エチレン−
α−オレフイン共重合体の場合と同様の理由で共
重合体100重量部に対して1.1〜10重量部である。
変性スチレン−ブタジエンブロツク共重合体水
添物を得る方法も変性エチレン−α−オレフイン
共重合体の場合と同様であるが、さらに本発明に
おいては、エチレン−α−オレフイン共重合体と
スチレン−ブタジエンブロツク共重合体水添物を
予め混練しておいて、この混練物に不飽和カルボ
ン酸またはその誘導体をグラフト変性するここと
によつて目的の組成物を得ることもできる。
本発明において、変性ポリエチレン−α−オレ
フイン共重合体と変性スチレン−ブタジエンブロ
ツク共重合体水添物との割合は60／40〜90／10で
あり、変性エチレン−α−オレフイン共重合体の
割合が60重量％より少ないと接着剤のせん断強さ
が低下し、逆に90重量％より多いと変性スチレン
−ブタジエンブロツク共重合体水添物による改良
効果が少ない。
本発明の組成物は、さらに目的に応じてポリオ
レフイン、スチレン−ブタジエンブロツク共重合
体水添物、粘着付与剤、可塑剤、充填剤、顔料、
安定剤、紫外線吸収剤等を添加することができ
る。
本発明の組成物は、熱可塑性であるため、各種
の樹脂を共押出する際の接着層として使用できる
ほか、押出ラミネーシヨンへの応用や、フイルム
化することによるフイルム接着剤としての使用も
可能であり、以下の実施例において示したよう
に、多種の被着体と接着可能であることから極め
て広範な用途に応用でき、各種素材の新たな組合
せにより新規な機能性複合材料の可能性を高める
ことができる。
以下に本発明の実施例を示すが、本発明がこれ
らの実施例によつて限定されるものでないことは
いうまでもない。
なお以下の例で使用した接着性樹脂、被着体、
接着方法および測定方法は次の通りである。
(i) 接着性樹脂
変性エチレン−プロピレン共重合体
エチレン−プロピレン共重合体（エチレン53重
量％、密度0.88ｇ／cm3、MI＝1.2）にメタクリル
酸メチルを、ジクミルパーオキサイドを用いてグ
ラフト重合した。反応は30mmφ押出機を用い200
℃で行なつた。メタクリル酸メチル量とジクミル
パーオキサイド量を変化させることにより、グラ
フト量が0.8PHR、1.2PHR、1.7PHR、2.8PHR、
及び7.6PHRの５種のものを得た。このグラフト
量は赤外分光光度計を用いて定量した。
変性エチレン−ブテン−１共重合体
エチレン−ブテン−１共重合体（エチレン80重
量％、密度0.89ｇ／cm3、MI＝７）に無水マレイ
ン酸を、２，５−ジメチル−２，５−ジｔ−ブチ
ルパーオキサイドを用いてグラフト付加した。反
応は30mmφ押出機を用い、230℃で行なつた。グ
ラフト量は、ナトリウムメチラートによる滴定の
結果、0.8PHR及び1.3PHRの２種であつた。
変性ポリエチレン
市販の商品ライネツクスFUL−60（旭化成工業
製、密度0.92ｇ／cm3、MI＝１）を用いた。
変性エチレン−酢酸ビニル共重合体および変性
エチレン−アクリル酸エチル共重合体
エチレン−酢酸ビニル共重合体（エチレン72重
量％、MI＝20）およびエチレン−アクリル酸エ
チル共重合体（エチレン80重量％、MI＝20）に
変性エチレン−ブテン−１共重合体の場合と同じ
方法で無水マレイン酸をグラフト付加した。グラ
フト量はそれぞれ1.2PHR、1.3PHRであつた。
変性スチレン−ブタジエンブロツク共重合体水
添物(1)〜(3)
市販の商品Kraton G1650（Shell Chemical製、
Ｓ−Ｂ−Ｓの水添物、スチレン含量28重量％、密
度0.91ｇ／cm3）に変性エチレン−プロピレン共重
合体の場合と同じ方法でメタクリル酸メチルをグ
ラフトしたものを変性スチレン−ブタジエンブロ
ツク共重合体水添物(1)とした。なお、水添物(1)の
グラフト量は1.0PHR、1.5PHR、2.5PHRおよび
8.1PHRの４種類のものを得た。
上記Kraton G1650に変性エチレン−ブテン−
１共重合体の場合と同じ方法で無水マレイン酸を
グラフトしたものを変性スチレン−ブタジエンブ
ロツク共重合体水添物(2)とした。なお水添物(2)の
グラフト量は1.3PHRであつた。
ブロツク構造がＢ−Ｓ−Ｂ−Ｓ型のテーパー部
分を有するスチレン−ブタジエンブロツク共重合
体（スチレン含量40重量％、MI＝10）にニツケ
ルオクタネート−トリエチルアルミニウム系触媒
を用いて水素添加を行なつた（密度0.92ｇ／cm3）。
次いで前記変性エチレン−ブテン−１共重合体の
場合と同じ方法で無水マレイン酸をグラフトし、
得られた樹脂を変性スチレン−ブタジエンブロツ
ク共重合体水添物(3)とした。水添物(3)のグラフト
量は0.9PHRと1.6PHRであつた。
(ii) 被着体
本実施例で用いた被着体は次のとおりである。
(a) ポリアクリロニトリル系フイルム：アクリロ
ニトリル含有率94重量％、200μ厚
(b) ポリフツ化ビニルフイルム：テドラー
100BG30WH（Du Pont製、商品名）、25μ厚
(c) ポリエチレンフイルム：HDPE、200μ厚
(d) ポリプロピレンフイルム：200μ厚
(e) ABSフイルム：200μ厚
(f) ポリメタクリル酸メチルフイルム：200μ厚
(g) エチレン−ビニルアルコール共重合体フイル
ム：200μ厚
(h) ポリアミドフイルム：ナイロン６、40μ厚
(i) ポリエステルフイルム：PET、40μ厚
(j) アラミド織維織物：ケブラー29（Du Pont製、
商品名）1000デニール、平織
(k) ポリアミド織物：ナイロン66、840デニール、
平織
(l) ポリエステル織物：PET、1000デニール、
平織
(iii) 接着方法
以下の実施例および比較例の接着性樹脂組成物
をプレス成形法で200μ厚のフイルムとし、該フ
イルムを各種被着体とアルミニウム支持層
（100μC厚）にはさんで、温度180℃及び圧力30
Kg／cm2の条件でプレス接着した。
(iv) 測定方法
剥離強さは、25mm幅に切断した接着試験片を用
い、引張試験機でＴ型剥離試験を行なうことによ
つて求めた。なお剥離速度は25mm／minとした。
せん断強さは、接着面積25×25mm2の接着試験片
を用い、せん断速度50mm／minで測定した。
実施例および比較例
前記した各種接着性樹脂組成物を用いて、各種
の被着体に対する接着特性を測定した。結果は第
１表〜第４表に示す通りであつた。これらの結果
から、本発明の接着性樹脂組成物は常温および低
温における接着特性に優れており、また数多くの
被着体と接着可能な、極めて優れた組成物である
ことが明らかである。
The present invention relates to a polyolefin polymer composition with excellent adhesive properties. It is known that polyolefins are graft-modified with unsaturated carboxylic acids such as maleic anhydride or derivatives thereof for the purpose of improving the adhesive properties of polyolefins. It is already used as an adhesive layer for polyethylene coating of large-diameter pipes. In addition, many proposals have been made regarding modified polyolefin compositions for the purpose of improving adhesion, and a blend of two types of polyolefin polymers (Japanese Patent Publication No. 1989-1999-1) has been proposed.
Publication No. 18251, Japanese Patent Publication No. 1982-19259, Japanese Patent Application Publication No. 1983
-13718, etc.), blends of modified polyolefins and elastomers (JP-A-52-80334, JP-A-52-123443, JP-A-55-104373)
(see Japanese Patent Publication No. 56-9942, etc.) or blends with other additives (Japanese Patent Publication No. 55-9942, etc.)
66981, etc.). however,
These inventions are aimed at improving the adhesive strength to specific adherends, and the adhesion to polyacrylonitrile resins and fluorine resins, which are generally difficult to adhere to, is insufficient. In particular, it was hardly possible to adhere to compositions based on modified polyethylene or modified polypropylene. It has also been proposed to use a modified block copolymer of a monovinyl-substituted aromatic compound and a conjugated diene as a modifier for ethylene copolymers (JP-A-55-13719; Showa 55-13727
This block copolymer does not have very good thermal stability and tends to form a gel during graft modification, making it difficult to graft a large amount of unsaturated carboxylic acid, etc. If 1 part by weight or more of the graft was added to 100 parts by weight, the adhesive performance would actually deteriorate. In order to obtain a polyolefin polymer that adheres well to a wide range of adherends, the present inventor conducted a search for various modified polyolefins, and found that ethylene and α
It has been found that a copolymer with -olefin graft-modified with an unsaturated carboxylic acid or a derivative thereof (hereinafter simply referred to as a modified polyethylene-α-olefin copolymer) has the most excellent adhesive performance. However, this modified polyethylene-α-olefin copolymer alone does not have sufficient adhesive performance at low temperatures, and when used as an adhesive layer of a laminate, there is a risk of peeling at temperatures below 0°C. Therefore, in order to further improve the adhesive performance of the modified polyethylene-α-olefin copolymer, especially the low temperature adhesive performance, the present inventors
As a result of many studies on various compounding agents, we decided to use a modified styrene-butadiene block copolymer (hereinafter simply referred to as a modified styrene-butadiene block copolymer) in which an unsaturated carboxylic acid or a derivative thereof is grafted onto a hydrogenated styrene-butadiene block copolymer. By selecting a hydrogenated copolymer (referred to as a hydrogenated copolymer) and increasing the amount of graft addition compared to conventional techniques, it is possible to not only improve the desired low-temperature adhesion performance but also increase the types of adherends that can be bonded. However, they discovered that it is possible to obtain an adhesive resin composition that can be used in an extremely wide range of applications, and completed the present invention. That is, the adhesive resin composition according to the present invention includes: A: 100 parts by weight of ethylene-α-olefin copolymer and 1.1 parts by weight of an unsaturated carboxylic acid or a derivative thereof.
B: A modified product obtained by grafting 1.1 to 10 parts by weight of an unsaturated carboxylic acid or a derivative thereof to 100 parts by weight of a hydrogenated styrene-butadiene block copolymer. The composition is characterized in that the proportion of component A is 60 to 90% by weight and the proportion of component B is 40 to 10% by weight. The ethylene-α-olefin copolymer used in the present invention is a soft copolymer represented by ethylene-propylene copolymer, ethylene-butene-1 copolymer, etc., and preferably contains 10 to 90% ethylene by weight. %, the density is in the range of 0.86 to 0.91, and the melt index (190℃, 2.16Kg)
is about 0.1 to 100. This ethylene-α
- Examples of unsaturated carboxylic acids or derivatives thereof to be grafted onto the olefin copolymer include acrylic acid, methacrylic acid, maleic acid, fumaric acid,
Examples include itaconic acid, crotonic acid, and derivatives of these carboxylic acids such as acid anhydrides, esters, and acid amides, but especially acrylic acid, methacrylic acid,
and esters thereof, maleic acid, and maleic anhydride are preferred because they have excellent adhesive strength. These unsaturated carboxylic acids or derivatives thereof may be used alone or in combination of two or more, and the amount added by grafting reaction is based on 100 parts by weight of the ethylene-α-olefin copolymer. 1.1
~10 parts by weight. If it exceeds this range, the processability of the graft-modified product will decrease, and if it is less than this range, it will have poor adhesive properties. Any conventionally known method can be used to graft-modify the ethylene-α-olefin copolymer with an unsaturated carboxylic acid or a derivative thereof. An example of this method is to carry out a heating reaction in a suitable solvent. In addition, in the case of a graft reaction using a radical generator, a considerable amount of unreacted monomer may generally remain, but in the present invention, this unreacted material can be removed by a method such as vacuum drying. Preferably, the actual amount of graft after removal is within the range of 1.1 to 10 parts by weight as described above. Hydrogenated styrene used in the present invention
The butadiene block copolymer is a block copolymer obtained by hydrogenating 80% or more of the butadiene portion of a block copolymer having one or more styrene blocks and one or more butadiene blocks, and preferably contains 10 to 60% by weight of styrene. The density is in the range of 0.88 to 0.94, and the melt index (200°C, 5 kg) is about 10 or less.
The block structure of this block copolymer is (S-
B)n, (S-B)n-S, (S-B)mX (however,
S is polystyrene block, B is butadiene block, n is an integer of 1 to 5, m is an integer of 2 to 7, X
(indicates a polyfunctional compound in which m polymer chains are bonded) may have either a linear structure or a branched structure, and may also contain a tapered portion or a partially random portion. As the unsaturated carboxylic acid or its derivative to be grafted onto this hydrogenated styrene-butadiene block copolymer, those used for the above-mentioned modified ethylene-α-olefin copolymer can be used as they are; In the composition, modified ethylene-α-
The olefin copolymer and the hydrogenated modified styrene-butadiene block copolymer are preferably graft-modified with the same unsaturated carboxylic acid or its derivative, but they can be used even if they are graft-modified with different ones. be able to. The amount added by the graft reaction in the hydrogenated modified styrene-butadiene block copolymer is
For the same reason as in the case of the α-olefin copolymer, the amount is 1.1 to 10 parts by weight per 100 parts by weight of the copolymer. The method for obtaining the hydrogenated modified styrene-butadiene block copolymer is the same as that for the modified ethylene-α-olefin copolymer, but in the present invention, the method for obtaining the hydrogenated product of the ethylene-α-olefin copolymer and styrene-butadiene The desired composition can also be obtained by kneading the hydrogenated block copolymer in advance and graft-modifying the kneaded product with an unsaturated carboxylic acid or a derivative thereof. In the present invention, the ratio of the modified polyethylene-α-olefin copolymer to the hydrogenated modified styrene-butadiene block copolymer is 60/40 to 90/10, and the ratio of the modified ethylene-α-olefin copolymer is 60/40 to 90/10. If it is less than 60% by weight, the shear strength of the adhesive will decrease, and if it is more than 90% by weight, the improvement effect of the hydrogenated modified styrene-butadiene block copolymer will be small. The composition of the present invention may further include polyolefin, hydrogenated styrene-butadiene block copolymer, tackifier, plasticizer, filler, pigment,
Stabilizers, ultraviolet absorbers, etc. can be added. Since the composition of the present invention is thermoplastic, it can be used as an adhesive layer when coextruding various resins, and can also be applied to extrusion lamination or used as a film adhesive by forming it into a film. As shown in the examples below, it can be applied to an extremely wide range of applications because it can be bonded to a wide variety of adherends, and new combinations of various materials open up the possibility of creating new functional composite materials. can be increased. Examples of the present invention are shown below, but it goes without saying that the present invention is not limited to these Examples. The adhesive resin, adherend,
The adhesion method and measurement method are as follows. (i) Adhesive resin-modified ethylene-propylene copolymer Ethylene-propylene copolymer (ethylene 53% by weight, density 0.88 g/cm 3 , MI=1.2) is grafted with methyl methacrylate using dicumyl peroxide. Polymerized. The reaction was carried out using a 30 mmφ extruder.
It was carried out at ℃. By changing the amount of methyl methacrylate and dicumyl peroxide, the amount of grafting can be adjusted to 0.8PHR, 1.2PHR, 1.7PHR, 2.8PHR,
and 5 types of 7.6PHR were obtained. The amount of grafting was determined using an infrared spectrophotometer. Modified ethylene-butene-1 copolymer Maleic anhydride was added to ethylene-butene-1 copolymer (ethylene 80% by weight, density 0.89 g/cm 3 , MI=7), and 2,5-dimethyl-2,5- Graft addition was carried out using di-t-butyl peroxide. The reaction was carried out at 230°C using a 30mmφ extruder. As a result of titration with sodium methylate, the amount of grafting was determined to be 0.8 PHR and 1.3 PHR. Modified polyethylene Commercially available product Linex FUL-60 (manufactured by Asahi Kasei Industries, density 0.92 g/cm 3 , MI=1) was used. Modified ethylene-vinyl acetate copolymer and modified ethylene-ethyl acrylate copolymer Ethylene-vinyl acetate copolymer (ethylene 72% by weight, MI=20) and ethylene-ethyl acrylate copolymer (ethylene 80% by weight, MI=20) was grafted with maleic anhydride in the same manner as in the case of the modified ethylene-butene-1 copolymer. The amount of grafting was 1.2PHR and 1.3PHR, respectively. Modified styrene-butadiene block copolymer hydrogenated products (1) to (3) Commercially available product Kraton G1650 (manufactured by Shell Chemical,
A modified styrene-butadiene block is obtained by grafting methyl methacrylate onto a hydrogenated product of S-B-S (styrene content: 28% by weight, density: 0.91 g/cm 3 ) in the same manner as the modified ethylene-propylene copolymer. This was designated as hydrogenated copolymer (1). In addition, the amount of grafting of hydrogenate (1) is 1.0PHR, 1.5PHR, 2.5PHR and
I got 4 types of 8.1PHR. The above Kraton G1650 is modified with ethylene-butene.
A hydrogenated modified styrene-butadiene block copolymer (2) was obtained by grafting maleic anhydride in the same manner as in the case of Copolymer 1. The amount of hydrogenated compound (2) grafted was 1.3 PHR. A styrene-butadiene block copolymer (styrene content: 40% by weight, MI = 10) having a tapered part with a B-S-B-S block structure was hydrogenated using a nickel octanate-triethylaluminum catalyst. Natsuta (density 0.92g/cm 3 ).
Next, maleic anhydride is grafted in the same manner as in the case of the modified ethylene-butene-1 copolymer,
The obtained resin was designated as a hydrogenated modified styrene-butadiene block copolymer (3). The amount of hydrogenated compound (3) grafted was 0.9 PHR and 1.6 PHR. (ii) Adherent The adherend used in this example is as follows. (a) Polyacrylonitrile film: Acrylonitrile content 94% by weight, 200μ thickness (b) Polyfluorinated vinyl film: Tedlar
100BG30WH (manufactured by Du Pont, product name), 25μ thickness (c) Polyethylene film: HDPE, 200μ thickness (d) Polypropylene film: 200μ thickness (e) ABS film: 200μ thickness (f) Polymethyl methacrylate film: 200μ thickness ( g) Ethylene-vinyl alcohol copolymer film: 200μ thick (h) Polyamide film: Nylon 6, 40μ thick (i) Polyester film: PET, 40μ thick (j) Aramid woven fabric: Kevlar 29 (manufactured by Du Pont,
Product name) 1000 denier, plain weave (k) polyamide fabric: nylon 66, 840 denier,
Plain weave (l) polyester fabric: PET, 1000 denier,
Plain weave (iii) Adhesion method The adhesive resin compositions of the following Examples and Comparative Examples were press-molded into a 200 μ thick film, and the film was sandwiched between various adherends and an aluminum support layer (100 μC thick). Temperature 180℃ and pressure 30
Press bonding was carried out under conditions of Kg/cm 2 . (iv) Measuring method Peel strength was determined by performing a T-peel test using a tensile tester using adhesive test pieces cut into 25 mm widths. Note that the peeling speed was 25 mm/min. The shear strength was measured using an adhesive test piece with an adhesive area of 25 x 25 mm 2 at a shear rate of 50 mm/min. Examples and Comparative Examples Using the various adhesive resin compositions described above, adhesive properties to various adherends were measured. The results were as shown in Tables 1 to 4. From these results, it is clear that the adhesive resin composition of the present invention has excellent adhesive properties at room temperature and low temperature, and is an extremely excellent composition capable of adhering to a large number of adherends.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
100重量部に不飽和カルボン酸またはその誘導
体1.1〜10重量部をグラフト付加した変性物と、 Ｂ ：水素滴加されたスチレン−ブタジエンブロ
ツク共重合体100重量部に不飽和カルボン酸ま
たはその誘導体1.1〜10重量部をグラフト付加
した変性物 を含んで成り、前記成分Ａの割合が60〜90重量
％で成分Ｂの割合が40〜10重量％であることを
特徴とする接着性樹脂組成物。[Claims] 1 A: Ethylene-α-olefin copolymer
A modified product obtained by grafting 1.1 to 10 parts by weight of an unsaturated carboxylic acid or its derivative to 100 parts by weight; B: 1.1 to 1.1 parts by weight of an unsaturated carboxylic acid or its derivative to 100 parts by weight of a styrene-butadiene block copolymer to which hydrogen droplets have been added. An adhesive resin composition comprising a modified material grafted with ~10 parts by weight, wherein the proportion of component A is 60 to 90% by weight and the proportion of component B is 40 to 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8881081A JPS57205440A (en) | 1981-06-11 | 1981-06-11 | Adhesive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8881081A JPS57205440A (en) | 1981-06-11 | 1981-06-11 | Adhesive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57205440A JPS57205440A (en) | 1982-12-16 |
| JPH0326236B2 true JPH0326236B2 (en) | 1991-04-10 |
Family
ID=13953241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8881081A Granted JPS57205440A (en) | 1981-06-11 | 1981-06-11 | Adhesive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57205440A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5278246A (en) * | 1981-08-13 | 1994-01-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer and a process for producing the same |
| US5272209A (en) * | 1981-08-13 | 1993-12-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer composition |
| DE3280472T2 (en) * | 1981-08-13 | 1996-11-14 | Asahi Chemical Ind | Modified block copolymer |
| US5272208A (en) * | 1981-08-13 | 1993-12-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer composition |
| US4427828A (en) * | 1981-09-01 | 1984-01-24 | The Firestone Tire & Rubber Company | Impact resistant polymeric compositions containing polyamides, maleic anhydride adducts of hydrogenated polymers and graft copolymers thereof |
| US5371141A (en) * | 1985-07-31 | 1994-12-06 | Shell Oil Company | High impact resistant blends of thermoplastic polyamides and modified block copolymers |
| US4994508A (en) * | 1987-07-16 | 1991-02-19 | Asahi Kasei Kogyo Kabushiki Kaisha | Specific hydrogenated block copolymer composition and process for producing the same |
| US5070143A (en) * | 1989-03-09 | 1991-12-03 | Morton International, Inc. | Adhesive blend of polyolefins and grafted block copolymer of polystyrene |
| FR2717487B1 (en) * | 1994-03-16 | 1998-06-26 | Atochem Elf Sa | Coextrusion binder composition and coextruded multilayer complex in which said composition is used as an adhesive layer. |
| KR100549709B1 (en) * | 1999-05-13 | 2006-02-08 | 삼성토탈 주식회사 | Adhesive polyolefin compounds |
| JP4498009B2 (en) * | 2004-05-14 | 2010-07-07 | 三井化学株式会社 | Coating agent |
| JP4498051B2 (en) * | 2004-07-29 | 2010-07-07 | 三井化学株式会社 | Coating agent |
-
1981
- 1981-06-11 JP JP8881081A patent/JPS57205440A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57205440A (en) | 1982-12-16 |
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