JPH01149865A - Surface treating solution for aluminum and alloy thereof - Google Patents
Surface treating solution for aluminum and alloy thereofInfo
- Publication number
- JPH01149865A JPH01149865A JP30799287A JP30799287A JPH01149865A JP H01149865 A JPH01149865 A JP H01149865A JP 30799287 A JP30799287 A JP 30799287A JP 30799287 A JP30799287 A JP 30799287A JP H01149865 A JPH01149865 A JP H01149865A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- polyacrylic acid
- water
- film
- ink
- 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.)
- Pending
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000956 alloy Substances 0.000 title abstract description 5
- 229910045601 alloy Inorganic materials 0.000 title abstract 2
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 31
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims description 38
- 238000004381 surface treatment Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 22
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 21
- 150000003623 transition metal compounds Chemical class 0.000 claims description 17
- 229920000620 organic polymer Polymers 0.000 claims 1
- 238000011282 treatment Methods 0.000 abstract description 41
- 239000000976 ink Substances 0.000 abstract description 35
- 239000011347 resin Substances 0.000 abstract description 30
- 229920005989 resin Polymers 0.000 abstract description 30
- 238000000576 coating method Methods 0.000 abstract description 29
- 239000011248 coating agent Substances 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 17
- 238000002845 discoloration Methods 0.000 abstract description 15
- 238000012545 processing Methods 0.000 abstract description 10
- 238000009835 boiling Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- 229910000765 intermetallic Inorganic materials 0.000 abstract 2
- 230000007704 transition Effects 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 14
- 239000003973 paint Substances 0.000 description 14
- 238000007639 printing Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- 235000013361 beverage Nutrition 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000010422 painting Methods 0.000 description 4
- 239000003788 bath preparation Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- 238000002048 anodisation reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 230000002747 voluntary effect Effects 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019501 NaVO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004649 discoloration prevention Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はアルミニウムおよびアルミニウム合金の表面処
理液に関し、さらに詳しくは、高温水に接する部材用と
して耐蝕性に浸れ、かつ、密着性に優れたアルミニウム
およびアルミニウム合金の表面処理液に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a surface treatment liquid for aluminum and aluminum alloys, and more specifically, it is a surface treatment liquid for aluminum and aluminum alloys that is corrosion resistant and has excellent adhesion for use in parts that come into contact with high-temperature water. Related to surface treatment liquids for aluminum and aluminum alloys.
［従来技術］
一般に、アルミニウムおよびアルミニウム合金は、美観
、成形加工性および耐蝕性等に優れた特色を有している
ため、飲料容器、そのキャップ、また、建築材料等に広
く使用されている。[Prior Art] In general, aluminum and aluminum alloys have excellent features such as good appearance, moldability, and corrosion resistance, and are therefore widely used in beverage containers, their caps, and building materials.
しかしながら、アルミニウムおよびアルミニウム合金は
、高温水に暴露されると黒く変色したり、また、高温の
水蒸気に暴露されると白く変色することがあり、そのた
め、この黒色変色および白色変色を防止するには、アル
ミニウムおよびアルミニウム合金に変色を防止するため
の表面処理液が必要とされている。However, aluminum and aluminum alloys can turn black when exposed to high-temperature water or turn white when exposed to high-temperature steam, so there is no way to prevent this black and white discoloration. There is a need for a surface treatment solution to prevent discoloration on aluminum and aluminum alloys.
そして、この変色防止処理法において飲料容器部材では
、アルミニウムおよびアルミニウム合金の表面に燐酸ク
ロメート処理を行なったり、燐酸クロメート処理後樹脂
塗装を行なう方法がある。In this discoloration prevention treatment method, for beverage container members, there is a method in which the surface of aluminum and aluminum alloy is subjected to phosphoric acid chromate treatment, or a method in which resin coating is applied after phosphoric acid chromate treatment.
しかし、このような従来技術には以下説明するような問
題がある。However, such conventional technology has problems as described below.
即ち、燐酸クロメート処理を行なっても高温水或いは高
温水蒸気に暴露されると、このような処理を行なわない
アルミニウムおよびアルミニウム合金と同様に表面に黒
色変化または白色変色が発生して美観を損ない、実用」
二問題となる場合がある。In other words, even if phosphoric acid chromate treatment is performed, when exposed to high-temperature water or high-temperature steam, the surface will develop a black or white discoloration similar to aluminum and aluminum alloys that are not subjected to such treatment, impairing the aesthetic appearance and making it unsuitable for practical use. ”
There may be two problems.
また、燐酸クロメート処理液は、クロム酸塩、燐酸塩、
弗化物から構成されており、処理液の毒性が強く、処理
液の取り扱い、排水処理および排水処理により生成され
るスラッジの廃棄処分等に困難を来すという問題がある
。In addition, the phosphoric acid chromate treatment solution can contain chromate, phosphate,
It is composed of fluoride, and the treatment liquid is highly toxic, making it difficult to handle the treatment liquid, treat wastewater, and dispose of the sludge produced by wastewater treatment.
さらに、燐酸クロメート処理後に樹脂塗装を行なう方法
は、アルミニウムおよびアルミニウム合金表面に生成さ
れた燐酸クロメート皮膜により、アルミニウムおよびア
ルミニウム合金と樹脂皮膜との密着性を高め、高温水或
いは高温水蒸気との接触により発生する黒色変色または
白色変色を防止するためには、充分な性能が得られるが
、燐酸クロメート処理等の化成処理に比べて生産性やコ
ストの面で不利である。Furthermore, in the method of applying resin coating after phosphoric acid chromate treatment, the phosphoric acid chromate film formed on the surface of aluminum and aluminum alloys improves the adhesion between the aluminum and aluminum alloys and the resin film, and when it comes into contact with high-temperature water or high-temperature steam, Although sufficient performance can be obtained to prevent black discoloration or white discoloration that occurs, it is disadvantageous in terms of productivity and cost compared to chemical conversion treatments such as phosphoric acid chromate treatment.
しかして、飲料容器やキャップ等に用いられるアルミニ
ウムおよびアルミニウム合金においては、その外表面に
塗料を塗装焼き付けするだけでなく、成形加工前に装飾
のためのインキ印刷や樹脂塗装を行なうことがある。However, in the case of aluminum and aluminum alloys used for beverage containers, caps, etc., not only paint is baked on the outer surface, but also ink printing or resin coating is sometimes applied for decoration before molding.
従って、例えば、インキを印刷するものについては、絞
り加工等の成形加工後もインキの剥離が生じないという
良好な密着性が要求されるが、インキには多量の顔料が
含まれているため、塗料に比較しても加工密着性が劣り
、脱脂したアルミニウムおよびアルミニウム合金材に直
接インキを印刷しても密着性が悪く、これを補うために
０，５〜２ｇ／ｍのサイズコートを施した後に、インキ
を印刷する方法が採用されている。Therefore, for example, for products that print ink, good adhesion is required so that the ink does not peel off even after forming processes such as drawing, but since ink contains a large amount of pigment, Compared to paint, it has poor adhesion when processed, and even when ink is printed directly on degreased aluminum and aluminum alloy materials, adhesion is poor, so a size coat of 0.5 to 2 g/m was applied to compensate for this. Later, a method of printing ink was adopted.
そして、このサイズコートには、アルミニウムおよびア
ルミニウム合金材とインキの双方に対する密着性が良好
なエボキンエステル、塩化ビニル−酢酸ビニル共重合体
または変性ビニルが使用されている。This size coat uses Evokin ester, vinyl chloride-vinyl acetate copolymer, or modified vinyl, which has good adhesion to both aluminum and aluminum alloy materials and ink.
また、インキ印刷を行なう塗装方式は、通常、切り板を
片面ずつ塗装するウィケットタイプであり、（ザイズコ
ート塗布−焼き付は−インキ印刷→ツヤニス塗布→焼き
付けまたはサイズコート塗布−焼き付は−インキ印刷−
焼きイ」け−ツヤニス塗布→焼き付け）の順で行なわれ
ることから、工程が非常に複雑で、かつ、生産性の点で
問題があることも指摘されている。In addition, the coating method for ink printing is usually a wicket type in which the cut board is painted one side at a time. Print-
It has also been pointed out that because the process is performed in the following order: baking, applying gloss varnish, and then baking, the process is extremely complicated and there are problems in terms of productivity.
さらに、アルミニウムおよびアルミニウム合金材の塗装
下地処理の一般的な方法として化成処理法があり、この
方法はサイズコートに代わる処理法として用いると、コ
イルフオームで連続的に処理が可能であり、かつ、焼き
付は等が不必要になるため、生産上有利であるが、化成
処理法として代表的な燐酸クロメート処理や陽極酸化処
理を行なった場合にはインキに対する密着性が不足して
おり、深絞り加工のような強加工を行なった時には、密
着性の低下により剥離が生じ、また、耐蝕性が充分でな
いことから、上記のサイズコートに代わるものではない
。Furthermore, there is a chemical conversion treatment method as a general method for pre-painting aluminum and aluminum alloy materials, and when this method is used as a treatment method in place of size coating, it is possible to continuously treat the coil form, and, This is advantageous in terms of production because it eliminates the need for burning, etc. However, when phosphoric acid chromate treatment or anodization treatment, which is typical as a chemical conversion treatment, has insufficient adhesion to ink, deep drawing When subjected to strong processing such as machining, peeling occurs due to decreased adhesion, and corrosion resistance is not sufficient, so it cannot be used as a substitute for the above-mentioned size coat.
このようなことは、インキ印刷だけではなく、樹脂塗装
を行なう場合についても同様なことがある。This may occur not only in ink printing but also in resin coating.
［発明が解決しようとする問題点］
本発明は上記に説明した従来におけるアルミニウムおよ
びアルミニウム合金の表面処理液の種々の問題点に鑑み
、本発明者が鋭意研究を行ない、検討を重ねた結果、高
温水に接触する部材用として適している耐蝕性に優れた
皮膜が形成でき、また、インキ印刷または樹脂塗装の下
地皮膜として良好な密着性および耐蝕性を有し、さらに
、インキ印刷や樹脂塗装後に成形加工を行なってもイン
キや樹脂が剥離することがないという優れたアルミニウ
ムおよびアルミニウム合金の表面処理液を開発したので
ある。[Problems to be Solved by the Invention] In view of the various problems of conventional surface treatment liquids for aluminum and aluminum alloys as described above, the present inventor has conducted intensive research and has made numerous considerations. It can form a film with excellent corrosion resistance that is suitable for parts that come into contact with high-temperature water, and has good adhesion and corrosion resistance as a base film for ink printing or resin painting. They developed an excellent surface treatment solution for aluminum and aluminum alloys that does not cause ink or resin to peel off even after subsequent molding.
［問題点を解決するための手段］
本発明に係るアルミニウムおよびアルミニウム合金の表
面処理液の特徴とするところは、重合度が２００〜１２
０００のポリアクリル酸或いはポリメタクリル酸の水溶
性有機高分子物質を０．１〜５０ｇ／ｌを含有し、さら
に、ＩＮ’ａ族、Ｖａ族、Ｖｉａ族の遷移金属化合物の
１種をポリアクリル酸、ポリメタクリル酸の含有量に対
する重量比で０３〜２．０を含有することにある。[Means for Solving the Problems] The surface treatment liquid for aluminum and aluminum alloys according to the present invention is characterized in that the degree of polymerization is 200 to 12.
000 polyacrylic acid or polymethacrylic acid in an amount of 0.1 to 50 g/l, and one type of transition metal compound of the IN'a group, Va group, and Via group is added to the polyacrylic acid. The weight ratio to the content of acid and polymethacrylic acid is 03 to 2.0.
なお、上記処理液にアンモニア水を含有させることもで
きる。In addition, aqueous ammonia can also be contained in the treatment liquid.
本発明に係るアルミニウムおよびアルミニウム合金の表
面処理液について、以下詳細に説明する。The surface treatment liquid for aluminum and aluminum alloys according to the present invention will be described in detail below.
本発明に係るアルミニウムおよびアルミニウム合金の表
面処理液において、使用するポリアクリル酸或いはポリ
メタクリル酸はＩＶａ族、Ｖａ族、ＶＩａ族の遷移金属
化合物と錯化合物を生成し、水や高温水にも不溶な皮膜
を形成する。In the surface treatment solution for aluminum and aluminum alloys according to the present invention, the polyacrylic acid or polymethacrylic acid used forms a complex compound with a transition metal compound of the IVa group, Va group, or VIa group, and is insoluble even in water or high-temperature water. Forms a thick film.
そして、この形成された皮膜はインキ印刷や樹脂塗装の
下地皮膜として良好な密着性を示し、また、耐蝕性にも
優れている。The formed film exhibits good adhesion as a base film for ink printing or resin coating, and also has excellent corrosion resistance.
さらに、ポリアクリル酸或いはポリメタクリル酸を使用
した皮膜は、燐酸クロメート皮膜または陽極酸化皮膜の
ような無機化合物のみの皮膜と比較して、その延性が高
く、加工後においても皮膜にクラックを生じ難く、また
、熱に対しても安定−丁−
であり、絞り加工後においても良好な密着性を示す。Furthermore, coatings using polyacrylic acid or polymethacrylic acid have higher ductility than coatings made only of inorganic compounds, such as phosphoric acid chromate coatings or anodized oxide coatings, and are less prone to cracking even after processing. It is also stable against heat and exhibits good adhesion even after drawing.
このポリアクリル酸或いはボ１月メタクリル酸の重合度
は、処理されるアルミニウムおよびアルミニウム合金の
用途に応じて適切に選ぶべきであり、アルミニウムおよ
びアルミニウム合金が高温水或いは高温水蒸気に暴露さ
れる場合やこれに相当する環境で使用される場合には、
ポリアクリル酸或いはポリメタクリル酸の重合度は、２
００未満では高温水に暴露された場合の黒色変色また高
温水蒸気に暴露された場合の白色変色を充分に抑制する
ことができず、また、アルミニウムおよびアルミニウム
合金が、インキ印刷や樹脂塗装に使用される場合には、
ポリアクリル酸或いはポリメタクリル酸の重合度は５０
０未満では成形加工前のインキや樹脂との密着性が良い
皮膜が得られるが、皮膜の延性が不充分で、成形加工後
の密着性が不足しているため、アルミニウムおよびアル
ミニウム合金に絞り加工等を行なった場合にはその加工
程度の大きい部位では密着性の低下が大きく、殺菌のた
めの沸騰水処理を行なうと、インキや樹脂に剥離の生ず
ることがある。The degree of polymerization of polyacrylic acid or methacrylic acid should be selected appropriately depending on the use of the aluminum and aluminum alloys to be treated, and should be used when aluminum and aluminum alloys are exposed to high-temperature water or steam. When used in an environment equivalent to this,
The degree of polymerization of polyacrylic acid or polymethacrylic acid is 2
If it is less than 0.0, black discoloration when exposed to high-temperature water or white discoloration when exposed to high-temperature steam cannot be sufficiently suppressed, and aluminum and aluminum alloys are not used for ink printing or resin coating. If
The degree of polymerization of polyacrylic acid or polymethacrylic acid is 50
If it is less than 0, a film with good adhesion to ink and resin before molding can be obtained, but the film has insufficient ductility and adhesion after molding is insufficient, so it is difficult to draw aluminum and aluminum alloys. If such processing is performed, the adhesion will be greatly reduced in areas that have been processed to a large degree, and if boiling water treatment is performed for sterilization, ink or resin may peel off.
また、ポリアクリル酸或いはポリメタクリル酸は重合度
または溶液濃度が大きくなるほど溶液粘度が増大すると
いう性質があり、高重合度または高濃度のポリアクリル
酸或いはポリメタクリル酸と■ａ族、Ｖａ族、Ｖｉａ族
の遷移金属化合物との混合処理液を水溶液として建浴し
た場合に、重合体と遷移金属化合物との化学反応によっ
て、さらに、粘度が上昇し、一部で皮膜成分の沈澱を生
じて浴安定性に欠けるようになる。In addition, polyacrylic acid or polymethacrylic acid has a property that the solution viscosity increases as the degree of polymerization or solution concentration increases. When a mixed treatment solution with a Via group transition metal compound is prepared as an aqueous solution, the viscosity further increases due to the chemical reaction between the polymer and the transition metal compound, and some coating components precipitate, causing the bath to deteriorate. It becomes less stable.
このような場合に、アンモニア水は建浴上の問題点を解
決する効果があるので含有させることがあり、このアン
モニア水はポリアクリル酸或いはポリメタクリル酸水溶
液を中和する作用があり、建浴中に重合体と遷移金属化
合物の化学反応を妨げ、粘度上昇を抑制して処理液を安
定にする効果がある。しかして、処理液に含有されたア
ンモニア水は表面処理液によって得られる効果を満足さ
せるためには、処理後の乾燥によって皮膜中から除去す
る必要があり、このアンモニア水の含有量は粘度上昇を
抑制し、かつ、皮膜成分の沈澱を生じさせない程度の量
とするのがよい。In such cases, ammonia water is sometimes added because it has the effect of solving problems in bath preparation.This ammonia water has the effect of neutralizing the polyacrylic acid or polymethacrylic acid aqueous solution, and is effective in solving bath preparation problems. It has the effect of interfering with the chemical reaction between the polymer and the transition metal compound, suppressing the increase in viscosity, and stabilizing the processing liquid. Therefore, the ammonia water contained in the treatment solution needs to be removed from the film by drying after treatment in order to achieve the effects obtained by the surface treatment solution, and the ammonia water content is determined to prevent the increase in viscosity. It is preferable to set the amount to an extent that suppresses the amount and does not cause precipitation of the film components.
また、ポリアクリル酸或いはポリメタクリル酸の重合度
力月２０００を越えると建浴性が悪くなり、工業的に実
施する場合には不適当である。Furthermore, if the degree of polymerization of polyacrylic acid or polymethacrylic acid exceeds 2,000 degrees, the bath preparation properties will deteriorate, making it unsuitable for industrial use.
よって、ポリアクリル酸或いはポリメタクリル酸の重合
度は２００〜１２０００とする。Therefore, the degree of polymerization of polyacrylic acid or polymethacrylic acid is set to 200 to 12,000.
次に、ポリアクリル酸或いはポリメタクリル酸の含有量
について説明すると、このポリアクリル酸或いはポリメ
タクリル酸の含有量が０．１ｇ／１未満では、乾燥後の
皮膜量が不足して皮膜が充分にアルミニウムおよびアル
ミニウム合金の表面を覆う状態にはならず、不連続な部
分が生じて部分的に黒色変色、白色変色を生じ、また、
密着性および耐蝕性も悪くなり、皮膜量を多くすること
も実際上困難であり、また、含有量が５０８／ｌを越え
ると皮膜量が多くなりすぎ、成形加工時に逆に皮膜にク
ラックが発生し易くなり、加工密着性が悪（なり、かつ
、皮膜量を少なくすることも困難となり、建浴の際に含
存させるアンモニア水の量も多くり不経済である。よっ
て、ポリアクリル酸或いはポリメタクリル酸の含有量は
０．１〜５０ｇ／ｌとする。Next, to explain the content of polyacrylic acid or polymethacrylic acid, if the content of polyacrylic acid or polymethacrylic acid is less than 0.1 g/1, the amount of film after drying will be insufficient and the film will not be formed sufficiently. It does not cover the surface of aluminum and aluminum alloys, and discontinuous areas occur, causing partial black discoloration and white discoloration, and
Adhesion and corrosion resistance deteriorate, and it is practically difficult to increase the amount of coating.Furthermore, if the content exceeds 508/l, the amount of coating becomes too large, and cracks occur in the coating during molding. Polyacrylic acid or The content of polymethacrylic acid is 0.1 to 50 g/l.
また、ＩＶａ族、■ａ族、ＶＩａ族の遷移金属化合物は
、ポリアクリル酸或いはポリメタクリル酸と錯化合物を
生成し、安定した皮膜が得られるものであり、この遷移
金属化合物としては、
ＮａＶＯ３、ＮＨ，ＶＯ３、ＶＯ（、ａＨいＶＯ３０，
、ＶＯＣｌ２、Ｎ ａｔ Ｔ ＩＦ ｅ、（ＮＨ４）２
ＴｉＦＧ、（ＮＨ４）２Ｔ ｉ（ＯＨ）２（Ｃ０３）２
、ＴＩ（ＳＯ４）２、Ｎａ、ＺｒＦｅ、（Ｎ■］４）２
ＺｒＦ６、（ＮＨ４）、Ｚｒ（ＯＨ）、（ＣＯ３）２、
Ｚ ｒ（Ｓ Ｏ４） ２、Ｎ ａ ２ Ｍ ｏ Ｏ４、
ＶＯ０３、Ｃｒ２Ｏ３、Ｃｒ （ＣＯ） ｏ、Ｃｒ２（
ＮＨ４）、（Ｓ ０４）４、Ｃｒｚ（ＳＯ４）３、Ｃｒ
（Ｃ２１〜Ｉ ３０２） ３、ＣｒＣ７Ｏｔが挙げら
れる。In addition, transition metal compounds of group IVa, group IIa, and group VIa form complex compounds with polyacrylic acid or polymethacrylic acid to obtain stable films, and these transition metal compounds include NaVO3, NH, VO3, VO (, aH VO30,
, VOCl2, N at T IF e, (NH4)2
TiFG, (NH4)2T i(OH)2(C03)2
, TI(SO4)2, Na, ZrFe, (N■]4)2
ZrF6, (NH4), Zr(OH), (CO3)2,
Z r(S O4) 2, N a 2 M o O4,
VO03, Cr2O3, Cr(CO) o, Cr2(
NH4), (S04)4, Crz(SO4)3, Cr
(C21-I302) 3, CrC7Ot.
この遷移金属化合物の含有量は、ポリアクリル酸或いは
ポリメタクリル酸の含有量に対する重量比で０．３〜２
０とするのが良く、０．３未満では樹脂量が過剰となり
、遷移金属化合物と錯化合物を生成していない遊離した
ポリアクリル酸或いはポリメタクリル酸が多くなりすぎ
、これが溶出し易く、高温水、高温水蒸気に暴露された
場合、この一部が溶出し皮膜に欠陥部を生じ、耐蝕性が
低下し、皮膜が溶出することが実用」二問題となり、ま
た、インキや樹脂塗装の密着性および耐蝕性が悪くなり
、例えば、殺菌等のために沸騰水処理を行うと、一部が
溶出し、皮膜が剥離することがあり、また、２０を越え
ると樹脂量が不足し、皮膜の延性が不充分で強加工を受
けた場合に皮膜が不連続となり、耐蝕性が低下し、また
、インキや樹脂塗装の加工後密着性が悪くなる。よって
、遷移金属化合物の含有量はポリアクリル酸或いはポリ
メタクリル酸の含有量に対する重量比で０．３〜２．０
とする。The content of this transition metal compound is 0.3 to 2 in weight ratio to the content of polyacrylic acid or polymethacrylic acid.
If it is less than 0.3, the amount of resin will be excessive, and there will be too much free polyacrylic acid or polymethacrylic acid that has not formed a complex compound with the transition metal compound, and this will easily elute. When exposed to high-temperature steam, a portion of this elutes and causes defects in the coating, reducing corrosion resistance and elution of the coating, which poses two practical problems.It also impairs the adhesion of inks and resin coatings. Corrosion resistance deteriorates and, for example, when treated with boiling water for sterilization, a portion of it may be eluted and the film may peel off.If it exceeds 20, the amount of resin will be insufficient and the ductility of the film will deteriorate. If insufficiently strong processing is applied, the film will become discontinuous, resulting in decreased corrosion resistance and poor adhesion of ink and resin coating after processing. Therefore, the content of the transition metal compound is 0.3 to 2.0 in weight ratio to the content of polyacrylic acid or polymethacrylic acid.
shall be.
［実 施 例］
本発明に係るアルミニウムおよびアルミニウム合金の表
面処理液の実施例と比較例について説明する。[Example] Examples and comparative examples of surface treatment liquids for aluminum and aluminum alloys according to the present invention will be described.
１１一
実施例１
アルミニウムおよびアルミニウム合金が高温水或いは高
温水蒸気に暴露される処理またはこれに相当する環境で
使用される場合に、最適な耐黒変性および耐白変性に優
れた皮膜を形成する表面処理液の例について説明する。11-Example 1 Surface that forms a film with optimal blackening resistance and whitening resistance when aluminum and aluminum alloys are exposed to high-temperature water or steam or used in an equivalent environment An example of the treatment liquid will be explained.
表面処理液および耐黒変性、耐白変性に関する評価は第
１表に示す。Table 1 shows the evaluation of the surface treatment solution and the resistance to blackening and whitening.
第１表における実施例１〜１１は、脱脂したアルミニウ
ム材に本発明に係るアルミニウムおよびアルミニウム合
金の表面処理液により皮膜を形成した。In Examples 1 to 11 in Table 1, films were formed on degreased aluminum materials using the surface treatment solution for aluminum and aluminum alloys according to the present invention.
この皮膜形成は、表面処理液をデイツプまたはロールコ
ータ−により塗布した後、室温〜３００°Ｃの温度にお
いて乾燥した。乾燥時間は実施温度により異なる。This film was formed by applying a surface treatment liquid using a dip or roll coater and then drying at a temperature of room temperature to 300°C. Drying time varies depending on the operating temperature.
耐黒変性は、沸騰水（水道水）に３０分間浸漬した後の
表面の黒色変化を評価し、耐白変性は圧力容器内におい
て１２０℃の温度の蒸気に３０分間暴露した後の白色変
色を評価した。Black discoloration resistance evaluates the black change on the surface after being immersed in boiling water (tap water) for 30 minutes, and white discoloration resistance evaluates the white discoloration after being exposed to steam at a temperature of 120°C for 30 minutes in a pressure vessel. evaluated.
比較例１は脱脂済みアルミニウム材を実施例と同様の方
法で評価した。In Comparative Example 1, a degreased aluminum material was evaluated in the same manner as in the Examples.
比較例２は燐酸クロメート処理を行なったアルミニウム
材を実施例と同様の方法で評価した。In Comparative Example 2, an aluminum material treated with phosphoric acid chromate was evaluated in the same manner as in the example.
比較例５はポリアクリル酸の重合度が２００以下のもの
をＩＶａ族の遷移金属化合物との混合処理液とし、実施
例と同様の方法で皮膜を形成し、実施例と同様の方法で
評価した。Comparative Example 5 uses polyacrylic acid with a degree of polymerization of 200 or less as a mixed treatment solution with a IVa group transition metal compound, forms a film in the same manner as in the example, and evaluates in the same manner as in the example. .
比較例７は処理液中のポリアクリル酸含有量が０．１ｇ
／ｌ以下と少ない場合を、実施例と同様の方法で皮膜を
形成し、実施例と同様の方法で評価した。In Comparative Example 7, the polyacrylic acid content in the treatment liquid was 0.1 g.
In the case where the amount was as low as /l or less, a film was formed in the same manner as in the example and evaluated in the same manner as in the example.
比較例９、ＩＯは処理液中のポリアクリル酸含有量に対
する遷移金属化合物含有量が少ない場合、また、過剰の
場合について、実施例と同様の方法で皮膜を形成し、実
施例と同様の方法で評価した。Comparative Example 9: For IO, a film was formed in the same manner as in Example when the transition metal compound content was small or excessive relative to the polyacrylic acid content in the treatment solution, and It was evaluated by
この第１表より、本発明に係るアルミニウムおよびアル
ミニウム合金の表面処理液は、比較例に比べて耐黒変性
および耐白変性に格段に優れた皮膜を形成することがイ
つかる。From Table 1, it can be seen that the surface treatment liquid for aluminum and aluminum alloys according to the present invention forms a film that is much more resistant to blackening and whitening than the comparative example.
実施例２
アルミニウムおよびアルミニウム合金を、飲料容器等の
ギャップとして使用するのに最適なインキ密着性に優れ
た皮膜を形成する表面処理液の例である。Example 2 This is an example of a surface treatment liquid that forms a film with excellent ink adhesion that is ideal for use as gaps in beverage containers and the like on aluminum and aluminum alloys.
表面処理液およびインキ密着性に関する評価を第１表に
示す。Table 1 shows evaluations regarding the surface treatment liquid and ink adhesion.
実施例１〜１１は、脱脂したアルミニウム材に本発明に
係るアルミニウムおよびアルミニウム合金の表面処理液
により、実施例Ｉにおいて説明したような方法で、塗布
乾燥し皮膜を形成したものに、ザイズコート無しで直接
黒色のインキを３μｍの厚さに印刷した後、ビニル系の
ツヤニスを５μｍの厚さに塗布し、１７０℃×１０分間
焼きイ」１フ、印刷面が外面になるように貫き絞り加工
（絞りと同時にトリミング加工を行なう加工）を行なっ
ノこ。In Examples 1 to 11, a surface treatment solution for aluminum and aluminum alloy according to the present invention was applied to a degreased aluminum material by the method described in Example I, and a film was formed by drying and no size coating was applied. After directly printing black ink to a thickness of 3 μm, apply vinyl gloss varnish to a thickness of 5 μm, bake at 170°C for 10 minutes, and punch through so that the printed surface is the outside surface. (a process that performs trimming at the same time as drawing).
評価は加工を行なったものを３０分間沸騰水中に浸漬し
、側壁部のインキの剥離の有無を５点法て行なった。For evaluation, the processed product was immersed in boiling water for 30 minutes, and a 5-point method was used to check for peeling of the ink on the side wall.
比較例Ｉは、脱脂済みアルミニウム材に直接黒色のイン
キ印刷を行ない、実施例と同様の方法により評価した。In Comparative Example I, black ink was printed directly on a degreased aluminum material, and evaluation was made in the same manner as in the Examples.
比較例２．３．４は燐酸クロメート処理および陽極酸化
処理を行なったアルミニウム材に、直接黒色のインキ印
刷を行ない、実施例と同様の方法により評価した。In Comparative Examples 2.3.4, black ink was directly printed on an aluminum material that had been subjected to phosphoric acid chromate treatment and anodization treatment, and evaluation was performed in the same manner as in the examples.
比較例５．６はポリアクリル酸またはポリメタクリル酸
の重合度が２００以下および１２０００を越えるのもの
を、ＩＶａ族の遷移金属化合物との混合処理液とし、実
施例と同様の方法で皮膜を形成し、黒色のインキ印刷を
行ない実施例と同様の方法により評価した。In Comparative Example 5.6, polyacrylic acid or polymethacrylic acid with a polymerization degree of 200 or less and more than 12,000 was used as a mixed treatment solution with a IVa group transition metal compound, and a film was formed in the same manner as in the example. Then, black ink printing was performed and evaluation was performed in the same manner as in the examples.
比較例７．８は処理液中のポリアクリル酸含有量が０．
１ｇ／ｌ以下および５［１ｇ／ｌを越える場合を、実施
例と同様の方法により皮膜を形成し、黒色のインキ印刷
を行ない、実施例と同様の方法で評価した。In Comparative Examples 7 and 8, the polyacrylic acid content in the treatment liquid was 0.
In cases where the concentration was 1 g/l or less and 5 [1 g/l or more], a film was formed by the same method as in the example, black ink printing was performed, and evaluation was made in the same manner as in the example.
比較例９．１０は処理液中のポリアクリル酸含有量に対
する遷移金属化合物含有量が少ない場合、また、過剰の
場合について実施例と同様の方法により皮膜を形成し、
黒色のインキ印刷を行ない、実施例と同様の方法で評価
した。In Comparative Examples 9 and 10, films were formed by the same method as in Examples when the transition metal compound content was small or excessive relative to the polyacrylic acid content in the treatment solution,
Black ink printing was performed and evaluation was performed in the same manner as in the examples.
比較例ＩＩは脱脂済みアルミニウム材にザイズコート（
関西ペイント製、ＸＪ−Ｃ１１９Ｆ。Comparative Example II is a size coat (
Manufactured by Kansai Paint, XJ-C119F.
１８０°ＣＸｌ０分間焼き付け）を施した塗装材料を作
成し、その上に黒色のインキ印刷を行ない、実施例と同
様の方法で評価した。A coating material was prepared which had been baked at 180° C.
第１表より本発明に係るアルミニウムおよびアルミニウ
ム合金の表面処理液により形成された皮膜は、何れもイ
ンキ密着性において優れた特性を示し、比較例１〜１１
と比較してもそれ以上のインキ密着性を示している。Table 1 shows that the films formed with the surface treatment solution for aluminum and aluminum alloys according to the present invention all exhibited excellent properties in terms of ink adhesion, and Comparative Examples 1 to 11
It shows even better ink adhesion than that.
実施例３
樹脂塗装を行なった場合の密着性および耐蝕性について
の例である。Example 3 This is an example of adhesion and corrosion resistance when resin coating is applied.
アルミニウム材の皮膜の種類および樹脂との密着性、さ
らに、耐蝕性に関する評価を第１表に示す。Table 1 shows the type of coating on the aluminum material, the adhesion to the resin, and the evaluation regarding corrosion resistance.
実施例１〜１１は脱脂したアルミニウム材に本発明に係
るアルミニウムおよびアルミニウム合金の表面処理液に
より実施例１に説明した方法で塗布乾燥して皮膜を形成
したものに、変性ビニル系樹脂塗料を４μｍの厚さに塗
装した後、１９０℃×１０分焼き付け、その塗装面が外
面になるように絞り率６０％の絞り加］−を行ない、側
壁に１ｍｍ間隔の基盤目をカッターナイフで１００個入
れ、スコッヂテープ（商品名）を圧着・剥離し、塗装の
剥離の有無を調査した。In Examples 1 to 11, a surface treatment solution for aluminum and aluminum alloy according to the present invention was applied to a degreased aluminum material by the method described in Example 1 and dried to form a film, and then a modified vinyl resin paint was applied to a thickness of 4 μm. After painting to the thickness of , Scodge tape (trade name) was applied and peeled off, and the presence or absence of peeling of the paint was investigated.
また、耐蝕性は変性ビニル系樹脂塗料を０．５μｍの厚
さに塗装した後、１９０℃×１０分焼き付け、塩水噴霧
５００時間後の腐蝕の程度を評価した。Corrosion resistance was evaluated by coating a modified vinyl resin paint to a thickness of 0.5 μm, baking at 190° C. for 10 minutes, and evaluating the degree of corrosion after 500 hours of salt water spraying.
比較例１は脱脂済みアルミニウム材を実施例と同様の方
法で変性ビニル系樹脂塗料を塗装して評価した。Comparative Example 1 was evaluated by coating a degreased aluminum material with a modified vinyl resin paint in the same manner as in the example.
比較例２．３．４は燐酸クロメート処理および陽極酸化
処理を行なったアルミニウム材に実施例と同様の方法で
変性ビニル系樹脂塗料を塗装して評価した。Comparative Examples 2.3.4 were evaluated by applying a modified vinyl resin paint to an aluminum material that had been subjected to phosphoric acid chromate treatment and anodizing treatment in the same manner as in the examples.
比較例５．６はポリアクリル酸またはポリメタクリル酸
の重合度が２００以下および＋２０００を越えるものを
、■ａ族の遷移金属化合物との混合処理液とし、実施例
と同様の方法で皮膜を形成し、実施例と同様の方法で変
性ビニル系樹脂塗料を塗装して評価した。In Comparative Example 5.6, polyacrylic acid or polymethacrylic acid with a polymerization degree of 200 or less and more than +2000 was used as a mixed treatment solution with a group A transition metal compound, and a film was formed in the same manner as in the example. Then, a modified vinyl resin paint was applied and evaluated in the same manner as in the examples.
比較例７．８は処理液中のポリアクリル酸含有量がＯ，
１，ｇ／ｌ以下および５０ｇ／ｌを越える場合を、実施
例と同様の方法で皮膜を形成し、実施例と同様の方法で
変性ビニル系樹脂塗料を塗装して評価した。In Comparative Example 7.8, the polyacrylic acid content in the treatment solution was O,
1.g/l or less and cases exceeding 50 g/l were evaluated by forming a film in the same manner as in the examples and applying a modified vinyl resin paint in the same manner as in the examples.
比較例９、ＩＯは処理液中のポリアクリル酸含有量に対
する遷移金属化合物含有量が少ない場合、また、過剰の
場合について実施例と同様の方法で皮膜を形成し、実施
例と同様の方法で変性ビニル系樹脂塗料を塗装して評価
した。Comparative Example 9: For IO, a film was formed in the same manner as in the example when the transition metal compound content was small or excessive relative to the polyacrylic acid content in the treatment solution; A modified vinyl resin paint was applied and evaluated.
比較例１１は脱脂済みアルミニウム材にサイズコート（
関西ペイント製、ＸＪ−ＣＩ １９Ｆ。Comparative Example 11 is a size coat (
Manufactured by Kansai Paint, XJ-CI 19F.
１８０°Ｃ×１０分間焼き付け）を施した塗装材料を作
成し、その上に、実施例と同様の方法で変性ビニル系樹
脂塗料を塗装して評価した。A coating material was prepared which had been baked at 180°C for 10 minutes, and a modified vinyl resin paint was coated thereon in the same manner as in the examples for evaluation.
第１表より、本発明に係るアルミニウムおよびアルミニ
ウム合金の表面処理液により形成した皮膜は、何れも樹
脂塗料との密着性において優れ、また、耐蝕性において
も非常に良好な特性を示していることがわかる。From Table 1, it can be seen that the films formed using the surface treatment liquid for aluminum and aluminum alloys according to the present invention have excellent adhesion to resin paints and also exhibit very good corrosion resistance. I understand.
［発明の効果］
以上説明したように、本発明に係るアルミニウムおよび
アルミニウム合金の表面処理液は」二記の構成であるか
ら、アルミニウムおよびアルミニウム合金の表面に形成
された皮膜は、樹脂塗装を行なわなくても高温水や高温
水蒸気に暴露されても黒色変色、白色変色の発生がなく
、燐酸クロメート処理や燐酸クロメート処理後樹脂塗装
わ行なう場合に比較して、処理が容易で処理後の水洗を
行なう必要がなく、生産性やコスト面から有利であり、
また、インキ印刷や樹脂塗装に対する密着性が良好で、
飲料容器、飲料容器のギャップ等におけるウィケットタ
イプ方式の生産性の問題がなく、化成処理法のインキ密
着性の問題がなく、深絞り加工によっても良好な密着性
や耐蝕性を有し、特に、インキに対する密着性が良く、
ザイズコートを省略し、直接インキ印刷を行なっても加
工後の密着性が良好で、加工後の殺菌のための沸騰水処
理を行なっても加工部のインキの剥離することがない優
れた下地皮膜であるという効果を有するものである。[Effects of the Invention] As explained above, since the surface treatment liquid for aluminum and aluminum alloys according to the present invention has the composition described in ``2'', the film formed on the surface of aluminum and aluminum alloys can be coated with a resin. There is no black discoloration or white discoloration even when exposed to high-temperature water or high-temperature steam, and compared to phosphoric acid chromate treatment or phosphoric acid chromate treatment followed by resin painting, treatment is easier and requires no washing with water after treatment. It is advantageous in terms of productivity and cost, as there is no need to
In addition, it has good adhesion to ink printing and resin coating,
There are no productivity problems with the wicket type method such as gaps between beverage containers, beverage containers, etc., there are no ink adhesion problems with chemical conversion treatment, and it has good adhesion and corrosion resistance even with deep drawing processing. Good adhesion to ink,
Excellent base film that has good adhesion after processing even when direct ink printing is performed without the need for a size coat, and the ink does not peel off from the processed area even when treated with boiling water for sterilization after processing. This has the effect of
手続補正書（自発）
昭和６２年１２月２８日
１ 事件の表示
昭和６２年特許願第３０７９９２号
２、発明の名称
アルミニウムおよびアルミニウム合金の表面処理液
か
３、補正をする者
事件との関係 特許出願人
住所 神戸市中央区脇浜町１丁目３番１８号名称 （１
１９） 株式会社 神戸製鋼所代表者 亀高素吉
４ 代理人
住所 東京都江東区南砂２丁目２番１５号藤和東陽町コ
ープ９０１号
５ 補正命令の日付 （自発）
６、補正の対象
明細書の発明の詳細な説明の欄
７ 補正の内容
（１）明細書第４頁１３行のｒ２ｇ／ｍｌを「２ｇ／ｍ
２」と補正する。Procedural amendment (voluntary) December 28, 1988 1 Case description 1988 Patent Application No. 307992 2 Title of invention Surface treatment liquid for aluminum and aluminum alloys
(3) Relationship with the case of the person making the amendment Patent applicant address 1-3-18 Wakihama-cho, Chuo-ku, Kobe City Name (1
19) Kobe Steel Co., Ltd. Representative: Sokichi Kametaka 4 Agent address: 901 Fujiwa Toyocho Co-op, 2-2-15 Minamisuna, Koto-ku, Tokyo 5 Date of amendment order (voluntary) 6. Invention of the specification subject to amendment Detailed explanation column 7 Contents of amendment (1) r2g/ml on page 4, line 13 of the specification was changed to “2g/m
2”.
Claims (2)
いはポリメタクリル酸の水溶性有機高分子物質を０．１
〜５０ｇ／ｌを含有し、さらに、IVａ族、Ｖａ族、VIａ
族の遷移金属化合物の１種をポリアクリル酸、ポリメタ
クリル酸の含有量に対する重量比で０．３〜２．０を含
有することを特徴とするアルミニウムおよびアルミニウ
ム合金の表面処理液。(1) A water-soluble organic polymer substance of polyacrylic acid or polymethacrylic acid with a degree of polymerization of 200 to 12,000 is added to 0.1
~50 g/l, and further contains IVa, Va, VIa
1. A surface treatment solution for aluminum and aluminum alloys, which contains one type of transition metal compound of the group A in a weight ratio of 0.3 to 2.0 relative to the content of polyacrylic acid or polymethacrylic acid.
求の範囲第１項記載のアルミニウムおよびアルミニウム
合金の表面処理液。(2) The surface treatment liquid for aluminum and aluminum alloys according to claim 1, which contains aqueous ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30799287A JPH01149865A (en) | 1987-12-05 | 1987-12-05 | Surface treating solution for aluminum and alloy thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30799287A JPH01149865A (en) | 1987-12-05 | 1987-12-05 | Surface treating solution for aluminum and alloy thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01149865A true JPH01149865A (en) | 1989-06-12 |
Family
ID=17975602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30799287A Pending JPH01149865A (en) | 1987-12-05 | 1987-12-05 | Surface treating solution for aluminum and alloy thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01149865A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170141748A (en) | 2015-04-24 | 2017-12-26 | 니혼 파커라이징 가부시키가이샤 | Surface treatment agents and metal materials for metal materials |
-
1987
- 1987-12-05 JP JP30799287A patent/JPH01149865A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170141748A (en) | 2015-04-24 | 2017-12-26 | 니혼 파커라이징 가부시키가이샤 | Surface treatment agents and metal materials for metal materials |
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