JPS596240A - Adhesion method using modified polyethylene resin composition - Google Patents
Adhesion method using modified polyethylene resin compositionInfo
- Publication number
- JPS596240A JPS596240A JP11480982A JP11480982A JPS596240A JP S596240 A JPS596240 A JP S596240A JP 11480982 A JP11480982 A JP 11480982A JP 11480982 A JP11480982 A JP 11480982A JP S596240 A JPS596240 A JP S596240A
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene
- composition
- ethylene
- melt index
- unsaturated carboxylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920013716 polyethylene resin Polymers 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 14
- 239000011342 resin composition Substances 0.000 title claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 42
- -1 polyethylene Polymers 0.000 claims description 42
- 229920000573 polyethylene Polymers 0.000 claims description 42
- 230000001070 adhesive effect Effects 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011949 solid catalyst Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 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
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000011247 coating layer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-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
- 238000002715 modification method Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
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】
本発明は接着性と防食性能に優れた変性ポリニゲ・レン
樹脂組成物に関するものであり、更にこれ金属いて鋼管
等の金属材料とポリエチレン樹脂とを接着する方法に係
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a modified polyurethane resin composition having excellent adhesive properties and anticorrosive properties, and further relates to a method for bonding a metal material such as a metal or steel pipe to a polyethylene resin.
従来、鋼管等の金属材料に防食性の保褥材としてポリエ
チレン樹脂覆することはよく知られているが、ポリエチ
レン樹脂そのものでは接着力にとほしいので接着成分と
して、無水マレイン酸等の不飽和カルボン酸や、各種極
性基を持つモノマーで変性したポリエチレン層を介して
接着を行うのが通常である。Conventionally, it is well known that metal materials such as steel pipes are coated with polyethylene resin as an anti-corrosion protection material, but polyethylene resin itself is required to have adhesive strength, so unsaturated carboxylic acid such as maleic anhydride is used as an adhesive component. Adhesion is usually achieved through a polyethylene layer modified with an acid or a monomer with various polar groups.
更に金属材料の表面処理やプライマー塗付等の前処理が
行われることもある。かかる用途に用いられる変性ポリ
エチレン樹脂の原料としては高圧法低密度ポリエチレン
、低圧法高密度ポリエチレン或いはこれらにゴム成分等
を混合したもの等各種樹脂が用いられている。しかしな
がら、現在までに提案されている樹脂成分でなま接着力
、接着の耐久性のバランスの良いものが少なく、接着力
には優れるが耐久性に劣るもの、耐久性は良いが接着力
が不足するというものが通例であった。木兄ゝ ＥＪ
箔らはかかる点の改良全試み、特定のポリエチレン樹脂
の配合物を変性することにより、接着フハ接着耐久性に
優れた変性ポリエチレン樹脂組成物がイ（）られること
全見出し本発明を達成した。Furthermore, pretreatment such as surface treatment of the metal material and application of a primer may be performed. Various resins such as high-pressure low-density polyethylene, low-pressure high-density polyethylene, and mixtures thereof with rubber components and the like are used as raw materials for modified polyethylene resins used in such applications. However, there are few resin components that have been proposed to date that have a good balance between raw adhesive strength and adhesive durability; some have excellent adhesive strength but have poor durability; others have good durability but lack adhesive strength It was customary to do so. Tree brother EJ
In an attempt to improve these points, foil et al. achieved the present invention by modifying a specific polyethylene resin formulation to create a modified polyethylene resin composition with excellent adhesive durability.
即ち本発明のオｌの発明は、マグネシウム、チタン、ハ
ロゲンを含む固体触媒成分と、有機アルミニウム化合物
とを組合せた触媒を用いて、エチレン及び少量の炭素数
４以上のび一オレフィンを共重合して得られるメルトイ
ンデックス０．１〜３０、’ＭＷ Ｏ，９１０〜０．９
４０のポリエチレン囚及びエチレン単独、あるいは少量
のα−オレフィンとエチレンとの共重合体であって、メ
ルトインデックス０．１〜５０で、上記ポリエチレン（
４）より高密度であるポリエチレンＣＢ）からなるポリ
エチレン組成物であって、全組成物重量中のポリエチレ
ン（ト）がＢ ／ Ａ十Ｂの比率で０．０５〜０．３５
であり、かつポリエチレン（ロ）及び／又１１０３）に
不飽和カルボン酸又はその線導体がグラフトしてあり、
該グラフト量が全ポリエチレン重量に７４して０．０５
〜５％であることを特徴とする接着性能の改善された変
成ポリエチレン樹脂組成物である。That is, the invention of the present invention involves copolymerizing ethylene and a small amount of an olefin with a carbon number of 4 or more using a catalyst that combines a solid catalyst component containing magnesium, titanium, and a halogen, and an organoaluminum compound. Obtained melt index 0.1-30, 'MW O, 910-0.9
40 polyethylene and ethylene alone, or a copolymer of a small amount of α-olefin and ethylene, with a melt index of 0.1 to 50, and the above polyethylene (
4) A polyethylene composition consisting of polyethylene (CB) having a higher density, in which the polyethylene (T) in the total composition weight is 0.05 to 0.35 in the ratio of B / A + B
and unsaturated carboxylic acid or its wire conductor is grafted onto polyethylene (b) and/or 1103),
The amount of grafting is 74 to the total polyethylene weight and 0.05
This is a modified polyethylene resin composition with improved adhesive performance, characterized in that the adhesive strength is 5%.
レン樹脂畔物とエポキシ系プライマ−ヲ絹合せて金属と
ポリエチレン樹脂と全接着する方法である。This is a method to completely bond metal and polyethylene resin by combining resin resin and epoxy primer with silk.
本発明に用いられるポリエチレン（Ａ） ｔｊ： 、マ
グネシウム、チタン、ハロゲンを含有する触媒成分を用
いて少量の炭素数４以上のα−オレフィンとエチレンを
共重合することによって得られるものであり、メルトイ
ンテックス０．１〜３０、密度０．９０〜０．９４５の
低密度ポリエチレンであ” 、ＪＱＩ常コセコモノマー
有率は１−１２モルチ程度である。本発明τパは０．９
１０〜０．９４０の密度が望ましい。 共重合するα−
オレフィンとして（１ブテン、ペンテン、ヘキセン、オ
クテン等があシ、ブテン、ヘキセン、メクテンの共重合
体が望ましい。又これらのα−オレフィンの混合物を共
重合したものであっても良い。Polyethylene (A) used in the present invention is obtained by copolymerizing ethylene with a small amount of α-olefin having 4 or more carbon atoms using a catalyst component containing magnesium, titanium, and halogen. It is a low-density polyethylene with an Intex of 0.1 to 30 and a density of 0.90 to 0.945, and the JQI standard monomer content is about 1 to 12 mol. The τ parameter of the present invention is 0.9.
A density of 10 to 0.940 is desirable. α- to copolymerize
As the olefin (butene, pentene, hexene, octene, etc., copolymers of butene, hexene, mectene, etc.) are preferred. Copolymers of mixtures of these α-olefins may also be used.
ポリエチレン（ＢＩ Ｕ 、エチレンのホモポリマーあ
るいは少量のα−オレフィンとのコポリマーであつて、
メルトインデックス０．１〜５０、密度はポリエチレン
■より高いものであり、望ましくは０．９４５以上もの
である、触媒はポリエチレン囚を製】青するのに用いら
れるものと同じであっても良いし、別のものであつ又も
良い。又共重合に用いられるα−メレフィンとしてはプ
ロピレン、ブテン等が用いられるが、よシ高級なα−オ
レフィンであっても良い。これらのび−オレフィンは通
常ポリマー中の含有率がｌＯモルチ以−ト、好ましくは
１モル以下となる垣で使用される。Polyethylene (BIU) is a homopolymer of ethylene or a copolymer with a small amount of α-olefin,
The melt index is 0.1 to 50, the density is higher than that of polyethylene, preferably 0.945 or more, and the catalyst may be the same as that used for producing blue polyethylene. , or something else is fine. Propylene, butene, etc. are used as the α-molefin used in the copolymerization, but higher α-olefins may also be used. These wide olefins are usually used in such a manner that their content in the polymer is less than 10 mol, preferably less than 1 mol.
本発明においてはポリエチレン代及び（８）ｋＢ／Ａ十
Ｂ＝（ＬＯ５〜０．３５ （重量）の比率で混合して用
いる。In the present invention, polyethylene is mixed and used at a ratio of (8)kB/A10B=(LO5 to 0.35 (weight)).
混合の比率は本発明においてλ彼であって、ポリエチレ
ン［Ｆ］）が少なすぎると接着耐久性の中でも耐水性能
が劣り、多すき゛ても耐熱性が低下するため好凍しくな
い。ｏ、ｉ〜０．２５の範囲が最も好適である。混合の
方法は、それぞれ囚、Φ）を別々に製造して後混合する
方法があシ、又重合反応時に多段階の重合方法をとり同
−触媒上で２種のポリエチレンを順次生成させる方法を
とっても良い。In the present invention, the mixing ratio is λ, and if there is too little polyethylene (F), the water resistance performance among the adhesive durability will be poor, and if it is too much, the heat resistance will decrease, so it is not good for freezing. The range of o, i to 0.25 is most preferred. As for the mixing method, there is a method in which the polyethylene and Φ) are prepared separately and then mixed together, and a method in which a multi-stage polymerization method is used during the polymerization reaction and two types of polyethylene are sequentially produced on the same catalyst. Very good.
ポリエチレン（ハ）、（Ｂの変性（グラフト）は、無水
マレイン酸等をラジカル発生剤とともに接触させること
により行う。変性方法は溶液中で行う方法、スラリー中
で行う方法、溶融混線法など、公知の方法のいずれを用
いても行うことが出来る。Modification (grafting) of polyethylene (C) and (B) is carried out by contacting maleic anhydride or the like with a radical generator. Modification methods include methods known in the art such as a method in a solution, a method in a slurry, and a melt mixing method. This can be done using any of the following methods.
又この変性及び混合を行うにあたっては、ポリマー（４
）、 ０３）のいずれか一方、あるいは双方を変性した
後混合する方法、及びあらかじめ両者を混合しておいて
変性を行う方法のどの方法をとってもよい。In addition, when performing this modification and mixing, the polymer (4
), 03), either one or both of them may be denatured and then mixed, or both may be mixed in advance and then denatured.
不飽和カルボン酸類のグラフト）４は上記ポリエチレン
混合物全体量に対して０．０５〜５ｗｔ％の範囲に入る
ようにするのが望ましい。不飽和カルボン酸類の量が少
いと接着力が低下するし、多すぎた場合には、着色等の
望ましくない現象が起る一方で、接着力の向上効果は少
なくなってしま気より好ましいグラフト量ｆｉ ０．０
７〜１ ｗｔ％である。It is desirable that the amount of the unsaturated carboxylic acid graft (4) falls within the range of 0.05 to 5 wt% based on the total amount of the polyethylene mixture. If the amount of unsaturated carboxylic acids is too small, the adhesive force will decrease, and if it is too large, undesirable phenomena such as coloring will occur, while the effect of improving the adhesion force will be reduced. fi 0.0
It is 7-1 wt%.
本発明に用いられる不飽和カルボン酸及びその誘導体と
しては、マレイン酸、フマル酸、アクリル酸、メタクリ
ル酸、シトラコン酸、エンドビシクロ（２，２，１）
５−ヘゲテン−２，３−ジカルボン酸等の不飽和カルボ
ン酸及びその無水物、エステル、アミド等の誘導体を挙
げることが出来る。内でも無水マレイン酸、アクリル酸
が好ましく、特に無水マレイン酸が好適である。Examples of unsaturated carboxylic acids and derivatives thereof used in the present invention include maleic acid, fumaric acid, acrylic acid, methacrylic acid, citraconic acid, endobicyclo(2,2,1)
Examples include unsaturated carboxylic acids such as 5-hegetene-2,3-dicarboxylic acid, and derivatives thereof such as anhydrides, esters, and amides. Among these, maleic anhydride and acrylic acid are preferred, with maleic anhydride being particularly preferred.
本発明の変性ポリエチレン樹脂組成物は、金属被偉材（
ポリエチレン樹脂）用接着層として有効に用いられるが
、かかる用途に用いるに際して、安定剤、着色剤、充填
材、その他各種添加物を加えて使用することも出来るの
は画然である。The modified polyethylene resin composition of the present invention can be used for metal covering materials (
Although it is effectively used as an adhesive layer for (polyethylene resin), it is obvious that stabilizers, colorants, fillers, and various other additives can also be added when used for such purposes.
以下に実施例によって本発明を更に具体的に説明する。The present invention will be explained in more detail below with reference to Examples.
なお、メルトインデックスはＡＳＴＭＤ−１２３８−５
７’ｌ’ に準じて測定したイ５１であり、密度はＡ
ＳＴＭ、 Ｄ １５０５ に準じて測定した。In addition, the melt index is ASTM D-1238-5.
7'l', and the density is A51.
Measured according to STM, D 1505.
実施例１
マグネシウムジエトキザイドと四塩化チタンの反応によ
って得られる固体触媒成分と、トリエチルアルミニウム
を用いて、イソブタン中でエチレンとブテン−１４，５
モルチの共重合を行い、 メルトインデックス０．８、
密度０．９２０の共重合体を得た。〔ポリエチレン（４
）〕
同じ触媒を用い、エチレンとプロピレン０．３モルチと
の共重合を行い、メルトインデックス２０゜密度０．９
７０の共重合体を得た。（ポリエチレン（Ｂ） ）囚ポ
リマー８０重量部、■）ポリマー２０重量部、無水マレ
イン酸０．１５重縫部、α、α′−ビスターシャリープ
チルバーオキシパラジイソグロビルベンゼン０．０２５
重量部を混合し、３０ＭφしΦ＝２４の単軸フルフライ
トスクリュー押出機を用い、２１Ｏ℃で溶融混練した。Example 1 Using a solid catalyst component obtained by the reaction of magnesium diethoxide and titanium tetrachloride and triethylaluminum, ethylene and butene-14,5 were prepared in isobutane.
Copolymerized with molch, melt index 0.8,
A copolymer with a density of 0.920 was obtained. [Polyethylene (4
)] Using the same catalyst, copolymerize ethylene and 0.3 mol of propylene to achieve a melt index of 20° and a density of 0.9.
70 copolymers were obtained. (Polyethylene (B)) 80 parts by weight of polymer, ■) 20 parts by weight of polymer, 0.15 parts by weight of maleic anhydride, 0.025 parts by weight of α,α'-bistershaributylbaroxyparadiisoglobilbenzene
Parts by weight were mixed and melt-kneaded at 210° C. using a 30Mφ, φ=24 single-screw full-flight screw extruder.
変性ポリエチレン樹脂組成物のメルトインデックスは１
．２、無水マレイン酸のグラフト重合量は０．１２ｗｔ
チであった。The melt index of the modified polyethylene resin composition is 1
．． 2. The amount of graft polymerization of maleic anhydride is 0.12wt
It was Chi.
接着強度及び耐熱性を次のようにして測定した。Adhesive strength and heat resistance were measured as follows.
鋼板（１０ｍｍ厚）の表面を（１，３ｍｍのスチールグ
リッドでプラスト処理したあと、この上にエポキシ系プ
ライマー（エポサームＰ ３３０三菱化成工業（株）製
、エボサームは登録商標）を約３０μの厚さで塗布した
ものを加熱炉で１４０ ’Ｃ程度に加熱し、その後該エ
ポキシ系グライマー上に前記変性ポリエチレン樹脂組成
物と高密度ポリエチレンがらなる２Ｊ＠の溶融シート（
変性ポリエチレン樹脂組成物４（）θμ、高密度ポリエ
チレン４ｍｍ、樹脂温度２３０℃）をエポキシ系プライ
マーと変性ポリエチレン樹脂組成物が接するように貼合
せて鋼板とポリエチレンの積層体を製造した。After the surface of the steel plate (10 mm thick) is plasted with a 1.3 mm steel grid, an epoxy primer (Epotherm P 330 manufactured by Mitsubishi Chemical Industries, Ltd., Evotherm is a registered trademark) is applied on top to a thickness of approximately 30 μm. The coated material was heated to about 140'C in a heating furnace, and then a molten sheet of 2J@ consisting of the modified polyethylene resin composition and high-density polyethylene (
A laminate of a steel plate and polyethylene was produced by bonding a modified polyethylene resin composition 4 ( ) θ μ, high density polyethylene 4 mm, resin temperature 230° C. so that the epoxy primer and the modified polyethylene resin composition were in contact with each other.
イ（ｔられたｔｆ４層体を室温まで冷却した後、該積層
体の接着強度、耐熱性について評価を行った。After cooling the tf4 layered product to room temperature, the adhesive strength and heat resistance of the layered product were evaluated.
接着強度は常法に従い、剥離速度１０ｍ卯漏１ｎ で９
０°剥離テストで測定した。耐熱性の評価は積層体より
１００ ｍｍ Ｘ １（１０ｍｍの試験サンプルを帯鋸
で切り出し、これを１００℃オーブン中に放置して端末
からの剥離状況を観察した。＃４共率−１１＃−茎況セ
観擦−した。結果は剥離が認められた日数で示した。Adhesive strength was determined according to the conventional method, with a peeling speed of 10 m and a leakage of 1 n.
Measured by 0° peel test. Heat resistance was evaluated by cutting out a 100 mm x 1 (10 mm) test sample from the laminate using a band saw, leaving it in an oven at 100°C and observing how it peeled off from the end. The conditions were observed and rubbed.The results were expressed as the number of days in which peeling was observed.
陰極剥離性能は、７１図に示したような構成の陰極剥離
テスト装置にかけ、テストロ０日での穴部からの最大剥
離進行距離によって評価を行なった。The cathode peeling performance was evaluated by using a cathode peeling test device configured as shown in FIG.
図においてｌは被覆層、２は鋼板、３は穴（５ｍｍφ入
４はガラスシリンダー、５は３襲食塩水、６は陽極（白
金）、７は直流電源（３■）である。結果を表−１に示
す。In the figure, l is a coating layer, 2 is a steel plate, 3 is a hole (with a diameter of 5 mm), 4 is a glass cylinder, 5 is a triple saline solution, 6 is an anode (platinum), and 7 is a DC power source (3■).The results are shown below. -1.
実施例２，３
原料ポリエチレンの比率を変えた他は実施例１と同様に
して実験を行い、結果を表−１に示す。Examples 2 and 3 An experiment was conducted in the same manner as in Example 1 except that the ratio of raw material polyethylene was changed, and the results are shown in Table 1.
実施例４
ポリエチレン（Ｉ３）のみに無水マレイン酸をグラフト
し、無水マレイン酸含量（１，８２ｗｔチ の変性ポリ
エチレンを作成し、実施例２と同じ比率でポリエチレン
（４）と混合した他は実施例１と同様に実験を行い接着
力の評価を行った。結果を表−１に示す。Example 4 Maleic anhydride was grafted only to polyethylene (I3) to create modified polyethylene with a maleic anhydride content (1.82 wt), and the same was mixed with polyethylene (4) in the same ratio as in Example 2. An experiment was conducted in the same manner as in 1 to evaluate the adhesive strength.The results are shown in Table 1.
実施例５
実施例１と同じポリエチレン囚、ポリエチレン（Ｊ３）
を用いてポリエチレン（４）のみ無水マレイン酸で変性
（実施例１と同じ第件すなわち（４）８０、無水マレイ
ン酸０．１５ 、パーオキライド０−０２５各重量部を
同様に混練。グラフト量０．１４ ｗｔ％。ペレ”ット
化。）
囚と（６）を同じ榮件でブレンドした。結果を表−１に
示す。Example 5 Same polyethylene as Example 1, polyethylene (J3)
Polyethylene (4) alone was modified with maleic anhydride (same as in Example 1, i.e. (4) 80, maleic anhydride 0.15, and peroxylide 0-025 parts by weight were kneaded in the same way. Grafting amount 0. 14 wt%. Pelletization) and (6) were blended under the same conditions. The results are shown in Table 1.
比較例１
ポリマー（２）のみを用いた他は実施例１と同様の実験
を行った。結宅を表−１に示す。Comparative Example 1 An experiment similar to Example 1 was conducted except that only polymer (2) was used. The results are shown in Table-1.
比較例２
ポリマー０３）のみを用いた他は実施例１と同様の実験
を行った。結果を表−１に示す。Comparative Example 2 An experiment similar to Example 1 was conducted except that only Polymer 03) was used. The results are shown in Table-1.
比較例３
高１１−ラジカル重合法で製造された低密度ポリエチレ
ン（メルトインデックス［１，４５、密度０．９２２）
をポリマー（Ａ）の代わりに用いた他は実施例１と同じ
実験を行った。結用を表−１に示す。Comparative Example 3 Low density polyethylene manufactured by high 11-radical polymerization method (melt index [1,45, density 0.922)
The same experiment as in Example 1 was conducted except that Polymer (A) was used instead of Polymer (A). The results are shown in Table-1.
オ１図は陰極剥離テスト装置の説明図である。
１・・・被覆層 ２・・・鋼板３・・・穴
４・・・ガラスシリンダー５・・・３
％食塩水 ６・・・陽極７・・・直流電源
−２コFigure 1 is an explanatory diagram of the cathode peeling test device. 1... Covering layer 2... Steel plate 3... Hole
4...Glass cylinder 5...3
% saline solution 6... Anode 7... DC power supply - 2 pieces
Claims (6)
触媒成分と、有機アルミニウム化合物とを組合せた触媒
を用いて、エチレン及び少晰の炭素数４以上のα−オレ
フィンを共重合して得られるメルトインデックス０．１
〜３０、密度０．９１０〜０．９４０のポリエチレン（
至）及びエチレン単独、あるいｕ少ｔのα−オレフィン
とエチレンとの共重合体であって、メルトインデックス
０．１〜５０で、上記ポリエチレン（４）よシ高密度で
あるポリエチレン（ト）からなるポリエチレン組成物で
あって、全組成物重量中のポリエチレン（５）がＢ／Ａ
＋Ｈの比率で０．０５〜０．３５であり、かつポリエチ
レン（４）及び／又は（ト）に不飽和カルボン酸又はそ
の誘導体がグラフトしておシ、該グラフト量が全ポリエ
チレン重量に対して０．０５〜５チであることを特徴と
する接着性能の改善された変成ポリエチレン樹脂組成物
。(1) A melt index of 0 obtained by copolymerizing ethylene and a small alpha-olefin having 4 or more carbon atoms using a catalyst that combines a solid catalyst component containing magnesium, titanium, and halogen with an organoaluminum compound. .1
~30, polyethylene with a density of 0.910 to 0.940 (
) and polyethylene (g), which is ethylene alone or a copolymer of ethylene with a small amount of α-olefin, and has a melt index of 0.1 to 50 and a higher density than the above polyethylene (4). A polyethylene composition consisting of B/A polyethylene (5) in the total composition weight
The ratio of A modified polyethylene resin composition with improved adhesive performance, characterized in that the adhesive strength is 0.05 to 5.
クリル酸である特許請求の範囲オ（１）項記載の組成物
。(2) The composition according to claim (1), wherein the unsaturated carboxylic acid is maleic anhydride and/or acrylic acid.
許請求の範囲オｉ１１項記載の組成物。(3) The composition according to claim 11, wherein the unsaturated carboxylic acid is maleic anhydride.
る分率が０．１〜０．２５ である特許請求の範囲オ
｛２｝填またはオ（３；項記載の組成物。(4) The composition according to claim (2) or (3), wherein the proportion of polyethylene [F]) based on the total weight of the composition is 0.1 to 0.25.
重量チである特許請求の範囲オ（３１項またはオ（４１
項記載の組成物。(5) Grafting amount of maleic anhydride is 0.07 to 1
Claims (31) or (41) that are heavy
Compositions as described in Section.
リエチレン（自）に不飽和カルポン酸類がグラフトして
いる特許請求の範囲オ（１》項、オ（２）項、オ（３）
項、オ（４）項またはオ（５１項記載の組成物。 （７｝ マグネシウム、チタン、ハロゲンを含む固体
触媒成分と、有機アルミニウム化合物とを組合せた触媒
を用いて、エチレン及び少量の炭素数４以上のα−オレ
フィンを共重合して得られるメルトインデックス０．１
〜３０、密度０．９１０〜０．９４０のポリエチレン（
至）及びエチレン単独、あるいは少量のび一オレフィン
とエチレントの共重合体であって、メルトインデックス
０．１〜５０で上記ポリエチレン（４）よυ高密度であ
るポリエチレン■からなるポリエチレン組成物であって
、全組成物重置中のポリエチレン（Ｂ）がＢ／Ａ＋Ｂの
比率で０．０５〜０．３５てあり、かつポリエチレン（
５）及び／又は（秒に不飽和カルボン酸又はその線導体
がグラフトしており、該グラフト量が全ポリエチレン重
量に対して０．０５〜５％である変成ポリエチレン樹脂
組成物とエポキシ系グライマーを組合せて金属とポリエ
チレン樹脂とを接着すること全特徴とするポリエチレン
樹脂と金属との接着方法。(6) Claims (e) (1), (e) (2), (e) (3) in which unsaturated carboxylic acids are grafted to at least polyethylene in polyethylene and (g).
The composition according to item 51, item 4) or item 51. Melt index 0.1 obtained by copolymerizing α-olefins of 4 or more
~30, polyethylene with a density of 0.910 to 0.940 (
) and a polyethylene composition consisting of ethylene alone or a copolymer of a small amount of olefin and ethylene, which has a melt index of 0.1 to 50 and a higher density than the polyethylene (4) above. , polyethylene (B) in the entire composition is in a ratio of B/A+B of 0.05 to 0.35, and polyethylene (
5) and/or (a modified polyethylene resin composition to which an unsaturated carboxylic acid or a wire conductor thereof is grafted, and the amount of grafting is 0.05 to 5% based on the total weight of the polyethylene, and an epoxy glymer) A method for bonding polyethylene resin and metal, which is characterized by bonding metal and polyethylene resin in combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11480982A JPS596240A (en) | 1982-07-03 | 1982-07-03 | Adhesion method using modified polyethylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11480982A JPS596240A (en) | 1982-07-03 | 1982-07-03 | Adhesion method using modified polyethylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS596240A true JPS596240A (en) | 1984-01-13 |
| JPH0413392B2 JPH0413392B2 (en) | 1992-03-09 |
Family
ID=14647222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11480982A Granted JPS596240A (en) | 1982-07-03 | 1982-07-03 | Adhesion method using modified polyethylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS596240A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5477236A (en) * | 1987-03-20 | 1995-12-19 | Hitachi, Ltd. | Method and apparatus for controlling movement of cursor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5225845A (en) * | 1975-08-25 | 1977-02-26 | Mitsui Petrochem Ind Ltd | Polyolefin composition having improved adhesivity with nylon resin |
| JPS58152077A (en) * | 1982-02-19 | 1983-09-09 | ケムプレクス・カンパニー | Adhesive blend |
| JPS58194967A (en) * | 1982-04-26 | 1983-11-14 | ケムプレクス・カンパニ− | Adhesive blend and complex structure |
-
1982
- 1982-07-03 JP JP11480982A patent/JPS596240A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5225845A (en) * | 1975-08-25 | 1977-02-26 | Mitsui Petrochem Ind Ltd | Polyolefin composition having improved adhesivity with nylon resin |
| JPS58152077A (en) * | 1982-02-19 | 1983-09-09 | ケムプレクス・カンパニー | Adhesive blend |
| JPS58194967A (en) * | 1982-04-26 | 1983-11-14 | ケムプレクス・カンパニ− | Adhesive blend and complex structure |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5477236A (en) * | 1987-03-20 | 1995-12-19 | Hitachi, Ltd. | Method and apparatus for controlling movement of cursor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0413392B2 (en) | 1992-03-09 |
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