JPH0319058B2 - - Google Patents
Info
- Publication number
- JPH0319058B2 JPH0319058B2 JP58069926A JP6992683A JPH0319058B2 JP H0319058 B2 JPH0319058 B2 JP H0319058B2 JP 58069926 A JP58069926 A JP 58069926A JP 6992683 A JP6992683 A JP 6992683A JP H0319058 B2 JPH0319058 B2 JP H0319058B2
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene
- resin
- weight
- layer
- modified
- 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 - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 16
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 229920013716 polyethylene resin Polymers 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920001684 low density polyethylene Polymers 0.000 claims description 7
- 239000004702 low-density polyethylene Substances 0.000 claims description 7
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 27
- 230000001070 adhesive effect Effects 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000006353 environmental stress Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000004898 kneading Methods 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
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- UIERETOOQGIECD-ARJAWSKDSA-N angelic acid Chemical compound C\C=C(\C)C(O)=O UIERETOOQGIECD-ARJAWSKDSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 230000000052 comparative effect Effects 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
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
本発明は樹脂−金属積層体に関し、さらに詳し
くは接着強度が高く、耐環境応力亀裂性、耐温塩
水性等が優れており、特に鋼管被覆用に好適であ
る樹脂−金属積層体に関するものである。
従来より、金属保護の目的等でポリオレフイン
を鉄、アルミニウム等の金属と積層したものが広
く用いられている。しかし、一般にポリオレフイ
ンは無極性であるため、金属に対する接着性が極
めて悪い。この接着性を改善するために、金属と
ポリオレフインの間に接着層として無水マレイン
酸変性ポリオレフインを用いる方法(特公昭42−
10757号公報等)が知られているが、いまだ接着
強度が十分でなく耐環境応力亀裂性(ESCR)に
乏しい。また、酸変性ポリオレフインに炭化水素
系合成エラストマーを配合して接着性を改良する
ことも提案されている(特開昭52−80334号公報)
が、耐熱性、耐溶剤性が低下するという問題点が
ある。
特に土中あるいは海水などの水中等に配置され
る鋼管の表面を被覆する場合には、接着強度など
の一次特性に加え、ESCR、耐温塩水性などの二
次特性にも優れていることが要求される。
そこで本発明者は、接着強度、ESCR等を優れ
た樹脂−金属積層体について鋭意検討した結果、
本発明を完成した。
すなわち本発明は、(A)不飽和カルボン酸または
その誘導体によつて変性された高密度ポリエチレ
ンまたは低密度ポリエチレン、あるいは該変性ポ
リエチレンと未変性ポリエチレン、エチレン−酢
酸ビニル共重合体、エチレン−プロピレンゴムお
よび熱可塑性ポリオレフインエラストマーのいず
れかとの混合物からなり、前記不飽和カルボン酸
またはその誘導体を0.001〜1.0重量%含有する変
性ポリエチレン樹脂55〜99重量%と密度0.900〜
0.930g/cm3、メルトインデツクス0.1〜25g/10
分のブテン−1重合体45〜1重量%からなる樹脂
層および(B)鉄あるいはアルミニウムからなる金属
層を積層してなる樹脂−金属積層体である。
(A)樹脂層(以下、A層という。)は、不飽和カ
ルボン酸またはその誘導体によつて変性された高
密度ポリエチレン(変性高密度ポリエチレン)ま
たは低密度ポリエチレン(変性低密度ポリエチレ
ン)、あるいは該変性ポリエチレンと未変性ポリ
エチレン、エチレン−酢酸ビニル共重合体、エチ
レン−プロピレンゴムおよび熱可塑性ポリオレフ
インエラストマーのいずれかとの混合物からな
り、前記不飽和カルボン酸またはその誘導体を
0.001〜1.0重量%含有する変性ポリエチレン樹脂
と、密度0.900〜0.930g/cm3、メルトインデツク
ス0.1〜25g/10分のブテン−1重合体45〜1重
量%からなるものである。
すなわち本発明で変性ポリエチレン樹脂とは、
変性高密度ポリエチレンまたは変性低密度ポリエ
チレン、あるいは該変性ポリエチレンと未変性ポ
リエチレン、エチレン−酢酸ビニル共重合体、エ
チレン−プロピレンゴムおよび熱可塑性ポリオレ
フインエラストマーのいずれかとの混合物を意味
する。変性されるポリエチレンとしては上記の如
く高密度ポリエチレンまたは低密度ポリエチレン
が用いられる。
ポリエチレンの変性に用いる不飽和カルボン酸
としてはアクリル酸、メタアクリル酸、マレイン
酸、フマル酸、イタコン酸、クロトン酸、シトラ
コン酸、ソルビン酸、メサコン酸、アンゲリカ酸
などがある。また、その誘導体としては酸無水
物、エステル、アミド、、イミド、金属塩などが
あり、例えば無水マレイン酸、無水イタコン酸、
無水シトラコン酸、アクリル酸メチル、メタアク
リル酸メチル、アクリル酸エチル、アクリル酸ブ
チル、マレイン酸モノエチルエステル、アクリル
アミド、マレイン酸モノアミド、マレイミド、N
−ブチルマレイミド、アクリル酸ナトリウム、メ
タアクリル酸ナトリウムなどを挙げることができ
る。
これらの不飽和カルボン酸またはその誘導体に
よつてポリエチレンを変性するには、その方法は
特に制限されず公知の種々の方法を用いて行なう
ことができる。例えばポリエチレンと無水マレイ
ン酸等を溶媒の存在下あるいは不存在下でラジカ
ル開始剤を添加し、加熱することにより進行す
る。反応に際しては、スチレンなどの他のビニル
モノマーあるいは液状ゴム、熱可塑性ゴムなどの
ゴム類を共存させることもできる。
このようにして得られた変性ポリエチレン中の
酸付加量は0.001〜5重量%、好ましくは0.5〜3
重量%である。変性ポリエチレン樹脂は前記の変
性ポリエチレンをそのまま用いてもよいが、好ま
しくは未変性ポリエチレン、エチレン−酢酸ビニ
ル共重合体、エチレン−プロピレンゴム、熱可塑
性ポリオレフインエラストマーのいずれかと混合
希釈して最終的に酸含有量を通常0.001〜1.0重量
%、好ましくは0.01〜0.6重量%、特に好ましく
は0.05〜0.4重量%の範囲とする。酸含有量が
0.001重量%未満であると、接着性が低下し、1.0
重量%を超えると、樹脂層の強度、ESCR等が低
下して実用に供し得なくなる。ここで未変性ポリ
エチレンとしては高密度ポリエチレン、中・低密
度ポリエチレン、直鎖状低密度ポリエチレンなど
を用いることができる。エチレン−酢酸ビニル共
重合体についても制限はないが、酢酸ビニル含量
10〜40重量%のものが好ましく用いられる。エチ
レン−プロピレンゴムとしては、例えばエチレン
−プロピレンコポリマー、エチレン−プロピレン
−ジエンタ−ポリマーなどが挙げられる。
変性ポリエチレン樹脂は(A)層のベースとなるも
のであつて、55〜99重量%、好ましくは85〜95重
量%の割合で用いられる。
次に、ブテン−1重合体は接着強度、ESCRを
改良するために加えられるものであり、ブテン−
1の単独重合体あるいは他のα−オレフイン、例
えばエチレン、プロピレン等との共重合体が用い
られる。この共重合体はブテン−1モノマーと他
のα−オレフインモノマーを原料として規則性重
合を行なうことにより得られる。なお、他のα−
オレフインモノマーを用いる場合、その含有量は
20重量%以下、好ましくは10重量%以下とすべき
である。
ブテン−1重合体は密度0.900〜0.930g/cm2、
好ましくは0.905〜0.920g/cm2、メルトインデツ
クス(MI)0.1〜25g/10分、好ましくは0.3〜
3.0g/10分のものが好適に用いられる。MIが0.1
g/10分未満であると、分散性が悪くなり、改質
効果が不十分となり、25g/10分を超えると、
ESCRが悪化して好ましくない。
ブテン−1重合体の配合量は45〜1重量%、好
ましくは15〜5重量%である。45重量%を超える
と、接着性が低下し、1重量%未満であると、接
着性が低下すると共にESCRの改良が不十分とな
る。
上記2成分を混練することにより(A)層の樹脂が
得られる。混練は常法により行なえばよく、たと
えば押出機、バンバリーミキサーなどを用いて行
なうことができる。
次に、B金属層(以下、(B)層という。)として
は鉄またはアルミニウムを用いる。
本発明の積層体は上記A層およびB層を積層す
ることにより得られる。この場合、A層の厚さは
200〜500μが適当である。積層方法としては、通
常行なわれている方法を適用すればよく、一般的
にはB層の表面を100〜150℃に加熱しておき、こ
れに表面温度180〜230℃としたA層のシートを積
層する。別法としてA層とB層を重ね130〜200℃
の温度および1〜10Kg/cm2の圧力で0.1〜10分間
加熱溶融圧着して積層体を得ることができる。本
発明ではA層にブテン−1重合体を加えているた
め、B層との接着強度が高く、低温度で短時間に
強固に接着させることができる。
本発明は上記積層体に加えて、ポリエチレン系
樹脂層と金属層との間に接着剤層を介した積層体
を当然含むものである。ここで接着剤層としては
公知の接着剤が用いられ、例えば熱可塑性エポキ
シ樹脂接着剤、熱硬化性エキポシ樹脂接着剤等が
ある。熱硬化性エポキシ樹脂接着剤にあつては、
あらかじめ金属表面に接着剤を塗布し、半硬化も
しくは硬化完了後、ポリエチレン系樹脂と融着積
層される。これら接着剤層の厚みとしては5〜
100μ程度で十分であり、この方法を採用するこ
とによつて層間接着強度をさらに向上させること
ができるばかりでなく、耐温水性を向上させるこ
とができる。本発明にあつては、すぐれた接着性
を有する樹脂層に対して必要によりさらにポリオ
レフイン、ポリアミド等の熱可塑性樹脂や金属な
ど他の材料を積層することができることは云うま
でもないことである。
以上に詳述したように、本発明の樹脂−金属積
層体は両者間の接着力が著しく高く、しかも耐溶
剤性、耐熱性、耐環境応力亀裂性などにすぐれた
ものである。したがつて、被覆鋼管のみならず、
建材、包装容器、食品容器などとして有効に使用
することができる。
次に、本発明を実施例により詳しく説明する。
なお、試験の評価は次のように行なつた。
90°剥離強度:A−B層間の剥離した強度を示し
ている。
温塩水剥離:樹脂−金属積層体を3%食塩水に80
℃で1週間浸漬した後、A層とB層の間で剥離
した面積を百分率で示した。
ESCR:ASTM−D−1693に準拠したf50値。
実施例1〜11および比較例1〜4
変性ポリエチレン樹脂およびブテン−1重合体
を第1表に示す配合割合でドライブレンドした
後、加熱混練してA層樹脂を得た。
次に、上記のA層樹脂シート(厚さ500μ)を
B層である金属板に重ね、さらにその上に密度
0.95g/cm2、MI0.15g/10分の高密度ポリエチレ
ンシート(厚さ2mm)を重ねて130℃、10Kg/cm2
で10分間加熱溶融圧着し、樹脂−金属積層体を製
造した。得られた積層体の試験結果を第1表に示
す。
The present invention relates to a resin-metal laminate, and more particularly to a resin-metal laminate that has high adhesive strength, excellent environmental stress cracking resistance, and resistance to hot salt water, and is particularly suitable for coating steel pipes. be. Conventionally, materials in which polyolefin is laminated with metals such as iron and aluminum have been widely used for the purpose of protecting metals. However, since polyolefins are generally nonpolar, their adhesion to metals is extremely poor. In order to improve this adhesion, a method using maleic anhydride-modified polyolefin as an adhesive layer between the metal and polyolefin (Japanese Patent Publication No.
10757, etc.), but the adhesive strength is still insufficient and the environmental stress cracking resistance (ESCR) is poor. It has also been proposed to improve adhesion by blending a hydrocarbon-based synthetic elastomer with acid-modified polyolefin (Japanese Patent Application Laid-open No. 80334/1983).
However, there is a problem that heat resistance and solvent resistance decrease. In particular, when coating the surface of steel pipes that are placed underground or in water such as seawater, it is important to have excellent primary properties such as adhesive strength, as well as secondary properties such as ESCR and resistance to hot salt water. required. Therefore, as a result of intensive study on resin-metal laminates with excellent adhesive strength, ESCR, etc., the present inventor found that
The invention has been completed. That is, the present invention provides (A) high-density polyethylene or low-density polyethylene modified with an unsaturated carboxylic acid or a derivative thereof, or the modified polyethylene and unmodified polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene rubber. and a thermoplastic polyolefin elastomer, 55 to 99% by weight of a modified polyethylene resin containing 0.001 to 1.0% by weight of the unsaturated carboxylic acid or its derivative, and a density of 0.900 to 0.90%.
0.930g/ cm3 , melt index 0.1~25g/10
This is a resin-metal laminate formed by laminating a resin layer consisting of 45 to 1% by weight of butene-1 polymer and (B) a metal layer consisting of iron or aluminum. (A) The resin layer (hereinafter referred to as layer A) is made of high-density polyethylene (modified high-density polyethylene) or low-density polyethylene (modified low-density polyethylene) modified with unsaturated carboxylic acid or its derivative, or It consists of a mixture of modified polyethylene and unmodified polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene rubber, and thermoplastic polyolefin elastomer, and contains the unsaturated carboxylic acid or its derivative.
It consists of a modified polyethylene resin containing 0.001 to 1.0% by weight and 45 to 1% by weight of butene-1 polymer having a density of 0.900 to 0.930 g/cm 3 and a melt index of 0.1 to 25 g/10 min. That is, the modified polyethylene resin in the present invention is
It means modified high-density polyethylene, modified low-density polyethylene, or a mixture of the modified polyethylene and any one of unmodified polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene rubber, and thermoplastic polyolefin elastomer. As the polyethylene to be modified, high-density polyethylene or low-density polyethylene is used as described above. Examples of unsaturated carboxylic acids used for modifying polyethylene include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid. In addition, its derivatives include acid anhydrides, esters, amides, imides, metal salts, etc., such as maleic anhydride, itaconic anhydride,
Citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N
-butylmaleimide, sodium acrylate, sodium methacrylate and the like. The method for modifying polyethylene with these unsaturated carboxylic acids or derivatives thereof is not particularly limited, and various known methods can be used. For example, the process proceeds by adding a radical initiator to polyethylene and maleic anhydride in the presence or absence of a solvent and heating the mixture. During the reaction, other vinyl monomers such as styrene or rubbers such as liquid rubber and thermoplastic rubber may also be present. The amount of acid addition in the modified polyethylene thus obtained is 0.001 to 5% by weight, preferably 0.5 to 3% by weight.
Weight%. The modified polyethylene resin described above may be used as it is, but it is preferably mixed and diluted with unmodified polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene rubber, or thermoplastic polyolefin elastomer, and finally acidified. The content is usually in the range of 0.001 to 1.0% by weight, preferably 0.01 to 0.6% by weight, particularly preferably 0.05 to 0.4% by weight. acid content
If it is less than 0.001% by weight, the adhesion will decrease and 1.0
If it exceeds % by weight, the strength, ESCR, etc. of the resin layer will decrease, making it impossible to put it into practical use. Here, as the unmodified polyethylene, high-density polyethylene, medium/low-density polyethylene, linear low-density polyethylene, etc. can be used. There are no restrictions on the ethylene-vinyl acetate copolymer, but the vinyl acetate content
10 to 40% by weight is preferably used. Examples of the ethylene-propylene rubber include ethylene-propylene copolymer and ethylene-propylene-dien terpolymer. The modified polyethylene resin serves as the base for layer (A) and is used in a proportion of 55 to 99% by weight, preferably 85 to 95% by weight. Next, butene-1 polymer is added to improve adhesive strength and ESCR;
A homopolymer of 1 or a copolymer with other α-olefins such as ethylene, propylene, etc. can be used. This copolymer is obtained by regular polymerization using butene-1 monomer and other α-olefin monomers as raw materials. In addition, other α−
When using olefin monomer, its content is
It should be less than 20% by weight, preferably less than 10% by weight. Butene-1 polymer has a density of 0.900 to 0.930 g/cm 2 ,
Preferably 0.905 to 0.920 g/cm 2 , melt index (MI) 0.1 to 25 g/10 min, preferably 0.3 to
3.0g/10 minutes is preferably used. MI is 0.1
If it is less than 25 g/10 minutes, the dispersibility will be poor and the reforming effect will be insufficient, and if it exceeds 25 g/10 minutes,
ESCR worsens, which is not desirable. The amount of butene-1 polymer blended is 45-1% by weight, preferably 15-5% by weight. When it exceeds 45% by weight, the adhesiveness decreases, and when it is less than 1% by weight, the adhesiveness decreases and the improvement in ESCR becomes insufficient. The resin of layer (A) is obtained by kneading the above two components. The kneading may be carried out by a conventional method, for example, using an extruder, a Banbury mixer, or the like. Next, iron or aluminum is used as the B metal layer (hereinafter referred to as (B) layer). The laminate of the present invention is obtained by laminating the above layer A and layer B. In this case, the thickness of layer A is
200 to 500μ is appropriate. As for the lamination method, it is sufficient to apply a commonly used method. Generally, the surface of the B layer is heated to 100 to 150°C, and then the A layer sheet with a surface temperature of 180 to 230°C is laminated. Laminate. Alternatively, stack A layer and B layer at 130-200℃.
A laminate can be obtained by heating, melting and pressing at a temperature of 1 to 10 kg/cm 2 for 0.1 to 10 minutes. In the present invention, since the butene-1 polymer is added to the A layer, the adhesive strength with the B layer is high, and strong adhesion can be achieved at low temperature in a short time. In addition to the above laminate, the present invention naturally includes a laminate with an adhesive layer interposed between the polyethylene resin layer and the metal layer. Here, a known adhesive is used as the adhesive layer, such as a thermoplastic epoxy resin adhesive or a thermosetting epoxy resin adhesive. Regarding thermosetting epoxy resin adhesives,
Adhesive is applied to the metal surface in advance, and after semi-curing or curing is completed, it is fused and laminated with polyethylene resin. The thickness of these adhesive layers is 5~
A thickness of about 100μ is sufficient, and by employing this method, not only the interlayer adhesive strength can be further improved, but also the hot water resistance can be improved. In the present invention, it goes without saying that other materials such as thermoplastic resins such as polyolefin and polyamide, and metals may be further laminated on the resin layer having excellent adhesive properties, if necessary. As detailed above, the resin-metal laminate of the present invention has extremely high adhesive strength between the two, and is also excellent in solvent resistance, heat resistance, environmental stress cracking resistance, etc. Therefore, not only coated steel pipes but also
It can be effectively used as building materials, packaging containers, food containers, etc. Next, the present invention will be explained in detail with reference to examples.
The evaluation of the test was conducted as follows. 90° peel strength: indicates the peel strength between layers A and B. Warm salt water peeling: Resin-metal laminate in 3% saline solution at 80°C
After being immersed at ℃ for one week, the area of peeling between layer A and layer B is expressed as a percentage. ESCR: f50 value according to ASTM-D-1693. Examples 1 to 11 and Comparative Examples 1 to 4 A modified polyethylene resin and a butene-1 polymer were dry blended in the proportions shown in Table 1, and then heated and kneaded to obtain an A-layer resin. Next, the above A-layer resin sheet (thickness 500μ) is layered on the B-layer metal plate, and the density
0.95g/cm 2 , MI 0.15g/10min high-density polyethylene sheets (thickness 2mm) are stacked at 130℃, 10Kg/cm 2
The resin-metal laminate was produced by heating and melting and pressing for 10 minutes. Table 1 shows the test results of the obtained laminate.
【表】【table】
Claims (1)
変性された高密度ポリエチレンまたは低密度ポリ
エチレン、あるいは該変性ポリエチレンと未変性
ポリエチレン、エチレン−酢酸ビニル共重合体、
エチレン−プロピレンゴムおよび熱可塑性ポリオ
レフインエラストマーのいずれかとの混合物から
なり、前記不飽和カルボン酸またはその誘導体を
0.001〜1.0重量%含有する変性ポリエチレン樹脂
55〜99重量%と密度0.900〜0.930g/cm3、メルト
インデツクス0.1〜25g/10分のブテン−1重合
体45〜1重量%からなる樹脂層および(B)鉄あるい
はアルミニウムからなる金属層を積層してなる樹
脂−金属積層体。1 High-density polyethylene or low-density polyethylene modified with an unsaturated carboxylic acid or its derivative, or the modified polyethylene and unmodified polyethylene, ethylene-vinyl acetate copolymer,
consisting of a mixture of ethylene-propylene rubber and a thermoplastic polyolefin elastomer, containing the unsaturated carboxylic acid or its derivative.
Modified polyethylene resin containing 0.001-1.0% by weight
A resin layer consisting of 45-1% by weight of a butene-1 polymer with a density of 0.900-0.930 g/cm 3 and a melt index of 0.1-25 g/10 min, and (B) a metal layer consisting of iron or aluminum. A resin-metal laminate made by laminating two layers.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6992683A JPS59196242A (en) | 1983-04-22 | 1983-04-22 | Resin-metal laminate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6992683A JPS59196242A (en) | 1983-04-22 | 1983-04-22 | Resin-metal laminate |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59196242A JPS59196242A (en) | 1984-11-07 |
JPH0319058B2 true JPH0319058B2 (en) | 1991-03-14 |
Family
ID=13416776
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6992683A Granted JPS59196242A (en) | 1983-04-22 | 1983-04-22 | Resin-metal laminate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59196242A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8820807D0 (en) * | 1988-09-05 | 1988-10-05 | Du Pont Canada | Reduction of corrosion of metals |
WO2022130833A1 (en) * | 2020-12-17 | 2022-06-23 | 昭和電工株式会社 | Method for manufacturing metallic member-resin member bonded body, and film |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5015874A (en) * | 1973-06-12 | 1975-02-19 | ||
JPS51122152A (en) * | 1975-04-18 | 1976-10-26 | Mitsui Petrochem Ind Ltd | Polyolefin composition with excellent adhesion to metals |
JPS5249266A (en) * | 1975-10-17 | 1977-04-20 | Mitsui Petrochemical Ind | Method of coating polyolefin on metallic substrate |
-
1983
- 1983-04-22 JP JP6992683A patent/JPS59196242A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5015874A (en) * | 1973-06-12 | 1975-02-19 | ||
JPS51122152A (en) * | 1975-04-18 | 1976-10-26 | Mitsui Petrochem Ind Ltd | Polyolefin composition with excellent adhesion to metals |
JPS5249266A (en) * | 1975-10-17 | 1977-04-20 | Mitsui Petrochemical Ind | Method of coating polyolefin on metallic substrate |
Also Published As
Publication number | Publication date |
---|---|
JPS59196242A (en) | 1984-11-07 |
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