JPH0562896B2 - - Google Patents
Info
- Publication number
- JPH0562896B2 JPH0562896B2 JP27623785A JP27623785A JPH0562896B2 JP H0562896 B2 JPH0562896 B2 JP H0562896B2 JP 27623785 A JP27623785 A JP 27623785A JP 27623785 A JP27623785 A JP 27623785A JP H0562896 B2 JPH0562896 B2 JP H0562896B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- electron beam
- adhesive
- polyacrylic acid
- metal plate
- 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.)
- Expired - Lifetime
Links
- 239000000853 adhesive Substances 0.000 claims description 48
- 230000001070 adhesive effect Effects 0.000 claims description 48
- 238000010894 electron beam technology Methods 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 229920002125 Sokalan® Polymers 0.000 claims description 28
- 239000004584 polyacrylic acid Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 239000002648 laminated material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920003002 synthetic resin Polymers 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000000057 synthetic resin Substances 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 238000011282 treatment Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- -1 tackifiers Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910000576 Laminated steel Inorganic materials 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
（産業上の利用分野）
本発明は金属板に電子線硬化型樹脂接着剤を使
用ラミネート金属板を製造する際金属板を予めポ
リアクリル酸水溶液で前処理して、金属板と接着
剤との密着性を大幅に向上させるラミネート金属
板の製造方法に関する。
（従来技術）
従来ラミネート鋼板の製造は熱硬化型樹脂の接
着剤を使用して行うのが一般的であつたが、近年
品質の向上、省資源、省エネルギー、高生産性な
どの観点から電子線硬化型樹脂のものを使用して
行うことが試みられている。これは電子線硬化型
樹脂の場合電子線により硬化させると高度に架橋
反応して、樹脂が非常に緻密になるため、接着強
度が高く、またラミネート材が熱劣化や外観変化
を受けやすいものであつても、熱影響を与えるこ
となくラミネートでき、高品質の製品を製造でき
るからである。
しかしながら接着剤の電子線硬化型樹脂は硬化
の際硬化反応が常温で急速に進行するため、接着
剤層が著しく収縮し、接着剤層中に大きな残留応
力が生じる。このため電子線硬化型樹脂の接着剤
を金属板に直接塗布してラミネートした場合、接
着強度は低いものであつた。特にこの接着強度は
熱硬化型樹脂接着剤に対して通常接着強度を向上
させる硬化のある機械的研摩、リン酸塩処理、ク
ロメート処理、酸洗などの前処理を施しても、あ
まり大きくならないものであつた。
（発明が解決しようとする問題点）
本発明はこのように電子線硬化型樹脂接着剤使
用によるラミネート金属板の製造方法にはまだ接
着強度を高くする方法が確立されていなかつたの
で、接着強度を高くすることができる製造方法を
提供するものである。
（問題点を解決するための手段）
本発明者らは電子線硬化型樹脂接着剤の接着強
度を向上させる方法について種々検討した結果、
前処理としてポリアクリル酸水溶液を使用し、か
つ接着剤を硬化させる際、ラミネート材のみなら
ず接着剤層をも貫通して前処理のポリアクリル酸
皮膜まで達する強度の電子線を照射すればよいこ
とを見出だした。本発明はかかる知見に基づいて
なされたもので、金属板をポリアクリル酸水溶液
で処理して、乾燥皮膜量で10〜100mg／m2の皮膜
を形成した後、電子線硬化型樹脂接着剤を塗布し
て、フイルム状ラミネート材をラミネートし、し
かる後にポリアクリル酸皮膜にまで達する強度の
電子線を照射して接着剤を硬化させることにより
フイルム状ラミネート材を金属板に接着すること
を特徴としている。
本発明において、金属板をポリアクリル酸水溶
液で処理すると電子線硬化型樹脂接着剤の接着強
度が向上する機構については理論的に十分解明さ
れていないが、これは次のように考えられる。す
なわちポリアクリル酸は極性基（−COOH）と
エチレン性二重結合とを有するので、ポリアクリ
ル酸皮膜は極性基が金属板の面に配向して、金属
板と強固に密着する。一方エチレン性二重結合は
ラミネート後接着剤を硬化させる際ポリアクリル
酸皮膜まで達する強度の電子線が照射されると、
電子線によりラジカルが発生するので、接着剤と
ラジカル重合し、化学的に結合する。このため接
着剤はポリアクリル酸皮膜を介して金属板に密着
するものと考えられる。
本発明で金属板の処理に使用するポリアクリル
酸水溶液としては、分子量が3000〜50000のポリ
アクリル酸を溶解したものを使用するのが好まし
い。これは分子量が3000未満の低分子量のもので
あると分子相互の凝集力が弱いため、比較強度が
弱く、皮膜のところから剥離してしまい、一方
50000を越える高分子量のものになると溶解しに
くくなつて、常時安定した水溶液に保つのが困難
になり、塗布作業が不安定になるとともに、均一
な皮膜を形成することができなくなるからであ
る。
金属板をポリアクリル酸水溶液で処理する方法
としては特に制限がなく、例えばスプレー法、浸
漬ロール絞り法、浸漬エアナイフ絞り法、ロール
コート法、刷毛塗り法、カーテンフローコート法
など従来の公知方法で処理すればよい。
しかし処理の際ポリアクリル酸皮膜が乾燥皮膜
量で10〜100mg／m2になるようにする必要がある。
皮膜量が10mg／m2未満であると皮膜表面のエチレ
ン性二重結合数が減少して、接着剤を硬化させる
際電子線を皮膜に達するまで照射しても、ラジカ
ル発生量が不足するため、接着剤とラジカル重合
が起こりにくくなり、充分な層間密着性が得られ
ず、逆に100mg／m2を越えるとラジカル発生量が
著しく増加して、ポリアクリル酸同志の架橋反応
が進行し、皮膜自体が硬く、脆くなる結果、硬化
に伴う内部応力に耐えられなくなり、接着剤との
接着強度、特に加工時の接着強度がかえつて低下
してしまう。また塗布後の乾燥は水分を蒸発させ
ればよく、強制乾燥させる場合には板温が40〜
120℃になる程度に加熱すればよい。
本発明では以上のようにしてポリアクリル酸皮
膜を形成した後電子線硬化型樹脂接着剤を塗布
し、さらにその上にフイルム状ラミネート材をラ
ミネートして、接着剤、ラミネート材を貫通して
ポリアクリル酸皮膜に達する強度の電子線を照射
し、硬化させる。接着剤の樹脂としては電子線に
よりラジカル重合可能なエチレン性不飽和二重結
合を有するものであればよく、例えば不飽和ポリ
エステル樹脂、ポリエステル（メタ）アクリレー
ト、エポキシ（メタ）アクリレート、ポリウレタ
ン（メタ）アクリレート、ポリアミド（メタ）ア
クリレートおよびポリオール（メタ）アクリレー
トなどのオリゴマー、あるいはエチレングリコー
ル（メタ）アクリレート、トリエチレングリコー
ル（メタ）アクリレート、テトラエチレングリコ
ールジ（メタ）アクリレート、トリメチロールプ
ロパントリ（メタ）アクリレート、他の（メタ）
アクリル酸エステル類、ジアリルフタレートメチ
レンビスアクリルアミド、トリアクリルイソシア
ネート、スチレン、（メタ）アクリロニトリル、
酢酸ビニルなどのモノマーである。接着剤には必
要に応じて他の重合体樹脂、粘着付与剤、顔料、
各種添加剤を配合してもよい。
電子線硬化型樹脂接着剤の塗布量は限定はない
が、通常乾燥塗布量で10〜30ｇ／m2塗布すればよ
い。
電子線硬化型樹脂接着剤の上にラミネートする
フイルム状ラミネート材は電子線により接着剤を
硬化させる際に接着剤と反応する合成樹脂フイル
ムが好ましいが、これは必須条件ではなく、他の
合成樹脂フイルムや金属箔であつてもよい。使用
できる合成樹脂フイルムとしては、塩化ビニル、
塩化ビニルー塩化ビニリデン共重合体、ポリエチ
レンおよびポリプロピレンなどのビニル系重合体
フイルム、ポリエチレンテレフタレート、アクリ
レートおよびポリカーボネートなどのエステル系
フイルム、ナイロン、イミドーアミド系などのア
ミド系フイルムなどがあり、また金属箔として
は、金、銀、Al、Cu、Feおよびステンレス鋼な
どがある。なお一般に使用されている電子線加速
器は最大加速電圧が200〜500KeV程度であるの
で、電子線の透過上合成樹脂フイルムの厚みは
400μm以下、金属箔の厚みは50〜100μmにするの
が好ましい。この場合電子線は線量５〜15Mrad
照射すればポリアクリル酸皮膜まで透過させるこ
とができる。
本発明により電子線硬化型樹脂接着剤を塗布す
る場合、必要であればポリアクリル酸水溶液塗布
前に従来一般に行われている機械的研摩、リン酸
塩処理、クロメート処理、酸洗などの塗装前処理
を施してもよい。
金属板は冷延鋼板、各種めつき鋼板、ステンレ
ス鋼板などの鋼板、アルミニウムに代表される非
鉄金属板いずれでもよい。
次に実施例により本発明を説明する。
（実施例）
亜鉛付着量60ｇ／m2の溶融亜鉛めつき鋼板（板
厚0.6mm）を表１に示すような分子量のポリアク
リル酸を溶解した水溶液で処理した後、100℃で
１分間乾燥して、乾燥皮膜量が５〜110mg／m2の
皮膜を形成した。その後この皮膜の上に表１に示
すような電子線硬化型樹脂を主成分とする接着剤
を塗布して、その上に厚みが100μmの軟質塩化ビ
ニルフイルムをラミネートし、フイルム側から加
速電圧200KeV、電子流20mAの条件で5Mrad電
子線を照射してラミネート鋼板を製造した。
次に以上のようにして製造したラミネート鋼板
に対してJIS Ｋ 6744「ポリ塩化ビニル金属積層
板」に規定された剥離試験（剥離強度測定）とエ
リクセン試験を行い、ラミネートフイルムの接着
性を調査した。表１にこの結果を示す、なおエリ
クセン試験の評価は次の基準によつた。
○ 剥離なし
△ 剥離50％未満
× 剥離50％以上
(Industrial Application Field) The present invention uses an electron beam-curable resin adhesive on a metal plate. When producing a laminated metal plate, the metal plate is pretreated with a polyacrylic acid aqueous solution to bond the metal plate and the adhesive. This invention relates to a method for manufacturing laminated metal plates that significantly improves adhesion. (Prior technology) Conventionally, laminated steel sheets were manufactured using thermosetting resin adhesives, but in recent years, electron beams have been used to improve quality, save resources, save energy, and increase productivity. Attempts have been made to use curable resin. This is because when electron beam-curable resins are cured with electron beams, they undergo a highly cross-linking reaction and become extremely dense, resulting in high adhesive strength and the laminate material being susceptible to thermal deterioration and changes in appearance. This is because even if there is a problem, it can be laminated without any heat effects, and high-quality products can be manufactured. However, since the curing reaction of the electron beam curable resin adhesive proceeds rapidly at room temperature during curing, the adhesive layer shrinks significantly and a large residual stress is generated in the adhesive layer. For this reason, when an adhesive made of an electron beam curable resin is applied directly to a metal plate and laminated, the adhesive strength is low. In particular, this adhesive strength does not increase significantly even if pre-treatments such as mechanical polishing, phosphate treatment, chromate treatment, pickling, etc., which normally improve the adhesive strength of thermosetting resin adhesives, are applied. It was hot. (Problems to be Solved by the Invention) The present invention solves the problem that the method for producing laminated metal plates using an electron beam curable resin adhesive has not yet established a method for increasing the adhesive strength. The purpose of the present invention is to provide a manufacturing method that can increase the (Means for Solving the Problems) As a result of various studies by the present inventors on methods for improving the adhesive strength of electron beam curable resin adhesives,
When using a polyacrylic acid aqueous solution as a pretreatment and curing the adhesive, it is sufficient to irradiate the electron beam with an intensity that penetrates not only the laminate material but also the adhesive layer and reaches the pretreatment polyacrylic acid film. I found out something. The present invention was made based on this knowledge, and after treating a metal plate with an aqueous polyacrylic acid solution to form a film with a dry film amount of 10 to 100 mg/ m2 , an electron beam curable resin adhesive is applied. The method is characterized in that the film-like laminate material is bonded to the metal plate by applying an adhesive, laminating the film-like laminate material, and then curing the adhesive by irradiating it with an electron beam of intensity that reaches the polyacrylic acid film. There is. In the present invention, the mechanism by which the adhesive strength of the electron beam curable resin adhesive is improved when a metal plate is treated with an aqueous polyacrylic acid solution has not been fully elucidated theoretically, but this is thought to be as follows. That is, since polyacrylic acid has a polar group (-COOH) and an ethylenic double bond, the polar groups of the polyacrylic acid film are oriented on the surface of the metal plate, and the polyacrylic acid film is tightly adhered to the metal plate. On the other hand, when the ethylenic double bond is irradiated with an electron beam strong enough to reach the polyacrylic acid film when curing the adhesive after lamination,
Since radicals are generated by the electron beam, they undergo radical polymerization with the adhesive and are chemically bonded. Therefore, it is thought that the adhesive adheres closely to the metal plate via the polyacrylic acid film. As the polyacrylic acid aqueous solution used in the treatment of metal plates in the present invention, it is preferable to use a polyacrylic acid solution having a molecular weight of 3,000 to 50,000. If the molecular weight is low (less than 3000), the cohesive force between the molecules is weak, so the strength is weak, and the film peels off.
If the molecular weight exceeds 50,000, it becomes difficult to dissolve, making it difficult to maintain a stable aqueous solution at all times, making the coating process unstable and making it impossible to form a uniform film. There are no particular restrictions on the method of treating a metal plate with an aqueous polyacrylic acid solution, and conventionally known methods such as a spray method, immersion roll drawing method, immersion air knife drawing method, roll coating method, brush coating method, curtain flow coating method, etc. Just process it. However, during the treatment, it is necessary to control the polyacrylic acid film to have a dry film amount of 10 to 100 mg/m 2 .
If the film amount is less than 10mg/ m2 , the number of ethylenic double bonds on the film surface will decrease, and even if the electron beam is irradiated until it reaches the film when curing the adhesive, the amount of radicals generated will be insufficient. , radical polymerization with the adhesive becomes difficult to occur, and sufficient interlayer adhesion cannot be obtained.On the other hand, when the amount exceeds 100mg/ m2 , the amount of radicals generated increases significantly, and the crosslinking reaction between polyacrylic acids progresses. As a result of the film itself becoming hard and brittle, it is unable to withstand the internal stress that accompanies curing, and the adhesive strength with the adhesive, particularly during processing, is reduced. In addition, drying after application can be done by evaporating the water, and if forced drying, the plate temperature should be 40~40℃.
Just heat it to 120℃. In the present invention, after forming a polyacrylic acid film as described above, an electron beam curable resin adhesive is applied, and a film-like laminate material is further laminated on top of the polyacrylic acid film, and the polyacrylic acid film is penetrated through the adhesive and laminate material to form a polyacrylic acid film. It is irradiated with an electron beam strong enough to reach the acrylic acid film and cured. The adhesive resin may be any resin having an ethylenically unsaturated double bond that can be radically polymerized by electron beams, such as unsaturated polyester resin, polyester (meth)acrylate, epoxy (meth)acrylate, polyurethane (meth)acrylate, etc. Oligomers such as acrylate, polyamide (meth)acrylate and polyol (meth)acrylate, or ethylene glycol (meth)acrylate, triethylene glycol (meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , other (meta)
Acrylic acid esters, diallylphthalate methylene bisacrylamide, triacryl isocyanate, styrene, (meth)acrylonitrile,
Monomers such as vinyl acetate. The adhesive may contain other polymer resins, tackifiers, pigments,
Various additives may be added. There is no limit to the amount of the electron beam curable resin adhesive applied, but it is usually sufficient to apply the dry amount of 10 to 30 g/m 2 . The film-like laminate material to be laminated on top of the electron beam-curable resin adhesive is preferably a synthetic resin film that reacts with the adhesive when it is cured by the electron beam, but this is not an essential condition, and other synthetic resins may be used. It may also be a film or metal foil. Synthetic resin films that can be used include vinyl chloride,
There are vinyl polymer films such as vinyl chloride-vinylidene chloride copolymer, polyethylene and polypropylene, ester films such as polyethylene terephthalate, acrylate and polycarbonate, and amide films such as nylon and imido-amide films.Metal foils include: These include gold, silver, Al, Cu, Fe and stainless steel. In addition, since the maximum acceleration voltage of commonly used electron beam accelerators is about 200 to 500 KeV, the thickness of the synthetic resin film is limited in terms of electron beam transmission.
It is preferable that the thickness of the metal foil is 400 μm or less, and the thickness of the metal foil is 50 to 100 μm. In this case, the electron beam dose is 5 to 15 Mrad.
If irradiated, it can penetrate to the polyacrylic acid film. When applying the electron beam curable resin adhesive according to the present invention, if necessary, the conventional methods of mechanical polishing, phosphate treatment, chromate treatment, pickling, etc. are performed before applying the polyacrylic acid aqueous solution. Processing may be performed. The metal plate may be a cold-rolled steel plate, various plated steel plates, steel plates such as stainless steel plates, or non-ferrous metal plates such as aluminum. Next, the present invention will be explained with reference to examples. (Example) A hot-dip galvanized steel plate (plate thickness 0.6 mm) with a zinc coating amount of 60 g/m 2 was treated with an aqueous solution containing polyacrylic acid having a molecular weight as shown in Table 1, and then dried at 100°C for 1 minute. A film having a dry film amount of 5 to 110 mg/m 2 was formed. Then, on top of this film, an adhesive mainly composed of electron beam curable resin as shown in Table 1 is applied, and a soft vinyl chloride film with a thickness of 100 μm is laminated on top of the adhesive, and an acceleration voltage of 200 KeV is applied from the film side. A laminated steel plate was manufactured by irradiating with a 5 Mrad electron beam at an electron current of 20 mA. Next, the laminated steel sheet manufactured as described above was subjected to a peel test (peel strength measurement) and an Erichsen test specified in JIS K 6744 "Polyvinyl chloride metal laminates" to investigate the adhesion of the laminate film. . The results are shown in Table 1.Evaluation of the Erichsen test was based on the following criteria. ○ No peeling △ Less than 50% peeling × 50% or more peeling
【表】【table】
【表】
表１に示すように、電子線硬化型樹脂接着剤塗
布前に分子量3000〜50000のポリアクリル酸を溶
解した水溶液で処理して乾燥皮膜量が10〜100
mg／m2の皮膜を形成すれば、接着剤の接着強度は
従来の化成処理を施した場合より向上する。
（効果）
以上のごとく、本発明によれば従来接着強度を
向上させるのに困難であつた電子線硬化型樹脂接
着剤使用によるラミネート金属板の接着強度を向
上させることができ、電子線硬化型樹脂接着剤使
用による高品質のラミネート金属板の製造が可能
になる。[Table] As shown in Table 1, before applying an electron beam curable resin adhesive, it is treated with an aqueous solution containing polyacrylic acid with a molecular weight of 3,000 to 50,000 to achieve a dry film weight of 10 to 100.
If a film of mg/m 2 is formed, the adhesive strength of the adhesive will be improved compared to when conventional chemical conversion treatment is applied. (Effects) As described above, according to the present invention, it is possible to improve the adhesive strength of laminated metal plates using an electron beam curable resin adhesive, which has been difficult to improve in the past. It becomes possible to manufacture high-quality laminated metal plates using resin adhesives.
Claims (1)
乾燥皮膜量で10〜100mg／m2の皮膜を形成した後、
電子線硬化型樹脂接着剤を塗布して、フイルム状
ラミネート材をラミネートし、しかる後にポリア
クリル酸にまで達する強度の電子線を照射して接
着剤を硬化させることによりフイルム状ラミネー
ト材を金属板に接着することを特徴とする電子線
硬化型樹脂接着剤によるラミネート金属板の製造
方法。 ２ ポリアクリル酸水溶液として、分子量が3000
〜50000のポリアクリル酸を溶解したものを使用
することを特徴とする特許請求の範囲第１項に記
載の電子線硬化型樹脂接着剤によるラミネート金
属板の製造方法。 ３ フイルム状ラミネート材として合成樹脂フイ
ルムをラミネートすることを特徴とする特許請求
の範囲第１項に記載の電子線硬化型樹脂接着剤に
よるラミネート金属板の製造方法。 ４ フイルム状ラミネート材として金属箔をラミ
ネートすることを特徴とする特許請求の範囲第１
項に記載の電子線硬化型樹脂接着剤によるラミネ
ート金属板の製造方法。[Claims] 1. Treating a metal plate with a polyacrylic acid aqueous solution,
After forming a film with a dry film amount of 10 to 100 mg/ m2 ,
The film-like laminate material is laminated by applying an electron beam-curable resin adhesive, and then the film-like laminate material is bonded to a metal plate by irradiating the film-like laminate material with an electron beam with an intensity that reaches up to polyacrylic acid and curing the adhesive. A method for producing a laminated metal plate using an electron beam curable resin adhesive. 2 As a polyacrylic acid aqueous solution, the molecular weight is 3000.
A method for manufacturing a laminated metal plate using an electron beam curable resin adhesive according to claim 1, characterized in that a solution of polyacrylic acid of 50,000 to 50,000 is used. 3. A method for producing a laminated metal plate using an electron beam curable resin adhesive according to claim 1, characterized in that a synthetic resin film is laminated as the film-like laminate material. 4 Claim 1, characterized in that metal foil is laminated as a film-like laminate material.
A method for producing a laminated metal plate using the electron beam curable resin adhesive described in 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27623785A JPS62135535A (en) | 1985-12-09 | 1985-12-09 | Production of laminated metal sheet by using electron beam-curable resin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27623785A JPS62135535A (en) | 1985-12-09 | 1985-12-09 | Production of laminated metal sheet by using electron beam-curable resin adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62135535A JPS62135535A (en) | 1987-06-18 |
| JPH0562896B2 true JPH0562896B2 (en) | 1993-09-09 |
Family
ID=17566606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27623785A Granted JPS62135535A (en) | 1985-12-09 | 1985-12-09 | Production of laminated metal sheet by using electron beam-curable resin adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62135535A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2640703B2 (en) * | 1991-12-26 | 1997-08-13 | 東洋鋼鈑株式会社 | Method for producing resin-coated metal plate by irradiation |
-
1985
- 1985-12-09 JP JP27623785A patent/JPS62135535A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62135535A (en) | 1987-06-18 |
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