JPS6114272A - Bondable polyethylene composition and metal laminate thereof - Google Patents
Bondable polyethylene composition and metal laminate thereofInfo
- Publication number
- JPS6114272A JPS6114272A JP13289884A JP13289884A JPS6114272A JP S6114272 A JPS6114272 A JP S6114272A JP 13289884 A JP13289884 A JP 13289884A JP 13289884 A JP13289884 A JP 13289884A JP S6114272 A JPS6114272 A JP S6114272A
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- Prior art keywords
- polyethylene
- metal
- adhesive
- weight
- polyethylene composition
- Prior art date
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Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、接着性が特に優れ、低温でも接着可能であシ
耐熱水性、耐塩水性にも優れた接着性ポリエチレン組成
物、及びこの接着性ポリエチレン組成物゛を金属の少な
くとも一面に積層してなる金属積層体に・関す暮。Detailed Description of the Invention [Field of Industrial Application] The present invention provides an adhesive polyethylene composition that has particularly excellent adhesive properties, can be bonded even at low temperatures, and has excellent hot water resistance and salt water resistance, and the adhesive polyethylene composition that has excellent adhesive properties. A life related to a metal laminate formed by laminating a polyethylene composition on at least one surface of metal.
従来、金属の耐食性、外観２食品衛生上の改善のために
金属管（例えば鋼管）の内外面、金属板。Traditionally, metal plates have been used on the inner and outer surfaces of metal pipes (such as steel pipes) and metal plates to improve corrosion resistance and appearance of metals and food hygiene.
電線、ケーブル等に中低工法高密度ポリエチレン又は高
圧法低密度ポリエチレンを不飽和カルボン酸類でグラフ
トした変性ポリエチレンで積層（接着）することが知ら
れている。It is known that electric wires, cables, etc. are laminated (adhered) with modified polyethylene obtained by grafting medium-low construction method high-density polyethylene or high-pressure method low-density polyethylene with unsaturated carboxylic acids.
しかしながら、従来の中低圧法・及び高圧法ポリエチレ
ンをグラフト変性した変性ポリエチレンは鋼、鉄、アル
ミニウム等の金属に対する接着性が十分ではない。However, modified polyethylene obtained by graft-modifying conventional medium-low-pressure polyethylene and high-pressure polyethylene does not have sufficient adhesion to metals such as steel, iron, and aluminum.
そこで、前記金属に積層（接着）する変性ポリエチレン
として、線状低密度ポリエチレンに不飽和カルボン酸類
をグラフトした変性ポリエチレンが提案された。Therefore, a modified polyethylene in which unsaturated carboxylic acids are grafted onto linear low density polyethylene has been proposed as a modified polyethylene to be laminated (adhered) to the metal.
しかし、前記弯性ポリエチレンも、金属に積層（接着）
した金属積層体の接着強度が小さく、耐熱水性、耐塩水
性が不十分であシ、特にラップシース用、土木建築用や
自動車用などの強い接着力はもちろんのこと耐久性も要
求される分野には使用することができないという欠点を
有している。However, the curved polyethylene is also laminated (adhered) to metal.
The adhesive strength of the metal laminate is low, and the hot water resistance and salt water resistance are insufficient, especially for fields that require not only strong adhesive strength but also durability, such as wrap sheaths, civil engineering construction, and automobiles. has the disadvantage that it cannot be used.
そこで２本発明者らは、金属との接着強度が大きく、耐
熱（温）水性、耐塩水性にも優れた接着性ポリエチレン
組成物、及びこのような接着性ポリエチレン組成物を金
属の少なくとも一面に積層してなる金属積層体を提供す
ることを目的として鋭意研究した結果９本発明を完成し
た。Therefore, the present inventors developed an adhesive polyethylene composition that has high adhesive strength with metal and excellent heat (warm) water resistance and salt water resistance, and a method for laminating such adhesive polyethylene composition on at least one surface of metal. The present invention was completed as a result of intensive research aimed at providing a metal laminate consisting of:
すなわち１本発明は、エチレンとα−オレフィンとの共
重合体であってメルトインデックスが０．０５〜２０９
／１０分１重量平均分子量／数平均分子量が２〜１０で
ある線状低密度ポリエチレンに不飽和カルボン酸類をグ
ラフトした変性ポリエチレンとスチレン系ポリマーとを
混合してなる接着性ポリエチレン組成物、及びエチレン
とα−オレフィンとの共重合体であってメルトインデッ
クスが０．０５〜２０９／１０分２重量平均分子Ｖ数平
均分子量が２〜１０である線状低密度ポリエチレンに不
飽和カルボン酸類をグラフトした変性ポリエチレンとス
チレン系ポリマーとを混合してなる接着性ポリエチレン
組成物を金属の少なくとも一面に積層してなる金属積層
体に関する。That is, 1 the present invention is a copolymer of ethylene and α-olefin, which has a melt index of 0.05 to 209.
/10 minutes1 Weight average molecular weight/An adhesive polyethylene composition prepared by mixing a modified polyethylene obtained by grafting unsaturated carboxylic acids with a linear low density polyethylene having a number average molecular weight of 2 to 10 and a styrene polymer, and ethylene. unsaturated carboxylic acids were grafted onto linear low-density polyethylene, which is a copolymer of polyethylene and α-olefin and has a melt index of 0.05 to 209/10 min2 and a weight average molecular V number average molecular weight of 2 to 10. The present invention relates to a metal laminate in which an adhesive polyethylene composition made by mixing modified polyethylene and a styrene polymer is laminated on at least one surface of metal.
本発明においては変性ポリオレフィンとして。In the present invention, as a modified polyolefin.
エチレンとα−オレフィン（ブテン−１，ヘキセン−１
，４−／ｌチルペンテンー１１オクテンー１）との共重
合体であってメルトインデックスが０．０５〜２０９／
１０分、好ましくは０．５〜１５グ／１０分９重量平均
分子量／数平均分子量（以下単にＭ ｗ ／ Ｍ Ｎと
略記することもある）が２〜１０゜好ましくは３〜５．
好ましくは融点が１１０〜 、。Ethylene and α-olefins (butene-1, hexene-1
, 4-/l chillpentene-11 octene-1) with a melt index of 0.05 to 209/l.
10 minutes, preferably 0.5 to 15 g/10 minutes9 Weight average molecular weight/number average molecular weight (hereinafter simply abbreviated as Mw/MN) is 2 to 10 degrees, preferably 3 to 5.
Preferably, the melting point is 110~.
１３０°Ｃであシ、密度が０．９１５°〜ｏ、ｑ３５ｙ
ｉ−であシ、α−オレフィン含量が３〜１７重量％であ
る線状低密度ポリエチレンに不飽和カルボン酸類をグラ
フトした変性ポリエチレンを使用することが必要である
。前記限定の範囲外の変性ポリエチレンを使用すると、
金属との接着強度が大きく、耐熱水性、耐塩水性に優れ
た接着性ポリエチレン組成物を得ることができない。前
記変性ポリエチレンはその一部を、好ましくはその９５
重量％以下、特に好ましくは９０重量−以下を未変性の
前記線状低密度ポリエチレンで置きかえたものであって
もよい。前記変性ポリエチレン（または変性ポリエチレ
ンの一部を未変性ポリエチレンで置きかえた変性ポリエ
チレン）は、メルトインデックスが０．５〜１５ｆ／１
０分であシ、不飽和カルボン酸類を１２当＃）１×１０
〜１×１０ モル含有するものが好ましい。130°C, density 0.915°~o, q35y
It is necessary to use a modified polyethylene obtained by grafting unsaturated carboxylic acids onto linear low-density polyethylene having an i-acrylic acid or α-olefin content of 3 to 17% by weight. If modified polyethylene outside the range of the above limitations is used,
It is not possible to obtain an adhesive polyethylene composition that has high adhesive strength to metal and excellent hot water resistance and salt water resistance. A part of the modified polyethylene is preferably 95% of the modified polyethylene.
Less than 90% by weight, particularly preferably 90% by weight or less, may be replaced by the unmodified linear low-density polyethylene. The modified polyethylene (or modified polyethylene in which a part of the modified polyethylene is replaced with unmodified polyethylene) has a melt index of 0.5 to 15 f/1.
0 minutes, unsaturated carboxylic acids 12 times) 1
Preferably, the content is 1×10 mol.
前記変性ポリエチレンは、前記線状低密度ポリエチレン
と不飽和カルボン酸類と有機過酸化物とをそれ自体公知
の方法によって過熱下に接触させることによって得るこ
とができる。例えば、前記線状低密度ポリエチレンと不
飽和カルボン酸類と有機過酸化物とを線状低密度ポリエ
チレンの融点以上で溶融混合するか、有機溶媒中で前記
各成分を混合することによって線状低密度ポリエチレン
に不飽和カルボン酸類をグラフトして変性ポリエチレン
を得ることができる。The modified polyethylene can be obtained by bringing the linear low-density polyethylene, an unsaturated carboxylic acid, and an organic peroxide into contact with each other under heating by a method known per se. For example, by melt-mixing the linear low-density polyethylene, unsaturated carboxylic acids, and organic peroxide at a temperature higher than the melting point of the linear low-density polyethylene, or by mixing each of the components in an organic solvent, Modified polyethylene can be obtained by grafting unsaturated carboxylic acids onto polyethylene.
前記不飽和カルボン酸類としては、無水マレイン酸、無
水イタコン酸、無水シトラコン酸、エンド−ビシクロ−
（２，２，１） −１，４，５，６，７，７−へキサク
ロロ−５−へブテン−２，６無水ジカルボン酸。Examples of the unsaturated carboxylic acids include maleic anhydride, itaconic anhydride, citraconic anhydride, endo-bicyclo-
(2,2,1)-1,4,5,6,7,7-hexachloro-5-hebutene-2,6 dicarboxylic anhydride.
シス−４−シクロヘキセン−１，２無水ジカルボン酸等
のα、β−不飽和カルボン、その無水物およびそのモノ
エステルがあげられる。また、前記有機過酸化物として
は２例えば、ｔ−ブチルハイドロパーオキサイド、ラウ
ロイルパーオキサイド、ｔ−ブチルパーオキシラウレー
ト、シクロヘキサノンパーオキサイド、２，５−ジメチ
ル−２，５−ジ（ペンソイルノ１々−オキシ）ヘキサン
、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオ
キシベンゾエート、メチルエチルケトンパーオキサイド
。Examples thereof include α,β-unsaturated carbons such as cis-4-cyclohexene-1,2 dicarboxylic anhydride, anhydrides thereof, and monoesters thereof. In addition, examples of the organic peroxides include t-butyl hydroperoxide, lauroyl peroxide, t-butyl peroxylaurate, cyclohexanone peroxide, 2,5-dimethyl-2,5-di(pensoylno-1) -oxy)hexane, t-butyl peroxyacetate, t-butyl peroxybenzoate, methyl ethyl ketone peroxide.
ジクミルパーオキサイド、ｔ−プチルクミルバーオキサ
イド等があげられる。Examples include dicumyl peroxide and t-butylcumyl peroxide.
本発明の接着性ポリエチレン組成物は、前記変性ポリエ
チレンとスチレン系ポリマーとを混合することによって
得られる。The adhesive polyethylene composition of the present invention is obtained by mixing the modified polyethylene and a styrenic polymer.
前記スチレン系ポリマーとしては、ポリスチレン、スチ
レン−ブタジェン共重合体、エチレン−スチレン共電“
合体、スチレンと化合物中に不飽和炭化水素とパーオキ
サイドの基を有するモノマーとの共重合体、スチレン−
酢酸ビニル共重合体。Examples of the styrene polymer include polystyrene, styrene-butadiene copolymer, and ethylene-styrene copolymer.
Copolymer of styrene and a monomer having unsaturated hydrocarbon and peroxide groups in the compound, styrene-
Vinyl acetate copolymer.
スチレンとビニルモノマー（側えばメタクリル酸メチル
、）との共重合体、ポリスチレンにエラストマーをブレ
ンドしたもの等が挙げられる。な誉。Examples include copolymers of styrene and vinyl monomers (such as methyl methacrylate), and blends of polystyrene with elastomers. Honor.
エラストマーは変性ポリエチレンとスチレン系ポリマー
との混合時に加えてもよい。前記スチレン系ポリ′マー
の量は、前記変性ポリエチレン１００重量部に対して１
〜１００重量部が好ましい。また前記ニジストマーとし
ては、ポリイソブチレン。The elastomer may be added at the time of mixing the modified polyethylene and the styrenic polymer. The amount of the styrenic polymer is 1 part by weight per 100 parts by weight of the modified polyethylene.
~100 parts by weight is preferred. Further, as the nidistomer, polyisobutylene is used.
ブタジェン−アクリロニトリル共重合ゴム、ポリブタジ
ェンゴム、クロロプレンゴム、エチレン−プロピレン共
重合ゴム、エチレン−プロピレン−非共役ジエン６成分
共重合ゴム、天然ゴム等が挙けられる。Examples include butadiene-acrylonitrile copolymer rubber, polybutadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene six-component copolymer rubber, natural rubber, and the like.
本発明の接着性ポリエチレン組成物は、前記特定の変性
ポリエチレンを使用し、変性ポリエチレンとスチレン系
ポリマーとを組み合わせて使用するので、接着性が特に
優れ、しかも低温でも接着可能であり、耐熱水性、耐塩
水性にも優れている。The adhesive polyethylene composition of the present invention uses the above-mentioned specific modified polyethylene and uses a combination of modified polyethylene and styrene polymer, so it has particularly excellent adhesive properties, can be bonded even at low temperatures, has hot water resistance, It also has excellent salt water resistance.
次に２本発明の金属積層体に用いる金属としては、鉄、
アルミニウム、銅、亜鉛、ニッケル、錫。Next, the metals used in the metal laminate of the present invention include iron,
Aluminum, copper, zinc, nickel, tin.
ステンレス等があげられる。Examples include stainless steel.
本発明の金属積層体は９本発明の接着性ポリエチレン組
成物を前記金属の少なくとも一面に積層することによっ
て得られる。例えば、接着性ポリエチレン組成物をフィ
ルム、シート状としておき金属（フィルム状、シート状
）ど熱圧着する方法。The metal laminate of the present invention can be obtained by laminating the adhesive polyethylene composition of the present invention on at least one surface of the metal. For example, a method in which an adhesive polyethylene composition is formed into a film or sheet and then thermocompressed onto a metal (film or sheet).
グイ外部でラミネートする方法、ダイ内部でラミネート
する方法、押出コーティングする方法あるいは粉体塗装
する方法等のそれ自体公知の方法に へ
よって得られる。金属は接着性ポリエチレン組成物と積
層する前に、それ自体公知の前処理９例えば溶剤脱脂、
酸洗、ショツトブラスト等の前処理が行われ、さらにプ
ライマー処理としてエポキシ系樹脂のプライマーを介す
ることにょシ、より大きな接着力を有する金属積層体を
得ることができる。It can be obtained by a method known per se, such as a method of laminating outside the die, a method of laminating inside the die, a method of extrusion coating, or a method of powder coating. Before lamination with the adhesive polyethylene composition, the metal is subjected to a pretreatment known per se9, e.g. solvent degreasing,
By performing pre-treatments such as pickling and shot blasting, and further applying an epoxy resin primer as primer treatment, a metal laminate having greater adhesive strength can be obtained.
本発明の金属積層体の構造としては１本発明の接着性ポ
リエチレン組成物と金属との２層構造を基本とするが、
必要に応じて種々の組合せが採用される。例えば、接着
性ポリエチレン組成物をはさんで両側に金属板を積層し
たサンドイッチ構造のもの、金属と積層した接着性ポリ
エチレン組成物にさらにポリオレフィン（例えばポリエ
チレン）を積層した構造のもの、これらの組合せ等が挙
げられ・特にポリオレフィンと金属とを積層するさいに
該接着性ポリエチレン組成物を介在させて融着させた金
属積層体が好適に挙げられる。The structure of the metal laminate of the present invention is basically a two-layer structure of the adhesive polyethylene composition of the present invention and metal.
Various combinations are adopted as necessary. For example, a sandwich structure in which metal plates are laminated on both sides with an adhesive polyethylene composition in between, a structure in which a polyolefin (e.g. polyethylene) is further laminated on an adhesive polyethylene composition laminated with metal, a combination of these, etc. In particular, a metal laminate in which a polyolefin and a metal are laminated with the adhesive polyethylene composition interposed and fused is preferably mentioned.
なお、前記金属は板であってもよくパイプであってもよ
い。Note that the metal may be a plate or a pipe.
以上９本発明の接着性ポリエチレン組成物は。 The above nine adhesive polyethylene compositions of the present invention are as follows.
前記の金属と高い接着力を示し、又高流動性および低温
接着性を示す。そして２本発明の接着性ポリエチレン組
成物は、高接着強度の外に耐熱水性。It exhibits high adhesion to the metals mentioned above, as well as high fluidity and low temperature adhesion. Second, the adhesive polyethylene composition of the present invention has high adhesive strength and hot water resistance.
・耐塩水性に優れるため、ケーブル、金属板、金属管内
外面の被覆に好適に使用することができる。・Because it has excellent salt water resistance, it can be suitably used for coating the inner and outer surfaces of cables, metal plates, and metal pipes.
本発明の接着性ポリエチレン組成物には、用途に応じて
酸化防止剤、紫外線吸収剤、難燃剤、無機有機充填剤、
顔料、帯電防止剤、金属繊維等を添加することができる
。The adhesive polyethylene composition of the present invention may contain antioxidants, ultraviolet absorbers, flame retardants, inorganic organic fillers,
Pigments, antistatic agents, metal fibers, etc. can be added.
以下に実施例および比較例を示す。以下の記載において
Ｍ工はメルトインデックスを意味する。Examples and comparative examples are shown below. In the following description, M means melt index.
以下の各側における試験方法を示す。The test method for each side is shown below.
試験方法
（１）接着強度
（Ａ） アルミニウムとの接着性
アセトンで脱脂した軟質アルミ板（０，２５Ｘ５０’Ｘ
１８０ｍｍ） （Ａｔ）に接着剤（変性ポリエチレン
組成物、ＡＤ）プレスシート（０，１５”Ｘ５０Ｘ１８
０閣）、Ｍｌｏ、１ ｔ７１０分、密度０．９３５１ｉ
’／−被覆用ポリエチレン（２×５０×１８０ ｍ）
（Ｐ Ｋ ）を順に積層し、圧縮成形機によシ１６０°
Ｃの温度で１０分間予熱後、 ６ 、Ｋｇ／ ｃｒ／ｒ
の圧力で２分間圧着して水中投下によシ急冷却して、金
属積層体（アルミ／ ｐ、 Ｄ ／ ｐ Ｅ ）を得た
。。Test method (1) Adhesive strength (A) Adhesion to aluminum Soft aluminum plate degreased with acetone (0.25 x 50'
180mm) (At) with adhesive (modified polyethylene composition, AD) press sheet (0,15"X50X18
0 cabinet), Mlo, 1 t710 min, density 0.9351i
'/-Polyethylene for coating (2 x 50 x 180 m)
(P K ) were laminated in order and placed in a compression molding machine at 160°.
After preheating for 10 minutes at a temperature of 6, Kg/cr/r
The metal laminates (aluminum/P, D/PE) were obtained by pressure bonding for 2 minutes at a pressure of .
一方、ポリエチレンを積層するかわシに上記軟質アルミ
板を使用して、接着剤を軟質アルミ板でサンドウィッチ
にする以外は上記と同様に実施して、金属積層体（アル
ミ／ＡＤ／アルミ）を得た。On the other hand, a metal laminate (aluminum/AD/aluminum) was obtained in the same manner as above except that the above soft aluminum plate was used as a base for laminating polyethylene and the adhesive was sandwiched between the soft aluminum plates. Ta.
これらの積層体を幅１０鰭×長さ１８０闘に切断し、イ
ンストロン社製引張試験機を使用し、引張速度１００
露／ ｍｉｎで１８０°剥離を実施する（チャート上の
剥離部分１００閣のうち前後２５簡を除いた中央５０閣
区間の最低値を読取る）。These laminates were cut into pieces of 10 fins wide x 180 fins long, and tested at a tensile speed of 100 using an Instron tensile tester.
Execute 180° peeling at dew/min (read the lowest value in the central 50 sections, excluding the 25 sections before and after the 100 sections on the chart that are separated).
（Ｂ） エポキシプライマー処理鋼板との接着性（Ｂ
−ｉ）；アセトンで脱脂した亜鉛メッキ鋼板（０，３×
５０×１８０鰭）に熱硬化性エポキシ柄脂（二液硬化型
、ハイビルドエポキシ樹脂塗料）を塗布して１００°Ｃ
Ｋ保たれたオープン中で３０分間硬化させた後、１４０
°Ｃのホットプレート上で接着剤プレスシート（０，１
５Ｘ５０Ｘ１ ａ ｏ祁）を積層し、１分間養生後、
Ｍ 工０．１ ｙ７１０分。(B) Adhesion to epoxy primer treated steel plate (B
-i); Galvanized steel sheet degreased with acetone (0.3×
50 x 180 fins) coated with thermosetting epoxy pattern resin (two-component curing type, high build epoxy resin paint) and heated to 100°C.
After curing for 30 minutes in the open at a temperature of 140
Glue press sheet (0,1
After stacking 5X50X1 aoq) and curing for 1 minute,
M engineering 0.1 y710 minutes.
密度０．９．２２ ｆｆ−の高圧法ポリエチレンシート
（２’Ｘ５０Ｘ１８ ｏ咽）を積層し、１００ｆ／ｄの
加重で３分間圧着して水中投下によシ急冷却する（予備
接着）。乾燥後、２００″Ｃのオープンに入れ２０グ／
−の加重で１分間圧着して水中投下によシ急冷却して金
属積層体（Ｂ−、、Ｉ）を得だ。High-pressure polyethylene sheets (2' x 50 x 18 o'clock) with a density of 0.9.22 ff- are laminated, pressure bonded for 3 minutes under a load of 100 f/d, and rapidly cooled by dropping into water (preliminary bonding). After drying, put it in the open at 200″C and weigh 20g/
The metal laminates (B-, , I) were obtained by pressure-bonding for 1 minute under a load of - and rapid cooling by dropping into water.
（Ｂ−１１）ｉアセトンで脱脂した亜鉛メッキ鋼板（０
，３Ｘ ５０ Ｘ １８０ＷＩ）に熱硬化性エポキシ樹
脂（二液硬化型、ハイビルドエポキシ樹脂塗料）を塗布
して、１００°Ｃに保たれたオープン中で３０分間硬化
させた後、１４０’（１”のホットプレート上で接着剤
プレスシート（Ｑ、１ ｊＸ５０Ｘ１８０−ｍ）を積層
し１分間養生後１Ｍ工０．Ｉ Ｖ／’Ｉ ０分。(B-11) i Galvanized steel sheet degreased with acetone (0
, 3X 50 The adhesive press sheets (Q, 1 x 50 x 180-m) were laminated on a hot plate and cured for 1 minute.
密度０．９２２ ｆ ／ ｃｒＡの高圧法ポリエチレン
プレスシート（２Ｘ５０Ｘ１．８０瓢）を積層し＋１０
０ ；。Laminated high-pressure polyethylene press sheets (2 x 50 x 1.80 gourd) with a density of 0.922 f/crA and +10
0 ;.
２／−の加重でろ分間圧着して水中投下にょシ急冷却し
て金属積層体（Ｂ−Ｉｔ）を得た。The metal laminate (B-It) was obtained by pressure-bonding with a load of 2/- for a period of time, followed by rapid cooling by dropping into water.
（Ｂ−１１１）ｉアセトンで脱脂した亜鉛メッキ鋼板（
０，３Ｘ５０Ｘ１８０簡）を６０″Ｃでクロメート処理
して乾燥する。次に１６０″Ｃのホットプレート上で熱
硬化性エポキシ樹脂〔二液硬化型、ビスフェノールＡ型
エポキシ樹脂（エポキシ当量：１９０）１００重量部に
、アミン型硬化剤（エポメート１３−００２）５０重量
部を混合使用〕を塗布し、十分硬化させた後、接着剤プ
レスシート（０，１５Ｘ５０Ｘ１８０■）を積層し、１
分間養生後２Ｍ工０．１１ｉ’／１０分、密度０．９２
２り／ｃＩＡの高圧法ポリエチレンプレスシー）（２ｘ
５０ｘ１８０ｍｍ）を積層し、１００１７’／ｃｒ／Ｉ
の加重で１分間圧着して水中投下により急冷却して金属
積層体（Ｂ−１［１）を得た。(B-111) i Galvanized steel sheet degreased with acetone (
0.3 x 50 x 180) was chromated at 60"C and dried. Next, on a hot plate at 160"C, a thermosetting epoxy resin [two-component curing type, bisphenol A type epoxy resin (epoxy equivalent: 190) 100 50 parts by weight of an amine-type curing agent (Epomate 13-002) was applied and sufficiently cured, and then an adhesive press sheet (0.15 x 50 x 180 cm) was laminated.
2M work 0.11i'/10 minutes after curing for minutes, density 0.92
2/cIA high pressure polyethylene press sea) (2x
50x180mm), 10017'/cr/I
The metal laminate (B-1[1) was obtained by pressing for 1 minute under a load of 100 mL and rapidly cooling by dropping into water.
以′上の積層体を幅１０謳に切断し、インストロン社製
引張試験機を使用し、引張速度５０朔、／ｌｌＩ］１ｎ
で９０°剥離を実施する（２分間測定した強度の平均値
で表わす）。The above laminate was cut into widths of 10 mm and tested using an Instron tensile tester at a tensile speed of 50 mm/llI]1n.
Peeling is carried out at 90° (expressed as the average value of the strength measured over 2 minutes).
屠体を沸とう水に浸漬し、１０００時間後の接着強度を
測定した。The carcass was immersed in boiling water, and the adhesive strength was measured after 1000 hours.
積層体を１００°Ｃのエアーオープン中で１０００時間
後の接着強度を測定した。The adhesive strength of the laminate was measured after 1000 hours in an air open environment at 100°C.
積層体の中心に直径５咽の穴をあけ、５０’Ｃ＋３％の
塩水に浸漬し１０００時間経過後の浸入度を測定した。A hole with a diameter of 5 mm was made in the center of the laminate, and the hole was immersed in 50'C + 3% salt water, and the degree of penetration was measured after 1000 hours had elapsed.
浸入された部分の面積を測定し、その面積に相当する半
径と穴の半径の差を浸入度とする。The area of the penetrated part is measured, and the difference between the radius corresponding to that area and the radius of the hole is defined as the degree of penetration.
値が小さい程耐塩水性がよいことを示す。The smaller the value, the better the salt water resistance.
実施例１
Ｍ Ｉ ２．Ｏｆｆ７１０分、密度０．９１９ ｆｆｃ
ｒＡ。Example 1 M I 2. Off710 minutes, density 0.919 ffc
rA.
融点１２３°Ｃ２分子量分布（気／ＭＮ）３．ブテン−
１含量４重量パーセントの線状低密度ポリエチレン（Ｌ
ＬＤＰ’Ｅ）にポリエチレン１２当シ無水マレイン酸０
．Ｉ Ｘ１０−’モルとｔ−ブチルハイドロパーオキサ
イド’０．０４ Ｘ １０−’モルとをリボンブレンダ
ーにて混合し、これを窒素雰囲気下にて２００°Ｃで単
軸押出機（スクリュー径５０■、 Ｌ／Ｄ ２４ ）を
用いて溶融混練することにより、ポリエチレン１ｇに対
して無水マレイン酸０．（］ ８ Ｘ １０−’モルが
グラフト化した変性ポリエチレン（ＭＩ＝１．５グ／１
０分、密度０．９１９２／−１融点１２３°Ｃ）を得た
。Melting point 123°C2 Molecular weight distribution (air/MN)3. Butene
1 content of 4% by weight linear low density polyethylene (L
LDP'E) with 12 parts of polyethylene and 0 parts of maleic anhydride
．． I X 10-' mol and t-butyl hydroperoxide '0.04 , L/D 24 ), the amount of maleic anhydride is 0.1 g per 1 g of polyethylene. (] 8 X 10-' moles grafted modified polyethylene (MI=1.5 g/1
0 minutes, density 0.9192/-1 melting point 123°C).
以上の無水マレイン酸変性ＬＬＤＰ１１００重量部にポ
リスチレン（旭化成スタイロン６６６）２５重量部をバ
ンバリーミキサ−を用い、１６０°Ｃで５分間混練して
、接着性ポリエチレン組成物を得た。25 parts by weight of polystyrene (Asahi Kasei Stylon 666) was mixed with 1100 parts by weight of the above maleic anhydride-modified LLDP using a Banbury mixer at 160°C for 5 minutes to obtain an adhesive polyethylene composition.
この組成物を前記の試験方法にしたがって試験した結果
を表１に示す。Table 1 shows the results of testing this composition according to the test method described above.
実施例２
実施例１の無水マレイン酸変性ＬＬＤＰＥ１００重量部
にポリスチレン（旭化成スタイロン６６６）１１重量部
をバンバリーミキサ−を用い、１６０°Ｃで５分間混練
して、接着性ポリエチレン組成物を得た。Example 2 100 parts by weight of the maleic anhydride-modified LLDPE of Example 1 was mixed with 11 parts by weight of polystyrene (Asahi Kasei Stylon 666) using a Banbury mixer at 160°C for 5 minutes to obtain an adhesive polyethylene composition.
この組成物を前記の試験方法にしたがって試験した結果
を表１に示す。Table 1 shows the results of testing this composition according to the test method described above.
実施例６
ぞ
実施例１＋使用したＬＬＤＰＥにポリエチレン１２当シ
無水マレイン酸０．１５Ｘ１０ モルとｔ−ブチルハ
イドロパーオキサイド０．０４８Ｘ１０モルとをリボン
ブレンダーにて混合し、これを窒素雰囲気下にて２００
°Ｃで単軸押出機（スクリュー径ｓ ０日、 Ｌ／Ｄ
２４’）を用いて溶融混練することによシ、ポリエチレ
ン１２に対して無水マレイン酸０．１５ Ｘ １０−’
モルがグラフト化した変性ポリエチレン（Ｍ工１．３ｆ
／１０分、密度Ｃ１，９１９ｇ／肩、融点１２己’ｃ
）を得た。Example 6 The LLDPE used in Example 1+ was mixed with 12 polyethylene, 0.15 x 10 moles of maleic anhydride, and 0.048 x 10 moles of t-butyl hydroperoxide in a ribbon blender.
Single screw extruder (screw diameter s 0 days, L/D
24') by melt-kneading 0.15 x 10-' of maleic anhydride to polyethylene 12.
Modified polyethylene grafted with moles (M engineering 1.3f
/10 minutes, density C1,919g/shoulder, melting point 12'c
) was obtained.
以上の無水マレイン酸変性ＵＬＤＰＢ１００重量部にポ
リスチレン（デンカスチｏ−／ｌ／（）Ｐ−１）３重量
部をバンバリーミキサ−で１６０°Ｃで５分間混練して
、接着性ポリエチレン組成物を得た。100 parts by weight of the above maleic anhydride-modified ULDPB was mixed with 3 parts by weight of polystyrene (Denkastio-/L/()P-1) in a Banbury mixer at 160°C for 5 minutes to obtain an adhesive polyethylene composition. .
Ｃ組成物を前記。試験方法に、えヵ、９１験
゛“した結果を表１に示す。C composition as described above. The test method is Eka, 91 trials.
The results are shown in Table 1.
実施例４
Ｍ工１２．０９７１０分、密度９１９グ／ｃＡ、融点１
２ろ゛Ｃ１分子量分布（Ｍｗ／ＭＮ）４．ブテン−１含
量４重量パーセントのＬＬＤＰＥにポリエチレン１２当
シ無水マレイン酸０．２５Ｘ１０ モル、ｔ−ブチル
ノ＼イドロバーオキサイド０．０９３Ｘ Ｉ Ｑ−’モ
ルとをリボンブレンダーにて混合し。Example 4 M process 12.09710 minutes, density 919 g/cA, melting point 1
2. C1 molecular weight distribution (Mw/MN)4. LLDPE having a butene-1 content of 4% by weight was mixed with polyethylene 12, 0.25×10 mol of maleic anhydride, and 0.093×IQ-' mol of t-butylhydrobar oxide in a ribbon blender.
以後実施例１と同様に行ない、ポリエチレン１２に対し
て無水マレイン酸０．２０Ｘ１０ モルがグラフト化
した変性ポリエチレン（Ｍ工１ｏ、ｓｙ／１０分、密度
０．９１９グ／７．融点１２３°Ｃ）を得た。Thereafter, the same procedure as in Example 1 was carried out, and modified polyethylene (M process 1o, sy/10 minutes, density 0.919 g/7, melting point 123°C) was prepared by grafting 0.20 x 10 moles of maleic anhydride to polyethylene 12. I got it.
以上の無水マレイン酸変性ＬＬＤＰＥ １０ ｏＮＮ郡
部ポリスチレン（旭化成スタイロン６６６）２５重量部
をバンバリーミキサ−を用い１６０°Ｃで５分間混練し
て、接着性ポリエチレン組成物を得た。この組成物を前
記の試験方法にしたがって試験した結果を表１に示す。25 parts by weight of the maleic anhydride-modified LLDPE 10 oNN Koribe polystyrene (Asahi Kasei Stylon 666) was kneaded for 5 minutes at 160°C using a Banbury mixer to obtain an adhesive polyethylene composition. Table 1 shows the results of testing this composition according to the test method described above.
比較例１
実施例１で得られた無水マレイン酸変性ポリエチレンを
用いて、前記の試験方法にしたがって試験した。その結
果を表１に示す。Comparative Example 1 Using the maleic anhydride-modified polyethylene obtained in Example 1, a test was conducted according to the test method described above. The results are shown in Table 1.
比較例２
実施例４で得られた無水マレイン酸変性ポリエチレンを
用いて、前記の試験方法にしだがって試験した。その結
果を表１に示す。Comparative Example 2 The maleic anhydride-modified polyethylene obtained in Example 4 was tested according to the test method described above. The results are shown in Table 1.
１１丁］乙１’ （６Ｌ ）実施例５
実施例１の無水マレイン酸変性ＬＬＤＰ’Ｅ１００重量
部にゴム人シポリスチレン（デンカポチロールＨニーＥ
＋−２）２３重量部をバンバリーミキサ−で１６０°Ｃ
で５分間混練して、接着性ポリエチレン組成物を得た。11 pieces] Otsu 1' (6L) Example 5 To 100 parts by weight of maleic anhydride-modified LLDP'E of Example 1, rubber polystyrene (Denkapotirol Hnie E) was added.
+-2) 23 parts by weight in a Banbury mixer at 160°C
The mixture was kneaded for 5 minutes to obtain an adhesive polyethylene composition.
この組成物を前記の試験方法にしたがって試験した結果
、を表２に示す。Table 2 shows the results of testing this composition according to the test method described above.
実施例６
実施例１の無水マレイン酸変性り、Ｌ、Ｄ Ｐ Ｅ １
００重量部に−チ・・と酢酸、ビ＝☆％゛・・・り共重
合体（日本油脂モディパ−３ＶＰＯ）１１重量部をバン
バリ−ミキサーで１６０°Ｃで・５分間混練して。Example 6 Maleic anhydride modification of Example 1, L, D P E 1
00 parts by weight, -chi..., acetic acid, and 11 parts by weight of Bi=☆%... resin copolymer (NOF Modiper-3VPO) were kneaded at 160°C for 5 minutes using a Banbury mixer.
接着性ポリエチレン組成物を得た。An adhesive polyethylene composition was obtained.
この組成物を前記の試験方法にしたがって試験した結果
を表２に示す。Table 2 shows the results of testing this composition according to the test method described above.
実施例７
１．．、実施例１の無水マレイン酸変性Ｌ：ｃ、Ｄｐ
ｉｉｏ。Example 7
1. ．． , Maleic anhydride modified L of Example 1: c, Dp
iio.
重量部にスチレンと化合物中に不飽和炭化水素部分とパ
ーオキサイド部分の両方の基を有するモノマーとのブロ
ック共重合体（日本油脂）・イノき−Ｓ５０ろＢ）２５
重量部をバンバリーミキサ−で１６０’Ｃで５分間混練
して、接着性ポリエチレン組成物を得た。Block copolymer of styrene and a monomer having both an unsaturated hydrocarbon moiety and a peroxide moiety in the weight part (NOF) Inoki-S50 filter B) 25
Parts by weight were kneaded in a Banbury mixer at 160'C for 5 minutes to obtain an adhesive polyethylene composition.
この組成物を前記の試験方法にしたがって試験した結果
を表２に示す。Table 2 shows the results of testing this composition according to the test method described above.
実施例８
実施例４の無水マレイン酸変性ＬＬＤＰＥ１００重量部
に、ポリスチレン（デンカポリスチロールａ Ｐ−１）
２９ Ｍ置部、エチレン−プロピレン共重合ゴム（タ
フマーＰ０１８０）１４重量部をノくンバリーミキサー
で１６０°Ｃで５分間混練して。Example 8 Polystyrene (Denka Polystyrene a P-1) was added to 100 parts by weight of the maleic anhydride-modified LLDPE of Example 4.
29 M, 14 parts by weight of ethylene-propylene copolymer rubber (Tafmer P0180) were kneaded at 160°C for 5 minutes in a Nokunbury mixer.
接着性ポリエチレン組成物を得た。An adhesive polyethylene composition was obtained.
この組成物を前記の試験方法にしたがって試験した結果
を表２に示す。Table 2 shows the results of testing this composition according to the test method described above.
Claims (2)
メルトインデックスが０．０５〜２０ｇ／１０分、重量
平均分子量／数平均分子量が２〜１０である線状低密度
ポリエチレンに不飽和カルボン酸類をグラフトした変性
ポリエチレンとスチレン系ポリマーとを混合してなる接
着性ポリエチレン組成物。(1) A copolymer of ethylene and α-olefin with a melt index of 0.05 to 20 g/10 min and a weight average molecular weight/number average molecular weight of 2 to 10. An adhesive polyethylene composition made by mixing modified polyethylene grafted with an acid and a styrene polymer.
メルトインデックスが０．０５〜２０ｇ／１０分、重量
平均分子量／数平均分子量が２〜１０である線状低密度
ポリエチレンに不飽和カルボン酸類をグラフトした変性
ポリエチレンとスチレン系ポリマーとを混合してなる接
着性ポリエチレン組成物を金属の少なくとも一面に積層
してなる金属積層体。(2) Linear low-density polyethylene, which is a copolymer of ethylene and α-olefin and has a melt index of 0.05 to 20 g/10 minutes and a weight average molecular weight/number average molecular weight of 2 to 10, has unsaturated carbon atoms. A metal laminate comprising an adhesive polyethylene composition made of a mixture of modified polyethylene grafted with an acid and a styrene polymer and laminated on at least one surface of metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13289884A JPS6114272A (en) | 1984-06-29 | 1984-06-29 | Bondable polyethylene composition and metal laminate thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13289884A JPS6114272A (en) | 1984-06-29 | 1984-06-29 | Bondable polyethylene composition and metal laminate thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6114272A true JPS6114272A (en) | 1986-01-22 |
Family
ID=15092125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13289884A Pending JPS6114272A (en) | 1984-06-29 | 1984-06-29 | Bondable polyethylene composition and metal laminate thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6114272A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762882A (en) * | 1985-07-08 | 1988-08-09 | Mitsubishi Chemical Industries Limited | Modified polyolefin resin and a composition containing the same |
| EP0412503A2 (en) * | 1989-08-07 | 1991-02-13 | Mitsui Petrochemical Industries, Ltd. | Adhesive resin composition, laminate comprising this composition as adhesive layer, and process for preparation thereof |
| US5250349A (en) * | 1989-08-07 | 1993-10-05 | Mitsui Petrochemical Industries, Ltd. | Retortable packaging laminate structure with adhesive layer |
| EP0791640A1 (en) * | 1996-02-21 | 1997-08-27 | Morton International, Inc. | Extrudable resin for polystyrene and laminate |
| WO2001018141A1 (en) * | 1999-09-03 | 2001-03-15 | E.I. Du Pont De Nemours And Company | Low activation temperature adhesive composition with high peel strength and cohesive failure |
| US6855432B1 (en) | 1999-09-03 | 2005-02-15 | E. I. Du Pont De Nemours And Company | Low activation temperature adhesive composition with high peel strength and cohesive failure |
| EP1808470A1 (en) * | 2006-01-16 | 2007-07-18 | Arkema France | Tie based on grafted polyethylene and on high-impact or crystal polystyrene with cohesive failure |
| WO2017038615A1 (en) * | 2015-08-28 | 2017-03-09 | Dic株式会社 | Lamination adhesive, multilayered film, and secondary cell using same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5871972A (en) * | 1981-10-08 | 1983-04-28 | ケムプレクス・カンパニー | Composite structure and manufacture |
| JPS59149943A (en) * | 1983-02-16 | 1984-08-28 | Sumitomo Chem Co Ltd | Adhesive resin composition |
-
1984
- 1984-06-29 JP JP13289884A patent/JPS6114272A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5871972A (en) * | 1981-10-08 | 1983-04-28 | ケムプレクス・カンパニー | Composite structure and manufacture |
| JPS59149943A (en) * | 1983-02-16 | 1984-08-28 | Sumitomo Chem Co Ltd | Adhesive resin composition |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762882A (en) * | 1985-07-08 | 1988-08-09 | Mitsubishi Chemical Industries Limited | Modified polyolefin resin and a composition containing the same |
| CN1083869C (en) * | 1989-08-07 | 2002-05-01 | 三井化学株式会社 | Adhesive resin composition, laminated plate containing said composition as binding layer and prepn. method thereof |
| EP0412503A2 (en) * | 1989-08-07 | 1991-02-13 | Mitsui Petrochemical Industries, Ltd. | Adhesive resin composition, laminate comprising this composition as adhesive layer, and process for preparation thereof |
| US5250349A (en) * | 1989-08-07 | 1993-10-05 | Mitsui Petrochemical Industries, Ltd. | Retortable packaging laminate structure with adhesive layer |
| EP0791640A1 (en) * | 1996-02-21 | 1997-08-27 | Morton International, Inc. | Extrudable resin for polystyrene and laminate |
| US6855432B1 (en) | 1999-09-03 | 2005-02-15 | E. I. Du Pont De Nemours And Company | Low activation temperature adhesive composition with high peel strength and cohesive failure |
| WO2001018141A1 (en) * | 1999-09-03 | 2001-03-15 | E.I. Du Pont De Nemours And Company | Low activation temperature adhesive composition with high peel strength and cohesive failure |
| CN100354385C (en) * | 1999-09-03 | 2007-12-12 | 纳幕尔杜邦公司 | Low activation temperature adhesive composition with high peel strength and cohesive failure |
| US7381770B1 (en) * | 1999-09-03 | 2008-06-03 | E. I. Du Pont De Nemours And Company | Low activation temperature adhesive composition with high peel strength and cohesive failure |
| EP1808470A1 (en) * | 2006-01-16 | 2007-07-18 | Arkema France | Tie based on grafted polyethylene and on high-impact or crystal polystyrene with cohesive failure |
| FR2896249A1 (en) * | 2006-01-16 | 2007-07-20 | Arkema Sa | BINDER BASED ON POLYETHYLENE GRAFT AND POLYSTYRENE SHOCK OR CRYSTAL WITH COHESIVE RUPTURE |
| WO2017038615A1 (en) * | 2015-08-28 | 2017-03-09 | Dic株式会社 | Lamination adhesive, multilayered film, and secondary cell using same |
| JP6143147B1 (en) * | 2015-08-28 | 2017-06-07 | Dic株式会社 | Laminate adhesive, multilayer film, and secondary battery using the same |
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