JPS62178320A - Method of adhesion between denatured polyolefin resin and metal - Google Patents
Method of adhesion between denatured polyolefin resin and metalInfo
- Publication number
- JPS62178320A JPS62178320A JP61019535A JP1953586A JPS62178320A JP S62178320 A JPS62178320 A JP S62178320A JP 61019535 A JP61019535 A JP 61019535A JP 1953586 A JP1953586 A JP 1953586A JP S62178320 A JPS62178320 A JP S62178320A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- metal
- polyolefin resin
- cooling
- adhesion
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 238000010583 slow cooling Methods 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 3
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 230000004927 fusion Effects 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 description 23
- 239000000853 adhesive Substances 0.000 description 22
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007500 overflow downdraw method Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000002987 primer (paints) Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920006281 multilayer packaging film Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は高い接着強度が要求される各種金属板や金属管
などの製造に好適な変性ポリオレフィン樹脂と金属との
接着方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method of adhering a modified polyolefin resin and metal, which is suitable for manufacturing various metal plates and metal tubes that require high adhesive strength.
（従来技術）
近年高耐食性材料としてポリエチレンやポリプロピレン
などを熱融着法で接着して被覆した鋼板や鋼管が注目さ
れているが、ポリオレフィン樹脂は無極性であるため、
接着性が劣り、一般に熱融着法で金属に接着しても接着
強度が非常に劣るものである。(Prior art) In recent years, steel plates and steel pipes coated with polyethylene, polypropylene, etc. bonded by heat-sealing have been attracting attention as highly corrosion-resistant materials, but since polyolefin resin is non-polar,
It has poor adhesive properties, and even if it is bonded to metal using a heat fusion method, the adhesive strength is generally very poor.
このポリオレフィン樹脂の接着性を改善する方法として
は、樹ｌｆｆ表面にコロナ放電処理や火炎処理を施して
樹脂内にカルボニル基等の極性基を導入する方法、ポリ
オレフィン？封脂に極性基を有する単量体く例えばカル
ボンＦｌりをグラフト共重合したり、オレフィンの単量
体と極性基を有する単量体（例えば不飽和カルボン酸）
とをランダム共重合したりして、ポリオレフィン樹脂を
変性し、変性ポリオレフィン樹脂にする方法などが従来
知られているが、前者の方法は設備や工程が複雑であり
、また接着性もあまり向上しない。このためあまり強い
接着強度を必要としない包装用多層フィルム製造などの
分野に利用されている。これに対して後者の方法は樹脂
内に極性基が導入されでいるため、接着性はかなり向上
する。このため比較的大きな接着強度を必要とする樹脂
被覆鋼管の製造など金属との接着の分野に利用されてい
る。As a method to improve the adhesiveness of this polyolefin resin, there is a method of introducing polar groups such as carbonyl groups into the resin by subjecting the surface of the tree LFF to corona discharge treatment or flame treatment. By graft copolymerizing a monomer with a polar group, such as carboxyl, into the sealing resin, or by graft copolymerizing an olefin monomer with a monomer having a polar group (for example, unsaturated carboxylic acid).
It is conventionally known to modify polyolefin resins to make modified polyolefin resins by random copolymerization with . For this reason, it is used in fields such as the production of multilayer packaging films that do not require very strong adhesive strength. On the other hand, in the latter method, since polar groups are introduced into the resin, the adhesiveness is considerably improved. For this reason, it is used in the field of bonding with metals, such as in the production of resin-coated steel pipes, which require relatively high bonding strength.
ところで変性ポリオレフィン樹脂の接着性は極性基の導
入量、すなわち変性量が多い程高くなるので、ある程度
変性量の多いものを使用する必要があったため、樹脂価
格が高くなることは避けられなかった。また変性ポリオ
レフィン樹脂と鋼管などの金属との接着は、従来ポリオ
レフィン樹脂のような結晶性高分子を熱融着法により金
属に接着する場合、樹脂を金属に熱融着させた後常温ま
で冷却固化させる過程で急冷すると、樹脂の結晶化が抑
制され、また残留応力も減少し、さらに老境界１ｔｉ
（Ｗｅａｋ １ｌｏｕｎｄａｒｙ Ｌａｙｅｒ）の生成
が抑制されるなどの理由から接着強度が向上するとのこ
とが一般的であったので、熱ＦｆＡ着後急冷していた。By the way, the adhesiveness of a modified polyolefin resin increases as the amount of polar groups introduced, that is, the amount of modification, increases, so it was necessary to use a resin with a certain amount of modification, which inevitably led to an increase in the price of the resin. In addition, when adhering modified polyolefin resin to metal such as steel pipes, conventionally when a crystalline polymer such as polyolefin resin is bonded to metal using a heat fusion method, the resin is heat fused to the metal and then cooled to room temperature to solidify. Rapid cooling during the process suppresses crystallization of the resin, reduces residual stress, and further reduces the aging boundary 1ti.
Since it was generally believed that the adhesive strength was improved due to the suppression of the formation of (Weak 1 Roundy Layer), etc., the adhesive was rapidly cooled after thermal FfA deposition.
しかしこの接着方法では変性量の多い樹脂を使用しても
まだその接着強度は十分とは言い難いものであった。However, in this adhesive method, even if a highly modified resin is used, the adhesive strength is still not sufficient.
（発明が解決しようとする問題点）
本発明は変性ポリオレフィン樹脂と金属との熱融着法に
よる接着方法において、従来価格の高い０４脂を使用し
なければならず、また接着強度もまだ十分でないことか
ら、変性量の少ない樹脂を使Ｊ１１シても接着強度をさ
らに高くすることができる接着方法を提供するものであ
る。(Problems to be Solved by the Invention) The present invention is a method for bonding a modified polyolefin resin and a metal using a heat fusion method, which requires the use of conventionally expensive 04 resin, and the adhesive strength is still insufficient. Therefore, it is an object of the present invention to provide an adhesion method that can further increase the adhesive strength even when a resin with a small amount of modification is used.
（問題点を解決するための手ｙｔ＞
本発明者らは変性ポリオレフィン樹゛脂と金属との接着
強度を向上させるために両者の接着機構と接着強度の関
係について鋭意研究した結果、樹脂に導入された極性基
を金属面方向に配向させれば変性量が少なくても金属と
の接着強度が高くすることができ、しかもその効果は金
属表面に表面処理が施されていてもあることを究明した
のである。(Measures to Solve the Problems) In order to improve the adhesive strength between modified polyolefin resin and metal, the inventors conducted extensive research on the relationship between the adhesive mechanism and adhesive strength of the two, and as a result, introduced the following into the resin. We found that by orienting the polar groups in the direction of the metal surface, it is possible to increase the adhesive strength with the metal even with a small amount of modification, and that this effect remains even if the metal surface is surface-treated. That's what I did.
そして極性基を金属面方向に配向させるには変性ポリオ
レフィン樹脂を溶融状態から常温まで冷却固化させる際
冷却速度を遅くすればよいことを見出し、本発明を完成
したのである。すなわち本発明は変性ポリオレフィン樹
脂を金属に熱融着させた後樹脂を冷却固化させて接着す
る接着方法において、樹脂を冷却固化させる際溶融状態
から常温まで１０℃／ｓｅｃ以下の冷却速度で徐冷する
ことにより接着強度を高めるようにしたのである。Then, they discovered that in order to orient the polar groups in the direction of the metal surface, it is sufficient to slow the cooling rate when cooling and solidifying the modified polyolefin resin from a molten state to room temperature, and completed the present invention. That is, the present invention is an adhesive method in which a modified polyolefin resin is thermally fused to a metal, and then the resin is cooled and solidified. By doing so, the adhesive strength was increased.
すなわち本発明はり（脂の熱融着後の冷却を従来とは逆
に徐冷することにより変性量の少ない樹脂を使用でき、
しかも接着強度を１−６くすることができるようにした
ものである。In other words, the beam of the present invention (by cooling slowly after thermal fusion of the fat, contrary to the conventional method, a resin with a small amount of modification can be used,
Furthermore, the adhesive strength can be increased to 1-6.
本発明において、冷却速度を１０℃／ｓｅｃ以下と遅く
するのは、１０℃／ｓｅｃより速くすると樹脂の極性基
が金属面方向に配向する萌に樹脂が固化してしまって、
高い接着強度が得られないからである。なお樹脂を徐冷
すると樹脂の極性基が金属面れる。In the present invention, the reason why the cooling rate is set to 10°C/sec or less is that if the cooling rate is faster than 10°C/sec, the resin will solidify in a state where the polar groups of the resin are oriented in the direction of the metal surface.
This is because high adhesive strength cannot be obtained. Note that when the resin is slowly cooled, the polar groups of the resin are exposed to the metal surface.
冷却速度を１０℃／ｓｅｃ以下にする手段としては公知
の徐冷カー法でよく、例えば熱融着後所定の温度に保持
した雰囲気中で徐冷速度を制御するような方法でよい。The means for controlling the cooling rate to 10° C./sec or less may be the known slow cooling Kerr method, for example, a method in which the slow cooling rate is controlled in an atmosphere maintained at a predetermined temperature after heat fusion.
本発明では変性ポリオレフィン樹脂の極性基を金属面方
向に配向させて接着強度を向上させるのであるから、変
性ポリオレフィンＩｆ脂として極性基を導入させたもの
であることが必要で、好ましいものを挙げれば、（Ａ）
ポリオレフィン（例えばポリエチレン、ポリプロピレン
、ポリ−１−１テンなど）に不飽和カルボン酸（例えば
アクリル酸、メタクリル酸、イタコン酸、マレイン酸な
ど）またはその無水物をグラフト共重合したもの、（Ｂ
）オレフィン単量体（例えばエチレン、プロピレン、１
−ブテンなど）と不飽和カルボン酸（例えばアクリル酸
、メタクリル酸など）とをランダム共重合させたものな
どがある。In the present invention, the polar groups of the modified polyolefin resin are oriented in the direction of the metal surface to improve adhesive strength, so it is necessary that the modified polyolefin If resin has polar groups introduced therein. Preferred examples include: ,(A)
(B
) Olefin monomers (e.g. ethylene, propylene, 1
-butene, etc.) and an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, etc.).
本発明の接着方法は金属への樹脂の熱融着のさせ方に関
係なく適用でき、例えば熱融着法が金属を予め樹脂の融
点前後の温度（１２０〜２５０ ”Ｃ）に加熱した後押
出機により金属上に溶融樹脂を押出す方法や金属を前記
のように加熱した後樹脂フィルムを金属上に供給して、
加熱ロールまたは加熱プレスで圧着する方法であっても
接着強度を向上させることができる。The bonding method of the present invention can be applied regardless of the method of heat-sealing the resin to the metal. For example, the heat-sealing method involves heating the metal in advance to a temperature around the melting point of the resin (120 to 250" C) and then extruding it. A method of extruding molten resin onto metal using a machine, or a method of heating the metal as described above and then supplying a resin film onto the metal,
Adhesive strength can also be improved by a method of pressure bonding using a heated roll or heated press.
また金属が材質的に鉄や非鉄金属であっても、またそれ
らの表面に化成処理、めっき、プライマー塗装などの表
面処理が施されたものであっても接着強度を向上させる
ことができる。Furthermore, the adhesive strength can be improved even if the metal is iron or nonferrous metal, or even if the surface of the metal has been subjected to surface treatment such as chemical conversion treatment, plating, or primer coating.
次に実施例により本発明を説明する。Next, the present invention will be explained with reference to Examples.
（実施例）
金属として、溶融亜鉛めっき鋼板、この鋼板にリン酸亜
鉛処理を施したものおよびリン酸亜鉛処理とプライマー
（ウレタン変性ビス７エ７−ル型エポキシプライマー）
を塗装したものの３種を用意して、これらの上に押出機
により厚さ０．２１１１１６に成形した変性ポリオレフ
ィン樹脂フィルムと膜厚ｉｌｉ！整用のアルミニウムス
ペーサーとを乗せで、所定温度に加熱した加熱プレスで
５ｋｇ／ｃＩ１１２の加圧力で３分間加圧することによ
り熱融着させた。その後加熱プレスより鋼板を取り出し
で、種々の冷却速度で常温まで冷却し、ＪＩＳ Ｋ ６
８５４に規定する１８０°剥離試験を行い、剥離強度を
測定した。(Example) Metals include hot-dip galvanized steel sheet, zinc phosphate treatment on this steel sheet, and zinc phosphate treatment and primer (urethane modified bis7er type epoxy primer)
Three types of coatings were prepared, and on top of these, a modified polyolefin resin film was molded using an extruder to a thickness of 0.211116 and a film thickness of ili! A heating press heated to a predetermined temperature was used to apply pressure at a pressure of 5 kg/cI112 for 3 minutes to thermally fuse the aluminum spacer. After that, the steel plate is taken out from the hot press and cooled to room temperature at various cooling rates, and JIS K 6
A 180° peel test specified in 854 was conducted to measure the peel strength.
表１はこの測定剥離強度を示したものであるが、冷却速
度を１０℃／ｓｅｃ以下にして接着したものは剥離強度
が高い。Table 1 shows the measured peel strength, and those bonded at a cooling rate of 10° C./sec or less had high peel strength.
（効果）
以上のごとく本発明は変性ポリオレフィン樹１１けを金
属に熱融着した後に徐冷して極性基を金属面方向に配向
させることにより接着強度を向上させるのであるから、
樹脂としては変性量の少ないものでもよく、しかも接着
強度を向上させることができる。(Effects) As described above, the present invention improves adhesive strength by heat-sealing 11 modified polyolefin resins to metal and then slowly cooling them to orient the polar groups in the direction of the metal surface.
The resin may be one with a small amount of modification, and the adhesive strength can be improved.
Claims (4)
樹脂を冷却固化させて接着する接着方法において、樹脂
を冷却固化させる際溶融状態から常温まで１０℃／ｓｅ
ｃ以下の冷却速度で徐冷することを特徴とする変性ポリ
オレフィン樹脂と金属との接着方法。(1) In an adhesion method in which a modified polyolefin resin is thermally fused to a metal, the resin is cooled and solidified, and the resin is cooled and solidified at a temperature of 10°C/se from a molten state to room temperature.
A method for bonding a modified polyolefin resin and a metal, characterized by slow cooling at a cooling rate of c or less.
和カルボン酸をグラフト共重合させて変性したものであ
ることを特徴とする特許請求の範囲第１項に記載の変性
ポリオレフィン樹脂と金属との接着方法。(2) The method for bonding a modified polyolefin resin and a metal according to claim 1, wherein the modified polyolefin resin is modified by graft copolymerizing a polyolefin with an unsaturated carboxylic acid.
和カルボン酸の無水物をグラフト共重合させて変性した
ものであることを特徴とする特許請求の範囲第１項に記
載の変性ポリオレフィン樹脂と金属との接着方法。(3) Adhesion between the modified polyolefin resin and metal according to claim 1, wherein the modified polyolefin resin is modified by graft copolymerizing polyolefin with an anhydride of an unsaturated carboxylic acid. Method.
和カルボン酸をランダム共重合させて変性したものであ
ることを特徴とする特許請求の範囲第１項に記載の変性
ポリオレフィン樹脂と金属との接着方法。(4) The method for adhering a modified polyolefin resin and metal according to claim 1, wherein the modified polyolefin resin is modified by randomly copolymerizing a polyolefin with an unsaturated carboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61019535A JPS62178320A (en) | 1986-01-31 | 1986-01-31 | Method of adhesion between denatured polyolefin resin and metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61019535A JPS62178320A (en) | 1986-01-31 | 1986-01-31 | Method of adhesion between denatured polyolefin resin and metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62178320A true JPS62178320A (en) | 1987-08-05 |
| JPH0559816B2 JPH0559816B2 (en) | 1993-09-01 |
Family
ID=12002021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61019535A Granted JPS62178320A (en) | 1986-01-31 | 1986-01-31 | Method of adhesion between denatured polyolefin resin and metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62178320A (en) |
Citations (8)
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|---|---|---|---|---|
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| JPS5342072A (en) * | 1976-09-28 | 1978-04-17 | Toyo Bearing Mfg Co | Apparatus for measuring flow rate through area |
| JPS5342071A (en) * | 1976-09-28 | 1978-04-17 | Toyo Bearing Mfg Co | Apparatus for measuring flow rate through area |
| JPS5610422A (en) * | 1979-07-06 | 1981-02-02 | Ube Ind Ltd | Method of sheathing steel pipe |
| JPS5722751A (en) * | 1980-06-16 | 1982-02-05 | Kendall & Co | Treating device used for cooling treatment |
| JPS5825692A (en) * | 1981-08-07 | 1983-02-15 | 三洋電機株式会社 | Display unit |
| JPS60242052A (en) * | 1979-05-21 | 1985-12-02 | ザ ダウ ケミカル カンパニ− | Metal-plastic-metal structure laminate for molding |
| JPS61148027A (en) * | 1984-12-24 | 1986-07-05 | Idemitsu Petrochem Co Ltd | Manufacture of metal-resin laminate |
-
1986
- 1986-01-31 JP JP61019535A patent/JPS62178320A/en active Granted
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4916549A (en) * | 1972-06-06 | 1974-02-14 | ||
| JPS5342072A (en) * | 1976-09-28 | 1978-04-17 | Toyo Bearing Mfg Co | Apparatus for measuring flow rate through area |
| JPS5342071A (en) * | 1976-09-28 | 1978-04-17 | Toyo Bearing Mfg Co | Apparatus for measuring flow rate through area |
| JPS60242052A (en) * | 1979-05-21 | 1985-12-02 | ザ ダウ ケミカル カンパニ− | Metal-plastic-metal structure laminate for molding |
| JPS5610422A (en) * | 1979-07-06 | 1981-02-02 | Ube Ind Ltd | Method of sheathing steel pipe |
| JPS5722751A (en) * | 1980-06-16 | 1982-02-05 | Kendall & Co | Treating device used for cooling treatment |
| JPS5825692A (en) * | 1981-08-07 | 1983-02-15 | 三洋電機株式会社 | Display unit |
| JPS61148027A (en) * | 1984-12-24 | 1986-07-05 | Idemitsu Petrochem Co Ltd | Manufacture of metal-resin laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0559816B2 (en) | 1993-09-01 |
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