JPS6040136A - Bonded structure of olefin resin and metal - Google Patents
Bonded structure of olefin resin and metalInfo
- Publication number
- JPS6040136A JPS6040136A JP58148557A JP14855783A JPS6040136A JP S6040136 A JPS6040136 A JP S6040136A JP 58148557 A JP58148557 A JP 58148557A JP 14855783 A JP14855783 A JP 14855783A JP S6040136 A JPS6040136 A JP S6040136A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- acrylic acid
- olefin resin
- metal
- primer
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
Abstract
Description
【発明の詳細な説明】
本発明はポリエチレンライニング王冠、ポリエチレンラ
イニング鋼管などへの使用を目的としたオレフィン樹脂
と金属の接着構造物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an olefin resin and metal adhesive structure intended for use in polyethylene lined crowns, polyethylene lined steel pipes, and the like.
従来・王冠・その他の容器蓋等の密封材として金属板に
表面保設塗料を塗布したものを、蓋、王冠に成型し、こ
の蓋及び王冠内面に密封材を装着して使用していた。こ
の密封材としてフルクジスフ、塩化ビニル樹脂プラスチ
ゾル等が使われているが、これらは前者は天然品である
ため価格が高い、作業性が悪い、内容物によっては異変
を生ずるなどの欠点があり、後者は密封材中に比較的多
量の可塑剤が含有されており、この可塑剤が内容物に抽
出され移行して転味転点を起す欠点があった。Conventionally, as a sealing material for crowns and other container lids, a metal plate coated with a surface preservation paint was molded into a lid or crown, and the sealing material was attached to the inner surface of the lid or crown. Flukjisuf, vinyl chloride resin plastisol, etc. are used as sealing materials, but the former is a natural product and has drawbacks such as being expensive, having poor workability, and causing abnormalities depending on the contents, while the latter However, the sealing material contained a relatively large amount of plasticizer, and this plasticizer was extracted and transferred to the contents, causing a turning point.
上述のごとく、これらの欠点を解決すべく、ポリオレフ
ィン樹脂のライナー付王冠、蓋が完成されたが、ポリオ
レフィン樹脂は金属への接着性が悪いため、王冠内にポ
リオレフィンライナーを物理的に嵌着させる方法がとら
れていたが、これはボトラーで打栓操作中にライナーの
脱落の危険があった。また、鋼管にも諸々の化学特性の
よいポリオレフィン樹脂を表面にライニングすべく種々
試みられたが、接着に問題があり実用化の障害となって
いた。As mentioned above, in order to solve these drawbacks, polyolefin resin crowns and lids with liners have been completed, but since polyolefin resin has poor adhesion to metal, it is necessary to physically fit the polyolefin liner inside the crown. However, there was a risk that the liner would fall off during the bottler's capping operation. Various attempts have also been made to line the surface of steel pipes with polyolefin resins that have good chemical properties, but problems with adhesion have hindered their practical application.
このためオレフィン樹脂のライナーを王冠内面に接着し
たりオレフィン樹脂を鋼管にライニングする方法として
金属表面にプライマーを施こし、これを接着剤として金
属とオレフィン樹脂を接着するに、このプライマーにエ
ポキシ ＝ フェノールｆｉｔ脂、エポキシ −アミノ
樹脂、エポキシ −アクリル樹脂、塩化ビニル−酢酸ビ
ニル樹脂等を使っているが何れも接着力が弱く、がっプ
ライヤーとしての被膜も弱いなどの欠点があった。For this reason, as a method of adhering an olefin resin liner to the inner surface of a crown or lining a steel pipe with olefin resin, a primer is applied to the metal surface, and this primer is used as an adhesive to bond the metal and olefin resin.Epoxy = phenol is added to this primer. Fit resins, epoxy-amino resins, epoxy-acrylic resins, vinyl chloride-vinyl acetate resins, etc., have been used, but all of them have drawbacks such as weak adhesive strength and weak coatings as pliers.
この欠点を除去すべく、エポキシ樹脂、エポキシ−７エ
ノール樹脂などをベース樹脂とし、酸化−ポリエチレン
を主接着剤成分として、その他エチレンコーポリマーな
どと共に分散してなる接着剤が提供された。しかし、接
着成分である酸化ポリエチレン、エチレンコーポリマー
などは、所定の接着強度を得るためには分子量の大きな
もの、Ｍ Ｆ Ｒ（’Ｍｅｌｔ ｆｌｏｗ ｒａｔｅ）
の比較的小さいものを使用する必要がある。従ってこの
ＭＦＲが小さく分子量が大きい樹脂を塗布して接着剤と
するためには、その樹脂を特殊な手段を用いて微粒子に
粉砕するしか方法がなく、従来は物理的に粉砕するため
、微粒子を均一化するには大変な手間を要した。また酸
化ポリエチレン樹脂は初期接着は得られるが、経時変化
して接着強度が低下するなどの欠点があった。In order to eliminate this drawback, adhesives have been provided in which an epoxy resin, epoxy-7 enol resin, or the like is used as a base resin, oxidized polyethylene is used as the main adhesive component, and other adhesives such as ethylene copolymers are dispersed therein. However, adhesive components such as polyethylene oxide and ethylene copolymers must have a large molecular weight or MFR ('Melt flow rate) in order to obtain the desired adhesive strength.
It is necessary to use a relatively small one. Therefore, in order to apply a resin with a low MFR and a large molecular weight and use it as an adhesive, the only way is to crush the resin into fine particles using special means. It took a lot of effort to make it uniform. Further, although oxidized polyethylene resin can provide initial adhesion, it has the disadvantage that adhesive strength deteriorates over time.
本発明は金属とオレフィン樹脂とをプライマ一層を介し
て接合するに、従来の欠点を除去し、強力でかつ完全な
接着及び被膜の強いプライマーを提供するものである。The present invention eliminates the conventional drawbacks in bonding metal and olefin resin through a single layer of primer, and provides a primer that provides strong and complete adhesion and a strong film.
本発明は、金属基体とオレフィン樹脂層とを接合するに
プライマ一層を介して行うが、このプライマ一層は高分
子量エポキシ樹脂溶液エチレン、アクリル酸、アクリル
酸エステルの三元重合体を必須成分とし、エチレン、エ
チレン−酢酸ビニルコーポリマー、エチレン−アクリル
酸コーポリマー、エチレン−マレイン酸コーポリマーな
どの一種以上を添加することを特長とするオレフィン樹
脂−金属接着剤構造物である。In the present invention, the metal substrate and the olefin resin layer are bonded through a single layer of primer, and this single layer of primer contains a terpolymer of high molecular weight epoxy resin solution ethylene, acrylic acid, and acrylic ester as an essential component, This is an olefin resin-metal adhesive structure characterized by adding one or more of ethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-maleic acid copolymer, and the like.
なお上記プライマーは
Ａ ？ｌｆ ： ｇ分子量エポキシをＭＩＢＫ、インブ
タノール、キシレン、メチルセロソルブ、ブチルセルソ
ルブ、Ｍ、ＥＫ、シクロヘギサノンなどの一種または二
種以上の混合溶剤系に４０％の濃度となるよう溶解した
溶液。The above primer is A? lf: A solution of g molecular weight epoxy dissolved to a concentration of 40% in one or more mixed solvents such as MIBK, imbutanol, xylene, methyl cellosolve, butyl cellosolve, M, EK, and cyclohegisanone.
Ｂ液：エチレン−アクリル酸−アクリル酸工Ｘ？ルと、
ポリエチレン、エチレン−酢酸ビニルコーポリマー、エ
チレン−アクリル酸コーポリマー、エチレン−マレイン
酸コーポリマーなどの一種もしくは二種以上を濃度が５
０％を越えない範囲で溶解した溶液。B liquid: Ethylene-acrylic acid-acrylic acid X? le and
One or more types of polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-maleic acid copolymer, etc. at a concentration of 5
A solution in which no more than 0% of the solution is dissolved.
のＡ液とＢ液を混合してプライマーとし°たものでちる
。Mix liquids A and B to use as a primer.
本発明のプライマーは微粒子が分散した均一な接着剤で
あり、ロールコータ−、スプレー塗布などに適している
。また該プライマーは金属基体に塗布するが、この金Ｊ
ＩＪ’体は鉄、銅、アルミニウム、亜鉛、不銹鋼、青銅
、白銅、ジュラルミン等各種金属でもあるいはこれらの
合金でも良い、またこれらの金属基体の表面に亜鉛、ス
ズ、クロム、等のメッキをほどこしてあってもかまわな
い。The primer of the present invention is a uniform adhesive in which fine particles are dispersed, and is suitable for roll coater, spray coating, etc. The primer is applied to a metal substrate, and this gold J
The IJ' body may be made of various metals such as iron, copper, aluminum, zinc, stainless steel, bronze, cupronickel, duralumin, etc., or alloys thereof, or by plating the surface of these metal bases with zinc, tin, chromium, etc. It doesn't matter if there is.
また、これらの金属基体にエポキシ −フェノール樹脂
、エポキシ −アミノ樹脂、エポキシ −アクリル樹脂
、塩化ビニル−酢酸ビニル樹脂等の防食を目的としたプ
ライマーを塗布してあっても本発明の接着効果が発揮さ
れる。Furthermore, the adhesive effect of the present invention is exhibited even if these metal substrates are coated with a primer for corrosion prevention such as epoxy-phenol resin, epoxy-amino resin, epoxy-acrylic resin, vinyl chloride-vinyl acetate resin, etc. be done.
こうして得られたプライマーを金属基体に塗布し、これ
にオレフィン樹脂のフィル または成型品等を置き、こ
れを加熱してプライマ一層に融着させた後冷却して金属
基体とオレフィン樹脂とを接着させると強力な接着力で
固着される。The primer obtained in this way is applied to a metal substrate, an olefin resin fill or molded product is placed on it, it is heated to fuse it to the primer layer, and then it is cooled to bond the metal substrate and olefin resin. It is fixed with strong adhesive force.
こうして得られた金属基体とオレフィン樹脂との接着力
は２５００ｇ／ｚ以上の強さを示し、その目的を充分け
だすものである。すなわち本発明によれば硬化剤を使用
しないで所定の物性が得られる、つまり、熱可塑性エポ
キシとして使用出来る、塗料ビヒクルとして効果がある
、熱可塑性として使用出来るので、接着成分のエチレン
コーポリマーに悪影響を及ぼさない、被膜が強くかつ弾
力性があるので金属基体を王冠等に加工するとき金属基
体に傷がつかず、金属基体を加工時の表面の傷を守るな
どすぐれ５た効果がある。The adhesive strength between the metal substrate and the olefin resin obtained in this manner was 2500 g/z or more, and the purpose was fully demonstrated. In other words, according to the present invention, the desired physical properties can be obtained without using a curing agent.In other words, it can be used as a thermoplastic epoxy, it is effective as a paint vehicle, and since it can be used as a thermoplastic, it does not have any adverse effects on the ethylene copolymer, which is an adhesive component. Since the coating is strong and elastic, the metal substrate is not scratched when it is processed into a crown etc., and it has excellent effects such as protecting the surface of the metal substrate from scratches during processing.
次に実施例を示す。Next, examples will be shown.
実施例１゜
プライマーを得るに次の配合でＡ、Ｂ液を作りこれを混
合して均一に分散させる。Example 1 To obtain a primer, prepare solutions A and B with the following formulations and mix them to uniformly disperse them.
の４０％溶液）
Ｂ液： ＬｕｐＯｌｅｎ Ａ２９１０Ｍ ２（ＢＡＳＦ
製、Ｍ Ｆ Ｒ６ｇ／ｌＱ ｉｉｎエチレン−アクリル
酸−ア
クリル酸エステル−コーホ
リ マ −）
Ｐｌｙｔａｃ Ｍろ００ １
（出光石油化手製ＭＦＲ１６９／
１０制エチレン−アクリル酸
コーポリマー）
メチルエチルケトン ２２
トルエン ２５
キシレン ２５
メチルイソブチルケトン ２５
このＡ液、Ｂ液を１＝１の割合で混合、均一に分散させ
て所望のプライマーを得た。Solution B: LupOlen A2910M 2 (BASF
MFR6g/lQiin ethylene-acrylic acid-acrylic acid ester copolymer) Plytac M001 (MFR169/10 ethylene-acrylic acid copolymer manufactured by Idemitsu Petrochemical Co., Ltd.) Methyl ethyl ketone 22 Toluene 25 Xylene 25 Methyl isobutyl Ketone 25 The A and B solutions were mixed at a ratio of 1=1 and uniformly dispersed to obtain a desired primer.
この得られたプライマーをあらかじめエポキシフェノー
ルプライマー溶液３０”Ｆ／１００ｄを塗布したブリキ
板に４０ｑ／１００ｄになる様均−に塗布した後これを
王冠にプレス成型する。この王冠を１００℃以上に予熱
しこの中に０．３ｇのオレフィン樹脂を供給し、冷却し
たパンチで王冠内にライナー全成型する。こうして得ら
れたライナーは接着強度が３５００ｇ／２．５ｔＭ以上
という強固な接着が得られた。The obtained primer is applied evenly to a tin plate coated with an epoxy phenol primer solution of 30"F/100d to a thickness of 40q/100d, and then press-molded into a crown. This crown is preheated to 100℃ or higher. 0.3 g of olefin resin was supplied into the tube, and the entire liner was molded into the crown using a cooled punch.The thus obtained liner had a strong bond with an adhesive strength of 3500 g/2.5 tM or more.
実施例２゜
Ａ液：ｘｐ−６２００
２００００Ｍ Ｋ Ｋの４０％溶液）
Ｂ液： Ｌｕｐｏｌｅｎ Ａ２９ ｌ ＱＭ ３（ＢＡ
ＳＦ製、Ｍ Ｆ Ｒ６ＶＩ Ｑ門ｒｎエチレン−アクリ
ル酸−
アクリル酸エステルコー
ポリマー）
ＫＡ、Ａ−９５００１
（ＵＯＯ製、エチレン−アクリル酸
コーポリマー）
メチルエチルケトン １５
トルエン １５
シクロヘキサノン ６０
このＡ液、Ｂ液を１００４６４の割合で混合、均一に分
散させて所望のプライマーを得る。Example 2 Solution A: 40% solution of xp-6200 20000M KK) Solution B: Lupolen A29 l QM 3 (BA
Manufactured by SF, MFR6VI Q (ethylene-acrylic acid-acrylic acid ester copolymer) KA, A-95001 (manufactured by UOO, ethylene-acrylic acid copolymer) Methyl ethyl ketone 15 Toluene 15 Cyclohexanone 60 Add these A and B solutions to 100464 Mix and distribute uniformly in the ratio of 1 to 2 to obtain the desired primer.
これを実施例１の方法で王冠内にライナーを成型した所
、王冠とライナーとの接着強度は３０００９／２．５α
以上の剥離強度を示した。When a liner was molded inside the crown using the method of Example 1, the adhesive strength between the crown and the liner was 30009/2.5α.
The peel strength was as follows.
実施例６゜
Ａ液：ＥＰ−６２００１００
（旭電化工業社製分子量
２００００ Ｍ Ｅ ｘの４０％溶液）Ｂ液： Ｌｕｐ
ｏｌｅｎ Ａ２９１０Ｍ ２．５（ＢＡＳＦ製、Ｍ Ｆ
Ｒ６９／１０＋＋ｉｎエチレン−アクリル酸−アク
リル酸エステルコーポリマー）
エバテートに−２０１０２
（住人化学製エチレンー酢酸ビニ
ルコーポリマー）
スミ力センＧ−８０６１，５
（住人化学製ポリエチレンＭＦＲ
２０９／１０制）
メチルエチルケトン ２０
シク四ヘキサノン ７４
このＡ液、Ｂ液を１：１の割合で混合、均一に分散させ
て所望のプライマーを得る。Example 6゜Liquid A: EP-6200100 (40% solution of molecular weight 20000M Ex manufactured by Asahi Denka Kogyo Co., Ltd.) Liquid B: Lup
olen A2910M 2.5 (manufactured by BASF, M F
R69/10++in ethylene-acrylic acid-acrylic acid ester copolymer) Evatate-20102 (Ethylene-vinyl acetate copolymer manufactured by Suminen Chemical) Sumirikisen G-8061,5 (Polyethylene MFR 209/10 system manufactured by Suminen Chemical) Methyl ethyl ketone 20 sq. Tetrahexanone 74 Mix liquid A and liquid B at a ratio of 1:1 and disperse uniformly to obtain a desired primer.
これを実施例１．の方法で王冠内にライナーを成型した
所王冠とライナーとの接着強度は２５００ｇ／２．５百
以上の剥離強度を示した。This is Example 1. When the liner was molded into the crown using the method described above, the adhesive strength between the crown and the liner showed a peel strength of 2500 g/2.500 or more.
この様に本発明によれば、従来充分な強度が得られなか
ったオレフィン樹脂と金属基体との接着が強固に行なえ
るすぐれた効果を有している理想的接着描造物である。As described above, the present invention provides an ideal adhesive image that has an excellent effect of firmly adhering an olefin resin and a metal substrate, which has not been able to have sufficient strength in the past.
特許出願人 内山工業株式会社Patent applicant Uchiyama Kogyo Co., Ltd.
Claims (1)
を介して接合されるオレフィン樹脂−金属接着構造物に
おいて、前記プライマ一層は高分子量エポキシ樹脂とエ
チレン、アクリル酸、アクリル酸エステルの三元重合体
を必須成分とし、エチレン、エチレン−酢酸ビニルコー
ポリマー、エチレン − アクリル酸コーポリマー、エ
チレ゛ン −マレイン酸コーポリマーなどの一種以上を
添加することを特長とするオレフィン樹脂−金属接着構
造物。In an olefin resin-metal adhesive structure in which gold m1Aflfi and an olefin resin layer are bonded via a single layer of primer, the single layer of primer contains a high molecular weight epoxy resin and a terpolymer of ethylene, acrylic acid, and acrylic acid ester as essential components. An olefin resin-metal adhesive structure characterized by adding at least one type of ethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-maleic acid copolymer, etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58148557A JPS6040136A (en) | 1983-08-12 | 1983-08-12 | Bonded structure of olefin resin and metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58148557A JPS6040136A (en) | 1983-08-12 | 1983-08-12 | Bonded structure of olefin resin and metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6040136A true JPS6040136A (en) | 1985-03-02 |
| JPH0376333B2 JPH0376333B2 (en) | 1991-12-05 |
Family
ID=15455414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58148557A Granted JPS6040136A (en) | 1983-08-12 | 1983-08-12 | Bonded structure of olefin resin and metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6040136A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6266538A (en) * | 1985-09-19 | 1987-03-26 | Sony Tektronix Corp | Shadow mask type cathode-ray tube |
| JPH06344506A (en) * | 1993-06-08 | 1994-12-20 | Mitsubishi Petrochem Co Ltd | Metal/resin laminate |
| JPH0714971U (en) * | 1993-08-20 | 1995-03-14 | 武盛 豊永 | Comfort |
| WO2020256038A1 (en) * | 2019-06-19 | 2020-12-24 | 昭和電工株式会社 | Composite multilayer body and metal-polyolefin bonded body |
-
1983
- 1983-08-12 JP JP58148557A patent/JPS6040136A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6266538A (en) * | 1985-09-19 | 1987-03-26 | Sony Tektronix Corp | Shadow mask type cathode-ray tube |
| JPH06344506A (en) * | 1993-06-08 | 1994-12-20 | Mitsubishi Petrochem Co Ltd | Metal/resin laminate |
| JPH0714971U (en) * | 1993-08-20 | 1995-03-14 | 武盛 豊永 | Comfort |
| WO2020256038A1 (en) * | 2019-06-19 | 2020-12-24 | 昭和電工株式会社 | Composite multilayer body and metal-polyolefin bonded body |
| JPWO2020256038A1 (en) * | 2019-06-19 | 2021-09-13 | 昭和電工株式会社 | Composite laminates and metal-polyolefin conjugates |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0376333B2 (en) | 1991-12-05 |
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