JPS62136274A - Method of applying radiation curable resin - Google Patents
Method of applying radiation curable resinInfo
- Publication number
- JPS62136274A JPS62136274A JP27623685A JP27623685A JPS62136274A JP S62136274 A JPS62136274 A JP S62136274A JP 27623685 A JP27623685 A JP 27623685A JP 27623685 A JP27623685 A JP 27623685A JP S62136274 A JPS62136274 A JP S62136274A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polyacrylic acid
- curable resin
- radiation
- coating
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 52
- 239000011347 resin Substances 0.000 title claims abstract description 52
- 230000005855 radiation Effects 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 32
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 39
- 239000011248 coating agent Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 6
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 230000002285 radioactive effect Effects 0.000 abstract 3
- 239000003973 paint Substances 0.000 description 16
- 238000010894 electron beam technology Methods 0.000 description 10
- 238000011282 treatment Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010422 painting Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- -1 )+77 grillisocyanate Chemical compound 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 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
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003999 initiator Substances 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
- 229920000647 polyepoxide Polymers 0.000 description 2
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 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
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 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
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は金属板に放射線硬化型、・樹脂を塗装する際金
属板を予めポリアクリル酸水溶液で前処理して、金属板
と放射線硬化型樹脂＠膜との塗膜密着法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention is a radiation-curable coating on a metal plate.When coating a metal plate with a resin, the metal plate is pre-treated with an aqueous polyacrylic acid solution. Regarding the method of adhesion of coating film with resin@membrane.
（従来技術）
従来塗装鋼板やラミネート鋼板などの製造は熱硬化型樹
脂の塗料や接着剤を使用して行うのが一般的であったが
、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が使用されるよう
になってきている。(Prior technology) Conventionally, painted steel plates and laminated steel plates were manufactured using thermosetting resin paints and adhesives, but in recent years, improvements in quality, resource saving, energy saving, and high productivity have been made. From these viewpoints, electron beam curable resins have come to be used.
例えば電子線硬化型樹脂の塗料を電子線により高度に架
橋反応させると、塗膜は非常にｍ密になるため、塗膜硬
度、耐汚染性、耐溶剤性などが者しく向上し、熱硬化型
塗料の塗装では得られない品質の塗装製品を製造するこ
とができる。For example, when electron beam curable resin paint is subjected to a high degree of crosslinking reaction with electron beams, the paint film becomes extremely dense, resulting in significant improvements in film hardness, stain resistance, solvent resistance, etc., and heat curing. It is possible to produce coated products with a quality that cannot be obtained by painting with mold paints.
しかしながら電子線硬化型樹脂の塗料は硬化の際硬化反
応が常温で急速に進行するため、塗膜の着しい収縮を伴
い、塗膜中に大きな残留応力が生じる。このため電子線
硬化型樹脂の塗料を金属板に直接塗装する場合、熱硬化
型樹脂の塗料に対しては塗膜密着性を向上させるＰ１１
械的研摩、リン酸塩処理、クロメート処理、酸洗などの
塗装前処理塗装した場合より劣るものであった。However, when curing electron beam curable resin paints, the curing reaction proceeds rapidly at room temperature, resulting in severe shrinkage of the paint film and the generation of large residual stress in the paint film. For this reason, when applying an electron beam-curable resin paint directly to a metal plate, P11, which improves the adhesion of the paint film to a thermosetting resin paint,
Pre-painting treatments such as mechanical polishing, phosphate treatment, chromate treatment, and pickling were inferior to those obtained by painting.
塗料や接着剤などにおける電子線硬化型樹脂の塗膜密着
性低下を改善する方法としては、金属板に電子線硬化型
樹脂を塗布する前に金属板との密着性の優れた熱硬化型
のエポキシ系樹脂塗料を下塗り塗装して、電子線硬化型
樹脂の硬化時の塗膜収縮を吸収する方法が知られている
。しかしこの方法はエポキシ系樹脂塗料の硬化にオーブ
ンのような設備を必要とするため、省資源、省エネルギ
ーなどの点でまだ問題があった。One way to improve the poor adhesion of electron beam curable resins in paints and adhesives is to apply a thermosetting resin that has excellent adhesion to the metal plate before applying the electron beam curable resin to the metal plate. A known method is to apply an undercoat of epoxy resin paint to absorb shrinkage of the paint film during curing of electron beam curable resin. However, since this method requires equipment such as an oven to cure the epoxy resin paint, there are still problems in terms of resource and energy conservation.
（発明が解決しようとする問題点）
本発明はこのように従来の塗装方法ではまだ種々の問題
点があったので、簡単な前処理で十分なる塗膜密着性の
得ら枕る放射線硬化型樹脂の塗装方法を提供するもので
ある。(Problems to be Solved by the Invention) As described above, the present invention has developed a radiation-curing type coating method that can obtain sufficient coating film adhesion with simple pretreatment, since there were still various problems with conventional coating methods. The present invention provides a resin coating method.
（問題点を解決するための手段）
本発明者らは放射線硬化型樹脂の塗膜密着性を向上させ
る塗装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、かつ放射線硬化型樹脂を
硬化させる際、放射線硬化型樹脂の塗膜を貫通して前処
理のポリアクリル酸皮膜まで達する強度の放射線を照射
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准
で処理して、乾燥皮膜量で１０〜１００ ｕ＋ｇ／＋ｎ
２の皮膜を形成した後、放射線硬化型樹脂液を塗布して
、ポリアクリル酸皮膜まで達する強度の放射線を照射し
て硬化させることをｖＦ徴としている。(Means for Solving the Problems) As a result of various studies on coating methods for improving coating adhesion of radiation-curable resins, the present inventors found that a polyacrylic acid aqueous solution was used as a pretreatment, and radiation-curable resins were It has been discovered that when curing the resin, it is sufficient to irradiate radiation with an intensity that penetrates the coating film of the radiation-curable resin and reaches the pre-treated polyacrylic acid film. The present invention was made based on this knowledge, and a metal plate is treated with aqueous polyacrylic acid to form a dry coating of 10 to 100 u+g/+n.
After forming the film No. 2, a radiation-curable resin liquid is applied and cured by irradiation with radiation strong enough to reach the polyacrylic acid film, which is the vF feature.
本発明において、金属板をポリアクリル酸水溶液で処理
すると放射線硬化型樹脂の塗膜密着性が向上する機構に
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（
−Ｃ００Ｈ）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放射
線硬化型樹脂を硬化させる際ポリアクリル酸皮膜まで達
する強度の放射線が照射されると、放射線によりラジカ
ルが発生するので、放射線硬化型樹脂とラジカル重合し
、化学的に結合する。このため放射線硬化型樹脂はポリ
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。In the present invention, the mechanism by which the coating adhesion of the radiation-curable resin 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. In other words, polyacrylic acid has a polar group (
-C00H) and an ethylenic double bond, the polar groups of the polyacrylic acid film are oriented on the surface of the metal plate and firmly adhere to the metal plate. On the other hand, when radiation-curable resin is cured, ethylenic double bonds are irradiated with radiation strong enough to reach the polyacrylic acid film, and the radiation generates radicals, which radically polymerizes with the radiation-curable resin and chemically Join. Therefore, it is thought that the radiation-curable resin adheres closely to the metal plate via the polyacrylic acid film.
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３，０００〜ＳＯ，ＯＯＯ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３，０００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、皮膜強度が弱く、皮膜のと
ころから剥離してしまい、一方５０，０００を越える高
分子量のものになると溶解しにくくなって、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。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 SO, OOO. If the molecular weight is less than 3,000, the cohesive force between the molecules is weak, so the film strength is weak and the film will peel off. This is because it becomes difficult to dissolve, making it difficult to maintain a stable aqueous solution at all times, making the coating operation unstable, and making it impossible to form a uniform film.
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７０−コート法など従来の公知方法で処理す
ればよい。There are no particular restrictions on the method for 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 70-coating method, etc. You can process it with
しかし処理の際ポリアクリル酸皮膜が乾燥皮膜ある。皮
膜量が１０１１１ｇ／＋２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、放射線硬化型樹脂を硬化
させる際放射線を皮・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、放射線硬化型樹脂塗膜との
ラジカル重合が起こりにくくなり、充分な層間蜜漬性が
得られず、逆に１００ ｍｇ／＋２を越えるとラジカル
発生量が者しく増加して、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、放射線硬化型樹脂の塗
膜密着性、特に加工時の密着性がかえって低下してしま
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か４０〜１２０°Ｃになる程度
に加熱すればよい。However, during processing, the polyacrylic acid film is a dry film. If the coating amount is less than 10111g/+2, the number of ethylenic double bonds on the coating surface will decrease, and even if radiation is irradiated until it reaches the coating/film when curing the radiation-curable resin, the amount of radicals generated will be insufficient. Therefore, radical polymerization with the radiation-curable resin coating film becomes difficult to occur, and sufficient interlayer absorption properties cannot be obtained.On the other hand, when the amount exceeds 100 mg/+2, the amount of radicals generated increases significantly, and the polyacrylic As the cross-linking reaction between acids progresses, the coating itself becomes hard and brittle, making it unable to withstand the internal stress that accompanies curing, and the coating adhesion of radiation-curable resins, especially during processing, deteriorates on the contrary. . Further, drying after application can be done by evaporating moisture, and in the case of forced drying, heating may be performed to an extent that the board temperature is 40 to 120°C.
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
した後放射線硬化型ｔＨ脂液を塗布し、ポリアクリル酸
皮膜に達する強度の放射線を照射し、硬化させる。樹脂
液の樹脂としては放射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チル樹脂、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）７
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ソ（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、ノアリル７タレ
ート、メチレンビスアクリルアミド、）＋７７グリルイ
ソシアネート、スチレン、（メタ）７クリロニトリル、
酢酸ビニルなどのモノマーである。放射線硬化型樹脂液
には同じ反応機構の反応性希釈剤を配合してもよく、顔
料や各種添加剤を配合してらよい。In the present invention, after forming a polyacrylic acid film as described above, a radiation-curable tH fat liquid is applied, and radiation of an intensity reaching the polyacrylic acid film is irradiated to cure it. Resins for the resin liquid include chilled resins with ethylenically unsaturated double bonds that can be radically polymerized by radiation, polyester (meth)acrylate, epoxy (meth)acrylate, polyurethane (meth)acrylate, and polyamide (meth)7.
Acrylates and oligomers such as polyol (meth)acrylates, or ethylene glycol (meth)acrylate, triethylene glycol (meth)acrylate, tetraethylene glycol so(meth)acrylate, trimethylolpropane tri(meth)acrylate, other (meth)acrylates Acrylic acid esters, noaryl 7-thaleate, methylene bisacrylamide, )+77 grillisocyanate, styrene, (meth)7-crylonitrile,
Monomers such as vinyl acetate. A reactive diluent having the same reaction mechanism may be added to the radiation-curable resin liquid, and pigments and various additives may also be added.
放射線硬化型樹脂の塗装塗膜厚は特に限定はなく、用途
に合わせて決定すればよい。硬化させる際の放射線照射
量は例えば放射線硬化型樹脂液の樹脂を電子線硬化型の
ものにして、乾燥塗膜厚で１０−５０μｆ１１塗装した
場合、１００ ＫｅＶ程度の加速電圧で５〜１５Ｍｒａ
ｄの＃ｉＩ量の電子線を照射すれば、硬化させることが
できるとともに、ポリアクリル酸皮膜とラジカル重合さ
せることができる。The coating thickness of the radiation-curable resin is not particularly limited and may be determined depending on the application. The amount of radiation irradiation during curing is, for example, when the radiation curable resin liquid is an electron beam curable resin and the dry coating thickness is 10-50 μf11, the amount of radiation irradiation is 5-15 Mra at an accelerating voltage of about 100 KeV.
By irradiating the electron beam in #iI amount of d, it can be cured and radically polymerized with the polyacrylic acid film.
なお樹脂を紫外線により硬化させる場合には樹脂液をク
リヤーまたは着色クリヤーにして、光重合開始剤を添加
する。光重合開始剤としては、ベンゾインメチルエーテ
ル、ベンゾインエチルエーテル、ベンゾインインプロピ
ルエーテル、ペンツインブチルエーテル、ベンゾ７エ／
ン／第３ ｉ＆アミン、ベンジルメチルケタール、２，
２−ジェトキシアセトフェノン、α−ヒドロキシイソブ
チロ７エ／ン、１ｆ１−ノクロロアセトフェノン、２−
クロロチオキサントンなどがあるが、これらを０．１〜
５重量％添加すれ１！′、２００ｎｍ−３５０ｎｍの紫
外線で硬化させることができる。なお着色クリヤー樹脂
液を塗布する場合は塗膜を薄くする。When the resin is cured by ultraviolet rays, the resin liquid is made clear or colored clear, and a photopolymerization initiator is added. As the photopolymerization initiator, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, pentwinbutyl ether, benzoin 7-ethyl ether,
/ 3rd i & amine, benzyl methyl ketal, 2,
2-jethoxyacetophenone, α-hydroxyisobutyro7ene, 1f1-nochloroacetophenone, 2-
There are chlorothioxanthone, etc., but these are 0.1~
Add 5% by weight 1! ', it can be cured with ultraviolet light of 200 nm to 350 nm. When applying colored clear resin liquid, the coating film should be thin.
本発明により放射線硬化型樹脂を塗装する場合、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。When coating a radiation-curable resin according to the present invention, if necessary, pre-painting treatments such as mechanical polishing, phosphate treatment, chromate treatment, pickling, etc., which are conventionally generally performed, are performed before applying the polyacrylic acid aqueous solution. It's okay.
また金属板は冷延鋼板、各種めっき鋼板、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。Further, the metal plate may be any of cold-rolled steel plates, various plated steel plates, steel plates such as stainless steel plates, and non-ferrous metal plates such as aluminum.
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）
亜鉛付着量Ｇ Ｏ９／＋６２の溶融亜鉛めっき鋼板（板
厚０．５ｎｖ＋）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、乾燥して祇燥皮
膜量が５〜１２０ ｒａｇ／ｍ２の皮膜を形成した。(Example) A hot-dip galvanized steel sheet (plate thickness 0.5 nv+) with a zinc coating amount G O9/+62 was treated with an aqueous solution containing polyacrylic acid having a molecular weight as shown in Table 1, and then dried to form a dry coating. A coating having an amount of 5 to 120 rag/m2 was formed.
その後この皮膜の上に表１に示すような種々の放射線硬
化型樹脂の樹脂液を塗布して、加速電圧１００ ＫｅＶ
、電子ａ１５ ＋ａへの条件で１０８ｒａｄ電子線を照
射して硬化させ、乾燥塗膜厚２０μｍの樹脂塗膜を形成
した。Thereafter, resin liquids of various radiation-curable resins as shown in Table 1 were applied onto this film, and an acceleration voltage of 100 KeV was applied.
, electron a15 +a was irradiated with a 108 rad electron beam to form a resin coating film with a dry coating thickness of 20 μm.
次にここで得られた塗ｘＡ鋼板に次のような塗膜密着性
試験を行った。Next, the following coating film adhesion test was conducted on the coated xA steel sheet obtained here.
（１）ゴバン目試験
塗装鋼板の塗膜面にカッターナイフで１＋ａ＋＋＋Ｘ１
τｎｌ１１のゴバン目を１００個切り刻み、そのゴバン
目部分にセロテープを貼り付けて剥離し、次の基準に従
って評価した。(1) Goban test: Apply 1+a+++X1 to the coating surface of the painted steel plate using a cutter knife.
100 gongs of τnl11 were cut into pieces, cellophane tape was applied to the goblets and peeled off, and evaluation was made according to the following criteria.
ｄ 塗膜剥離していないゴバン目数が８０以上のもの
Δ 塗膜剥離していないゴバン目数が８０未満５０以上
のもの
Ｘ 塗膜剥離していないゴバン目敗が５０未満のもの
（２）ゴバン目エリクセン試験
塗装鋼板に前記ゴバン目試験と同要領でゴバン目を切り
刻んだ後、そのゴバン目部分をエリクセン試験機で６１
１１１１１押し出して、セロテープを貼り付けて剥離し
、上記同基準で評価しｒこ。d Items with a goblin number of 80 or more that have not peeled off the paint film Δ Items with a gobane number of less than 80 and 50 or more that have not peeled off the paint film Goblin Erichsen Test After chopping the goblin marks on the coated steel plate in the same manner as in the above-mentioned goblin test, the goblin part was cut into 61 mm with an Erichsen tester.
11111 was extruded, cellophane tape was applied, peeled off, and evaluated using the same criteria described above.
表１にこの塗膜密着性試験結果をポリアクリル酸水溶液
および放射線硬化型樹脂の＋ｌ Ｍとともに示す。Table 1 shows the results of this coating film adhesion test along with the polyacrylic acid aqueous solution and +lM of the radiation curable resin.
表１に示すように、放射線硬化型樹脂液塗布前に分子［
３，０００〜５０，０００のポリアクリル酸を溶解下水
溶液で処理して乾燥皮膜量が１０〜１００ ｒａｇ／ｍ
２の皮膜を形成すれば、放射線硬化型樹脂の塗膜密着性
は従来の化成処理を施した場合より向上する。As shown in Table 1, the molecules [
3,000-50,000 polyacrylic acid is treated with a sewage solution to achieve a dry film amount of 10-100 rag/m
If the film No. 2 is formed, the coating adhesion of the radiation-curable resin will be improved compared to when conventional chemical conversion treatment is applied.
（効果）
以上のごとく、本発明の塗装方法は金属板をポリアクリ
ル酸水溶液で処理して、金属板と放射線硬化型樹脂の双
方に密着性の優れたポリアクリル酸皮膜を形成すること
により放射線硬化型樹脂の塗膜密着性を向上させるので
あるから、設備は簡単なものでよく、省資源、省エネル
ギーにすることができる。(Effects) As described above, the coating method of the present invention treats a metal plate with a polyacrylic acid aqueous solution to form a polyacrylic acid film with excellent adhesion on both the metal plate and the radiation-curable resin. Since the coating adhesion of the curable resin is improved, the equipment may be simple and resources and energy can be saved.
Claims (2)
皮膜量で１０〜１００ｍｇ／ｍ＾２の皮膜を形成した後
、放射線硬化型樹脂液を塗布して、ポリアクリル酸皮膜
まで達する強度の放射線を照射して硬化させることを特
徴とする放射線硬化型樹脂の塗装方法。(1) After treating a metal plate with a polyacrylic acid aqueous solution to form a film with a dry film amount of 10 to 100 mg/m^2, apply a radiation-curable resin liquid to achieve the strength of the polyacrylic acid film. A radiation-curable resin coating method characterized by curing by irradiating with radiation.
０〜５０，０００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
放射線硬化型樹脂の塗装方法。(2) As a polyacrylic acid aqueous solution, the molecular weight is 3,00
The method for coating a radiation-curable resin according to claim 1, characterized in that a solution of polyacrylic acid having a molecular weight of 0 to 50,000 is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27623685A JPH069675B2 (en) | 1985-12-09 | 1985-12-09 | Radiation-curable resin coating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27623685A JPH069675B2 (en) | 1985-12-09 | 1985-12-09 | Radiation-curable resin coating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62136274A true JPS62136274A (en) | 1987-06-19 |
| JPH069675B2 JPH069675B2 (en) | 1994-02-09 |
Family
ID=17566592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27623685A Expired - Lifetime JPH069675B2 (en) | 1985-12-09 | 1985-12-09 | Radiation-curable resin coating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH069675B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03221449A (en) * | 1990-01-29 | 1991-09-30 | Nippon Denkai Kk | Metal foil with ultraviolet cured water base resin, and metal coated laminate sheet with ultraviolet cured water base resin, and manufacture thereof and removing method of cured film thereof |
| JPH0539624U (en) * | 1991-10-30 | 1993-05-28 | 大日本スクリーン製造株式会社 | Particle remover |
-
1985
- 1985-12-09 JP JP27623685A patent/JPH069675B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03221449A (en) * | 1990-01-29 | 1991-09-30 | Nippon Denkai Kk | Metal foil with ultraviolet cured water base resin, and metal coated laminate sheet with ultraviolet cured water base resin, and manufacture thereof and removing method of cured film thereof |
| JPH0539624U (en) * | 1991-10-30 | 1993-05-28 | 大日本スクリーン製造株式会社 | Particle remover |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH069675B2 (en) | 1994-02-09 |
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