JPS61252150A - Resin laminate - Google Patents
Resin laminateInfo
- Publication number
- JPS61252150A JPS61252150A JP6332885A JP6332885A JPS61252150A JP S61252150 A JPS61252150 A JP S61252150A JP 6332885 A JP6332885 A JP 6332885A JP 6332885 A JP6332885 A JP 6332885A JP S61252150 A JPS61252150 A JP S61252150A
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- modified
- ethylene
- composition
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Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、耐久接着性、特に耐陰極剥離性と接着性に優
れた樹脂積層体に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin laminate having excellent durable adhesive properties, particularly excellent cathodic peeling resistance and adhesive properties.
(従来の技術)
近年、ポリオレフィンと金属との複合化は、腐蝕防止、
装飾等の表面機能向上、軽量化による省エネルギー等を
目的としてその市場を拡大しつつちる。(Prior art) In recent years, composites of polyolefin and metal have been developed to prevent corrosion,
The market is expanding with the aim of improving surface functionality such as decoration, and saving energy by reducing weight.
これらの中で、ガス、水、石油等の輸送用に地中埋設さ
れて用いられる鋼管は、防蝕を目的にポリエチレンが被
覆材に用いられている。従来、ポリエチレンを鋼管に接
着させるためカルボキシル基やグリシジル基等を導入し
た変性ポリエチレンが接着性樹脂として用いられている
。これらのポリエチレン被覆鋼管は長期間埋設して用い
られるため、耐塩水性、耐温水性等の耐久接着性が要求
される。特に、石油輸送用鋼管等では、パイプラインに
電気防蝕が施されているため、ASTMG−8に規定さ
れる耐陰極剥離性も要求される。Among these, steel pipes buried underground for transporting gas, water, oil, etc. are coated with polyethylene for the purpose of corrosion protection. Conventionally, modified polyethylene into which carboxyl groups, glycidyl groups, etc. have been introduced has been used as an adhesive resin in order to bond polyethylene to steel pipes. Since these polyethylene-coated steel pipes are used buried for long periods of time, they are required to have durable adhesive properties such as salt water resistance and hot water resistance. In particular, steel pipes for oil transportation, etc., are required to have cathodic peeling resistance as specified in ASTM G-8 because the pipelines are subjected to electrical corrosion protection.
(発明が解決しようとする問題点)
しかしながら、変性ポリエチレンは耐久接着性が低いた
め通常は鋼管の表面をリン酸塩、クロム酸塩等で化成処
理した上に変性ポリエチレンを被覆する事により耐久接
着性を改良する工夫がなされており、また、水素よりイ
オン化度が大の金属粉末(特公昭58−13585号公
報)、リン酸塩(特公昭54−18−297号公報)、
金属のハロゲン含有化合物(特公昭53−2448、同
60−2330号公報)、防錆顔料(特開昭59−21
9354号公報)、含水複塩(71!開昭60−115
38号公報)のほか金属酸化物、水酸化物、炭酸塩等各
種の無機化合物を変性ポリエチレンに添加して耐塩水性
を改良する工夫が行われている。(Problem to be solved by the invention) However, since modified polyethylene has low durable adhesive properties, the surface of the steel pipe is usually chemically treated with phosphate, chromate, etc., and then coated with modified polyethylene to provide durable adhesive. Efforts have been made to improve the properties of metal powders, which have a higher degree of ionization than hydrogen (Japanese Patent Publication No. 13585/1985), phosphates (Japanese Patent Publication No. 18/297/1987),
Metal halogen-containing compounds (Japanese Patent Publication Nos. 53-2448 and 60-2330), anti-rust pigments (Japanese Patent Publication No. 59-21
Publication No. 9354), hydrated double salt (71! Kaisho 60-115
Efforts have been made to improve salt water resistance by adding various inorganic compounds such as metal oxides, hydroxides, and carbonates to modified polyethylene.
しかし、これらのものでは特に厳しい耐陰極剥離性を満
足するものではなく、また、クロム酸塩処理液の排水処
理の問題がある。However, these products do not satisfy particularly strict cathode peeling resistance, and there is also a problem in wastewater treatment of the chromate treatment solution.
一方、特に厳しい耐陰極剥離性については、通常、エポ
キシ樹脂をプライマーとして用い、変性ポリエチレンを
その上に被覆する事により改良する工夫がなされている
。On the other hand, particularly severe cathodic peeling resistance is usually improved by using an epoxy resin as a primer and coating it with modified polyethylene.
しかし、エポキシ樹脂を塗布して硬化させた漫に、変性
ポリエチレンを被覆する工程が繁雑で高価であり、新た
な簡易な手法の開発が望まれている。However, the process of coating modified polyethylene on the epoxy resin that has been applied and cured is complicated and expensive, and there is a need for the development of a new and simpler method.
(問題点を解決するだめの手段)
本発明は、接着性が良好で、かつ、耐久接着性、特に耐
陰極剥離性の良好な金属表面への積層用樹脂を得ること
を目的にして、特定の変性ポリオレフィン組成物と塩化
カルシウムの定量からなる組成物がこの目的を達成する
ことを見い出して為された。(Another Means to Solve the Problems) The present invention aims to obtain a resin for lamination on metal surfaces that has good adhesion and durable adhesion, especially cathodic peeling resistance. It has been discovered that a composition consisting of a modified polyolefin composition of 1 and a quantity of calcium chloride achieves this objective.
即ち、本発明は、「下記の(Aまたは■の変性ポリオレ
フィン組成物100重量部とヒドラジン誘導体0.01
〜10重量部から実質的になる組成物を、金属の表直に
溶融状態で積層したことを特徴とする樹脂積層体
■ 不飽和カルボン酸又はその無水物を0.1〜10重
量大グラフトさせた変性高密度ポリエチレン0.1〜5
0重量部および密度0.945 f/ad以下の結晶性
エチレン−αオレフイン共重合体99.9〜50重量部
からなる変性ポリエチレン組成物(B)不飽和カルボン
酸又はその無水物を0.1〜10重t%グラフトさせた
変性結晶性プロピレン系重合体0.1〜50重量部およ
びエチレン含t3〜50重量%の結晶性プロピレン−エ
チレン共重合体99.9〜50重量部からなる変性ポリ
プロピレン組成物」である。。That is, the present invention provides ``100 parts by weight of the following modified polyolefin composition (A or
A resin laminate characterized in that a composition consisting essentially of ~10 parts by weight is laminated on the surface of metal in a molten state. modified high-density polyethylene 0.1-5
Modified polyethylene composition (B) consisting of 99.9 to 50 parts by weight of a crystalline ethylene-α olefin copolymer having a density of 0.945 f/ad or less and a density of 0.945 f/ad or less. A modified polypropylene consisting of 0.1 to 50 parts by weight of a modified crystalline propylene polymer grafted with ~10% by weight and 99.9 to 50 parts by weight of a crystalline propylene-ethylene copolymer containing 3 to 50% by weight of ethylene. composition”. .
(作用)
本発明で用いられる変性ポリオレフィン組成物は、上記
の(A)またはCB)のものである。(Function) The modified polyolefin composition used in the present invention is the one described in (A) or CB) above.
この囚、(B)を製造するのに用いる不飽和カルボン酸
又はその無水物としては、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、シトラコン酸、ク
ロトン酸、無水マレイン酸、無水イタコン酸、無水シト
ラコン酸等が挙げられるが、中でも無水マレイン酸が最
も好ましい。The unsaturated carboxylic acid or its anhydride used to produce this compound (B) includes acrylic acid, methacrylic acid,
Examples include maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and among them, maleic anhydride is most preferred.
グラフトに用いられる高密度ポリエチレンとしては、密
度が0.946 f/ad以上、好ましくは0.950
〜0.960 f/cdのエチレン系重合体であり、エ
チレンの単独型合本の外、プロピレン、ブテン、ヘキセ
ン等少量、例えば10モル%以下のα−オレフィンを含
む共重合体が該当する。The high density polyethylene used for grafting has a density of 0.946 f/ad or more, preferably 0.950
-0.960 f/cd is an ethylene-based polymer, and in addition to a single type combination of ethylene, copolymers containing a small amount of α-olefin such as propylene, butene, hexene, etc., for example, 10 mol % or less are applicable.
もう一方の、グラフトに用いられる結晶性プロピレン系
重合体としては、プロピレン単独型合本の外、エチレン
、ブテン、ヘキセン等少量、例えば30モル%以下のα
−オレフィンを含む共重合体が該当する。On the other hand, as the crystalline propylene polymer used for grafting, in addition to propylene single type combinations, small amounts such as ethylene, butene, hexene, etc., for example, 30 mol% or less α
-Copolymers containing olefins are applicable.
グラフトサせる方法は、これらの成分をパーオキサイド
若しくはアゾ化合物等のラジカル発生剤の存在下ないし
は不要であれば不存在下に溶融グラフトまたは溶液グラ
フト等通常の手法で行なわれる。The grafting method is carried out by a conventional method such as melt grafting or solution grafting of these components in the presence of a radical generator such as a peroxide or an azo compound, or in the absence if unnecessary.
得られる変性高密度ポリエチレンと変性結晶性プロピレ
ン系重合体に含有される不飽和カルボン酸又はその無水
物の含量は、0.1〜10重量%、好ましくは1〜8重
量%である。この範囲より少ないと金属に対する接着性
が劣り、この範囲より多いとゲルが多くなうたり、変性
時に結晶性プロピレン系重合体の分子量が大幅に低下し
、物性や接着性が低下して好ましくない。The content of the unsaturated carboxylic acid or its anhydride contained in the resulting modified high-density polyethylene and modified crystalline propylene polymer is 0.1 to 10% by weight, preferably 1 to 8% by weight. If it is less than this range, the adhesion to metal will be poor, and if it is more than this range, there will be a lot of gel, and the molecular weight of the crystalline propylene polymer will decrease significantly during modification, resulting in a decrease in physical properties and adhesiveness, which is undesirable. .
かかる変性ポリオレフィンは市販のものから適宜選択使
用できる。Such modified polyolefins can be appropriately selected from commercially available ones.
次に、グラフトされた変性高密度ポリエチレンや変性結
晶性プロピレン系重合体とブレンドするのに用いる結晶
性エチレン−αオレフィン共重合体および結晶性プロピ
レン−エチレン共重合体は次のものである。Next, the crystalline ethylene-α olefin copolymer and crystalline propylene-ethylene copolymer used for blending with the grafted modified high-density polyethylene and modified crystalline propylene polymer are as follows.
即ち、結晶性エチレン−αオレフィン共重合体としては
、密度が0.94 s t /j以下、好ましくは0.
910〜0.930 f/cdのエチレンとブテン、ヘ
キセン、オクテン、4−メチルペンテン−1等α−オレ
フィンとの共重合体である。密度が上記より大きいもの
は、積層体の低温耐衝撃性、耐久接着性等が劣るので好
ましくない。That is, the crystalline ethylene-α olefin copolymer has a density of 0.94 s t /j or less, preferably 0.94 s t /j or less.
It is a copolymer of 910 to 0.930 f/cd of ethylene and α-olefin such as butene, hexene, octene, 4-methylpentene-1, etc. If the density is higher than the above, the laminate will have poor low-temperature impact resistance, durable adhesion, etc., and is therefore not preferred.
また、結晶性プロピレン−エチレン共重合体としては、
エチレン含量3〜50重量%、好ましくは5〜45重量
%、特に好ましくは10〜40重量%のプロピレン系共
重合体であ抄、少量、例えば5モル%以下のブテン等地
のαオレフィンを共重合したものも含む。エチレン含量
が上記未満では積層体の低温耐衝撃性、耐久接着性等が
劣ることとなり、一方上記超過では積層体の耐熱接着性
、上に被覆される結晶性プロピレン系重合体との接着性
が劣るので好ましくない。In addition, as a crystalline propylene-ethylene copolymer,
A propylene copolymer with an ethylene content of 3 to 50% by weight, preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight is prepared, and a small amount, for example, 5 mol% or less of an α-olefin such as butene, is co-polymerized. Including polymerized products. If the ethylene content is less than the above, the low-temperature impact resistance and durable adhesion of the laminate will be poor, while if it exceeds the above, the heat-resistant adhesion of the laminate and the adhesion to the crystalline propylene polymer coated on top will be poor. I don't like it because it's inferior.
これらの変性樹脂と未変性樹脂の配合割合は次の通りで
ある。The blending ratios of these modified resins and unmodified resins are as follows.
即ち、変性高密度ポリエチレンと結晶性エチレン−αオ
レフィン共重合体の割合は、前者0.1〜50重量部お
よび後者99.9〜50重量部、好ましくは前者1〜3
0重着部および後者99〜70重量部である。前者がこ
の範囲より少ないと金属との接着性が劣り、一方、この
範囲を超えると物性および耐久接着性に劣り好ましくな
い。That is, the proportions of the modified high-density polyethylene and the crystalline ethylene-α olefin copolymer are 0.1 to 50 parts by weight for the former and 99.9 to 50 parts by weight for the latter, preferably 1 to 3 parts by weight for the former.
The latter is 99 to 70 parts by weight. If the former is less than this range, the adhesion to metals will be poor, while if it exceeds this range, the physical properties and durable adhesiveness will be poor, which is not preferred.
また、変性ポリプロピレンと結晶性プaピレン−エチレ
ン共重合体の割合としては、前者0.1〜50重量部お
よび後者99.9〜50重量部、好ましくは前者1〜3
0重量部および後者99〜70重量部である。前者がこ
の範囲より少ないと金属に対する接着性が劣り、この範
囲より多いと、物性および耐久接着性に劣るので好まし
くない。The ratio of the modified polypropylene to the crystalline polypropylene-ethylene copolymer is 0.1 to 50 parts by weight for the former and 99.9 to 50 parts by weight for the latter, preferably 1 to 3 parts by weight for the former.
0 parts by weight and 99 to 70 parts by weight of the latter. If the former is less than this range, the adhesiveness to metals will be poor, and if it is more than this range, the physical properties and durable adhesiveness will be poor, which is not preferable.
また、本発明で用いるヒドラジン誘、導体は、ヒドラジ
ン、ヒドラゾン、酸ヒドラジドの炭化水素基置換体であ
り、例えば、N−サリチロイル−N′−サリチリデンヒ
ドラジド、シュウ酸ビスベンジリデンヒドラジド、N、
N’−ビス(3−(3,5−ジ−t−7’チル−4−ヒ
ドロキシフェニル)プロピオニル〕ヒドラジド、−N、
N’−ビス(3,5−ジ−t−7’チル−4−ヒドロキ
シシンナモイル)ヒドラジン、シュウ酸ビス(シクロへ
キシリデンヒドラジド)等、ポリオレフィンの金属害防
止剤の中から適宜選んで用いることができる。Further, the hydrazine derivatives and conductors used in the present invention are hydrocarbon group-substituted products of hydrazine, hydrazone, and acid hydrazide, such as N-salicyloyl-N'-salicylidene hydrazide, bisbenzylidene oxalate hydrazide, N,
N'-bis(3-(3,5-di-t-7'thyl-4-hydroxyphenyl)propionyl)hydrazide, -N,
N'-bis(3,5-di-t-7'thyl-4-hydroxycinnamoyl)hydrazine, bis(cyclohexylidene hydrazide) oxalate, and other metal damage inhibitors for polyolefins, appropriately selected and used. be able to.
ヒドラジン誘導体の添加量は、前記(ロ)または(B)
の変性ポリオレフィン組成物100重量部に対して0.
01〜10重量部、好ましくは0.1〜5重量部、特に
好ましくは1〜5重量部である。この範囲よ9少ないと
耐陰極剥離性と接着性の改良効果が少なく、この範囲よ
り多いと変性ポリオレフィン組成物に対する分散性が悪
く、かつ、変性ポリオレフィン組成物の接着性低下が著
しくなるため好ましくない。The amount of the hydrazine derivative to be added is as specified in (B) or (B) above.
0.00% per 100 parts by weight of the modified polyolefin composition.
01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably 1 to 5 parts by weight. If it is less than this range by 9, the effect of improving cathodic peeling resistance and adhesion will be small, and if it is more than this range, the dispersibility for the modified polyolefin composition will be poor and the adhesiveness of the modified polyolefin composition will be significantly reduced, which is not preferable. .
本発明で用いる組成物は、上記の通り、変性ポリオレフ
ィン組成物とヒドラジン誘導体の各所定量から本質的に
成るものであり、ここで「本質的」とは、他の成分を少
量、例えば、30重量%以下の範囲で含むものも該当す
るという意味であり、他の成分としては、本発明で用い
る以外のαオレフイン系樹脂、αオレフイン系やスチレ
ン−ブタジェン系ゴム、安定剤、無機または有機の充填
剤等が挙げられる。As mentioned above, the composition used in the present invention consists essentially of a modified polyolefin composition and a predetermined amount of a hydrazine derivative, and "essentially" means a small amount of other components, for example, 30% by weight. % or less, and other components include α-olefin resins other than those used in the present invention, α-olefin and styrene-butadiene rubbers, stabilizers, and inorganic or organic fillers. agents, etc.
本発明の積層体は、上記の樹脂組成物を金属の表面に溶
融状態で積層したことを特徴とするものであるので、2
層のもののほかに、上記樹脂組成物の上にさらに他の樹
脂や金属、布等を積層したものでおつてもよい。The laminate of the present invention is characterized by laminating the above-mentioned resin composition on the surface of metal in a molten state.
In addition to the layer, the resin composition may be further laminated with other resins, metals, cloth, etc.
中でも、防錆、耐久性等の点で上記樹脂組成物の上に他
の樹脂を積層した3層以上の積層体が実用的に好ましい
。その際、変性ポリエチレン組成物の上には結晶性エチ
レン系重合体を、また、変性ポリプロピレン組成物の上
には結晶性グロビレン系重合体を積層するが、それぞれ
、変性樹脂組成物層よりも密度の高い樹脂を積層する方
が接着性および耐陰極剥離性が優れていて好まし50層
の厚みは、変性樹脂組成物層0.1〜0.5 mおよび
その上の結晶性ポリオレフィン層は1〜5鱈とするのが
成形性、耐久性の点で実用的である。Among these, from the viewpoint of rust prevention, durability, etc., a laminate of three or more layers in which the above resin composition is laminated with another resin is practically preferable. At that time, a crystalline ethylene polymer is laminated on top of the modified polyethylene composition, and a crystalline globylene polymer is laminated on top of the modified polypropylene composition, but each layer has a higher density than the modified resin composition layer. The thickness of the 50 layers is preferably 0.1 to 0.5 m for the modified resin composition layer and 1 m for the crystalline polyolefin layer on top of the layer, since the adhesiveness and cathodic peeling resistance are better when laminated with resins having a high ~5 cod is practical in terms of moldability and durability.
この変性樹脂組成物層の上に積層されるのに用いられる
結晶性エチレン系重合体としては、密度0.920〜0
.9soy/d、好ましくは0.930〜0.95o
y /−のエチレン単独重合体またはエチレンとブテン
、ヘキセン、オクテン、4−メチル−ペンテン−1等の
αオレフィンや酢酸ヒニルとの共重合体であり、そのM
FRは、好ましくは29/10分以下、特に好ましくは
o、sr/l。The crystalline ethylene polymer used to be laminated on this modified resin composition layer has a density of 0.920 to 0.
.. 9 soy/d, preferably 0.930-0.95o
y/- ethylene homopolymer or a copolymer of ethylene with α-olefin such as butene, hexene, octene, 4-methyl-pentene-1, or hinyl acetate, and its M
FR is preferably 29/10 minutes or less, particularly preferably o, sr/l.
分取下のものである。これにはカーボンブラック等の顔
料や安定剤・帯電防止剤等各種添加剤を配合したもので
もよい。It is under preparative separation. This may contain pigments such as carbon black, and various additives such as stabilizers and antistatic agents.
一方、上記変性樹脂組成物層の上に積層されるのに用い
られる結晶性プロピレン系重合体としては、プロピレン
−エチレン共重合体が好ましく、特にブロック共重合体
が好ましい。エチレン含量は0.5〜35重量%が好ま
しく、特に2〜25重t%が好ましい。また、MFRは
、好ましくは2f/10分以下、特に好ましくはo、s
r/lo分以下のものでおり、カーボンブラック等の顔
料や安定剤・帯電防止剤等各種添加剤をブレンドしたも
のでもよい。On the other hand, the crystalline propylene polymer used to be laminated on the modified resin composition layer is preferably a propylene-ethylene copolymer, particularly a block copolymer. The ethylene content is preferably 0.5 to 35% by weight, particularly preferably 2 to 25% by weight. Further, the MFR is preferably 2 f/10 min or less, particularly preferably o, s
r/lo or less, and may be a blend of pigments such as carbon black and various additives such as stabilizers and antistatic agents.
本発明で用いる金属としては、鋼、アルミニウム等各種
用いられるが、特に鋼管が好ましい。ブラスト処理また
はリン酸塩、クロム酸塩等の各種化成処理等も本発明の
耐陰極剥離性を更に向上させるので好ましい。Various metals such as steel and aluminum can be used as the metal used in the present invention, and steel pipes are particularly preferred. Blasting or various chemical conversion treatments such as phosphate and chromate are also preferred since they further improve the cathode peeling resistance of the present invention.
本発明の積1体は、金属の表面をブラスト処理、酸洗等
で表面洗浄した後、必要ちれば、リン酸塩、クロム酸塩
等の化成処理を施し、上記の変性ポリオレフィン組成物
と塩化カルシウムとからなる組成物を押出被覆、粉本塗
装、圧縮成形等公知の手法を用いて溶融状態で金属の表
面に積1−する事で得られる。The product of the present invention is prepared by cleaning the metal surface by blasting, pickling, etc., and then, if necessary, performing a chemical conversion treatment with phosphate, chromate, etc., and then forming the above modified polyolefin composition. It can be obtained by depositing a composition consisting of calcium chloride on the surface of a metal in a molten state using known techniques such as extrusion coating, powder coating, compression molding, etc.
(発明の効果)
本発明に依れば、リン酸塩、クロム酸塩等の化成処理を
施す事なく、また、現在耐陽極剥離性を改良する為に用
いられているエボキシグライマー等を施すことなく、耐
陰極剥離性と接着性に優れた積層体が得られる。(Effects of the Invention) According to the present invention, chemical conversion treatments such as phosphate and chromate are not required, and epoxy glitter, which is currently used to improve anodic peeling resistance, can be applied. A laminate with excellent cathode peeling resistance and adhesiveness can be obtained without any problems.
(実施例)
実施ガニ
無水マレイン酸変性高密度ポリエチレン(無水マレイン
酸含t1重量%、密度0.95 Q f/ad )20
重量部、エチレン−ブテン−1共重合体(MFRo、8
f/1G分、密度0.920 r/m) 80重量部に
、ヒドラジン誘導体を種々の割合でブレンドしたのち2
00℃の押出機で混練して組成物を得た。(Example) Example: Maleic anhydride-modified high-density polyethylene (maleic anhydride content t1% by weight, density 0.95 Q f/ad) 20
Parts by weight, ethylene-butene-1 copolymer (MFRo, 8
After blending 80 parts by weight of hydrazine derivatives in various proportions,
A composition was obtained by kneading in an extruder at 00°C.
この組成物と高密度ポリエチレン(MFRo、2?/l
O分、密度0.950 r/cd)とを200℃に設定
された共押出ダイスに供給し、160℃に予熱された2
0A鋼管(サンドブラスト処理)上に被覆し、鋼−W/
変性ポリエチレン組成物(0,4m)/高密度ポリエチ
レン(2,1m)の樹脂被覆鋼管を得た。This composition and high density polyethylene (MFRo, 2?/l)
O content, density 0.950 r/cd) was supplied to a coextrusion die set at 200°C, and 2
Coated on 0A steel pipe (sandblasting), steel-W/
A resin-coated steel pipe of modified polyethylene composition (0.4 m)/high density polyethylene (2.1 m) was obtained.
この樹脂被覆鋼管を用い、ASTM G−8により耐
陰極剥離性(1力月後の穴部よりの剥離距離)と、DI
N30670により接着強度(試験速度10m7分)を
測定した結果を第1表に示す。Using this resin-coated steel pipe, we tested the cathode peeling resistance (peeling distance from the hole after 1 month) and DI according to ASTM G-8.
Table 1 shows the results of measuring the adhesive strength (test speed: 10 m, 7 minutes) using N30670.
比較例1
実施例1で用いた変性ポリエチレン組成物においてヒド
ラジン誘導体を配合しない組成物を用い、一方、リン酸
塩処理およびクロム酸塩処理した20人鋼管をそれぞれ
用いる外は実施例1と同様にして樹脂被覆鋼管を得、測
定した結果を第1表に示す。Comparative Example 1 The procedure was the same as in Example 1, except that the modified polyethylene composition used in Example 1 did not contain a hydrazine derivative, and on the other hand, phosphate-treated and chromate-treated 20-man steel pipes were used. A resin-coated steel pipe was obtained, and the measurement results are shown in Table 1.
実施列2
無水マレイン酸変性ポリプロピレン(無水マレイン酸含
J15重1%、密度0.90 f/cd) 5重量部、
フロピレン−エチレンブロック共、! 合体(x−テレ
ン含量27重i%、MF R0,3f710分、密度0
.89 f/l:d ) 95重量部およびヒドラジン
誘導体5重量部の割合でブレンドし、230℃の押出機
で混練し組成物を得た。Example row 2 Maleic anhydride-modified polypropylene (containing maleic anhydride J15 1% by weight, density 0.90 f/cd) 5 parts by weight,
Flopylene-ethylene block together! Coalescence (x-terene content 27wt%, MF R0,3f710min, density 0
.. 89 f/l:d) and 5 parts by weight of the hydrazine derivative were blended and kneaded in an extruder at 230°C to obtain a composition.
この組成物とプロピレン−エチレンブロック共重合体(
エチレン含量10重量%、MFRt y710分、密度
0.90f/j)とを230℃に設定された共押出ダイ
スに供給し、180℃に予熱された20A′44管(サ
ンドブラスト処理)上に被覆し、鋼管/変性ポリプロピ
レン組成物(0,4m)/プロピレンーエチレンブロッ
ク共重合体(2,1m)の樹脂被覆鋼管を得九。評価結
果を第1表に示す。This composition and propylene-ethylene block copolymer (
Ethylene content 10% by weight, MFRt y 710 min, density 0.90 f/j) was fed into a coextrusion die set at 230°C and coated onto a 20A'44 tube (sandblasting) preheated to 180°C. A resin-coated steel pipe of steel pipe/modified polypropylene composition (0.4 m)/propylene-ethylene block copolymer (2.1 m) was obtained. The evaluation results are shown in Table 1.
比較例2
実施例2で用いた変性ポリプロピレン組成物においてヒ
ドラジン誘導体を配合しない組成物を用いる外は実施例
2と同様にして測定した結果を第1表に示す。Comparative Example 2 Table 1 shows the results of measurements carried out in the same manner as in Example 2, except that the modified polypropylene composition used in Example 2 did not contain a hydrazine derivative.
(以下余白)(Margin below)
Claims (1)
100重量部とヒドラジン誘導体0.01〜10重量部
から実質的になる組成物を、金属の表面に溶融状態で積
層したことを特徴とする樹脂積層体。 (A)不飽和カルボン酸又はその無水物を0.1〜10
重量%グラフトさせた変性高密度ポリエチレン0.1〜
50重量部および密度0.945g/cm^3以下の結
晶性エチレン−αオレフィン共重合体99.9〜50重
量部からなる変性ポリエチレン組成物 (B)不飽和カルボン酸又はその無水物を0.1〜10
重量%グラフトさせた変性結晶性プロピレン系重合体0
.1〜50重量部およびエチレン含量3〜50重量%の
結晶性プロピレン−エチレン共重合体99.9〜50重
量部からなる変性ポリプロピレン組成物[Claims] A composition consisting essentially of 100 parts by weight of the following modified polyolefin composition (A) or (B) and 0.01 to 10 parts by weight of a hydrazine derivative is laminated in a molten state on the surface of a metal. A resin laminate characterized by: (A) unsaturated carboxylic acid or its anhydride from 0.1 to 10
Weight% grafted modified high-density polyethylene 0.1~
Modified polyethylene composition (B) consisting of 50 parts by weight and 99.9 to 50 parts by weight of a crystalline ethylene-α-olefin copolymer having a density of 0.945 g/cm^3 or less. 1-10
Weight% grafted modified crystalline propylene polymer 0
.. A modified polypropylene composition consisting of 1 to 50 parts by weight and 99.9 to 50 parts by weight of a crystalline propylene-ethylene copolymer with an ethylene content of 3 to 50% by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6332885A JPS61252150A (en) | 1985-03-29 | 1985-03-29 | Resin laminate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6332885A JPS61252150A (en) | 1985-03-29 | 1985-03-29 | Resin laminate |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS61252150A true JPS61252150A (en) | 1986-11-10 |
Family
ID=13226072
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6332885A Pending JPS61252150A (en) | 1985-03-29 | 1985-03-29 | Resin laminate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61252150A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02232286A (en) * | 1989-03-03 | 1990-09-14 | Sekisui Chem Co Ltd | Adhesive composition |
JPH0892427A (en) * | 1994-09-27 | 1996-04-09 | Nippon Paper Ind Co Ltd | Water-based resin composition |
JP2010001340A (en) * | 2008-06-19 | 2010-01-07 | Tosoh Corp | Polyarylene sulfide composition |
-
1985
- 1985-03-29 JP JP6332885A patent/JPS61252150A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02232286A (en) * | 1989-03-03 | 1990-09-14 | Sekisui Chem Co Ltd | Adhesive composition |
JPH0892427A (en) * | 1994-09-27 | 1996-04-09 | Nippon Paper Ind Co Ltd | Water-based resin composition |
JP2010001340A (en) * | 2008-06-19 | 2010-01-07 | Tosoh Corp | Polyarylene sulfide composition |
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