JPH0788588B2 - Surface treatment agent and treatment bath for aluminum or its alloys - Google Patents
Surface treatment agent and treatment bath for aluminum or its alloysInfo
- Publication number
- JPH0788588B2 JPH0788588B2 JP63033755A JP3375588A JPH0788588B2 JP H0788588 B2 JPH0788588 B2 JP H0788588B2 JP 63033755 A JP63033755 A JP 63033755A JP 3375588 A JP3375588 A JP 3375588A JP H0788588 B2 JPH0788588 B2 JP H0788588B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- surface treatment
- weight
- film
- ppm
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、アルミニウム又はその合金の表面を処理する
ための処理剤及び処理浴に関し、特にアルミニウム又は
その合金からなる飲料缶等の処理に適した処理剤及び処
理浴に関する。TECHNICAL FIELD The present invention relates to a treating agent and a treating bath for treating the surface of aluminum or its alloy, and is particularly suitable for treating beverage cans and the like made of aluminum or its alloy. Treatment agent and treatment bath.
アルミニウム又はその合金の防食及び塗装下地の形成を
目的として、化成処理を施すことは、従来から広く行な
われている。その代表的な例として、クロム酸、リン
酸、弗化水素酸を含有する溶液でで処理する方法があ
る。この方法によると、耐沸水黒変性、塗膜との密着性
ともに良好な皮膜を得ることができるが、非常に毒性の
高い６価のクロムを含有しているため、人体への影響及
び廃水処理等に問題がある。そこで６価のクロムを含ま
ない溶液がこれまでに種々開発されている。Conventionally, chemical conversion treatment has been widely performed for the purpose of preventing corrosion of aluminum or its alloy and forming a coating base. A typical example thereof is a method of treating with a solution containing chromic acid, phosphoric acid and hydrofluoric acid. According to this method, it is possible to obtain a film that is resistant to blackening by boiling water and has good adhesion to the coating film, but since it contains hexavalent chromium, which is extremely toxic, it has an effect on the human body and wastewater treatment. Etc. has a problem. Therefore, various solutions containing no hexavalent chromium have been developed so far.
例えば、水溶性亜鉛塩、水溶性バナジン酸塩、水溶性フ
ッ化塩又は錯フッ化塩及びハロゲン元素の酸素酸塩等の
酸化剤を含むpHが３〜５の溶液で、アルミニウム又はア
ルミニウム合金を処理する方法（特開昭48−27935号公
報）や、バナジウム酸イオンを含むpH1.5〜3.0のリン酸
塩処理液で金属（特にアルミニウム）表面を処理する方
法（特開昭55−131176号公報）や、ジルコニウム、ホス
フェート及び有効フッ化物を含むpHが1.5〜4.0のアルミ
ニウム表面処理用コーティング溶液（特公昭56−33468
号公報）や、バナジウム化合物と、ジルコニウム化合物
又はケイフッ化化合物を含むアルミニウム又はアルミニ
ウム合金の化成処理液（特開昭56−136978号公報）など
が知られている。For example, a solution having a pH of 3 to 5 containing an oxidizing agent such as a water-soluble zinc salt, a water-soluble vanadate, a water-soluble fluoride salt or a complex fluoride salt, and an oxygen acid salt of a halogen element, and aluminum or an aluminum alloy is used. A treatment method (JP-A-48-27935) or a method of treating a metal (particularly aluminum) surface with a phosphate treatment solution containing vanadate ions and having a pH of 1.5 to 3.0 (JP-A-55-131176). And a coating solution for surface treatment of aluminum having a pH of 1.5 to 4.0 containing zirconium, phosphate and effective fluoride (Japanese Patent Publication No. 56-33468).
JP-A-56-136978) and a chemical conversion treatment liquid of aluminum or an aluminum alloy containing a vanadium compound and a zirconium compound or a silicofluoride compound are known.
しかしながら、特開昭48−27935号公報に記載されてい
る方法では、処理時間が３〜10分と長くなるため生産性
が劣り、しかも形成された皮膜が灰白色となるため飲料
缶等の用途のアルミニウム又はアルミニウム合金に適用
するには不適当である。更に、その上に塗布されるペイ
ント、インク、ラッカーなどの塗膜との密着性が不十分
であるという問題もある。However, in the method described in Japanese Patent Laid-Open No. 48-27935, the processing time becomes long, which is 3 to 10 minutes, so that the productivity is inferior, and the formed film becomes grayish white, so that it can be used in applications such as beverage cans. It is unsuitable for application to aluminum or aluminum alloys. Further, there is a problem that the adhesion with a coating film such as paint, ink or lacquer applied thereon is insufficient.
特開昭55−131176号公報に記載されている方法は、ノン
リンス方式であるため、飲料缶用には適用できず、、ま
た殺菌のために沸とう水で処理する際に精製皮膜が黒変
するという問題が生じ、更にペイントなどの塗膜との密
着性も満足できるものでない。Since the method described in JP-A-55-131176 is a non-rinsing method, it cannot be applied to beverage cans, and the purified film turns black when treated with boiling water for sterilization. However, the adhesion to a coating film such as paint is not satisfactory.
また、特開昭56−33468号公報に記載されているコーテ
ィング溶液は、新建液、即ち調製したばかりの新しい溶
液では、十分な性能を示すが、化成処理を繰り返し、フ
ッ素のエッチングによって溶液中にアルミニウムが蓄積
するに伴ない、上述の耐沸水黒変性、密着性が悪化す
る。また生成皮膜面の滑り性が悪いため、この溶液で処
理した缶の搬送が円滑に行えないという問題も生ずる。Further, the coating solution described in JP-A-56-33468 shows sufficient performance in a new building solution, that is, a fresh solution that has just been prepared, but the chemical conversion treatment is repeated to form a solution in the solution by etching fluorine. With the accumulation of aluminum, the above boiling water blackening resistance and the adhesiveness deteriorate. Further, since the slipperiness of the surface of the formed film is poor, there is a problem that the can treated with this solution cannot be transported smoothly.
更に、特開昭56−136978号公報に記載されている処理液
は、比較的高温、長時間の処理（好ましい範囲として、
50〜80℃、３〜５分間）を必要とするうえ、生成皮膜の
耐沸水黒変性及び塗膜との密着性が不十分である。また
生成皮膜が灰色であるため、飲料缶用途のアルミニウム
又はアルミニウム合金に適用するには不適当である。Further, the treatment liquid described in JP-A-56-136978 is a treatment at a relatively high temperature for a long time (as a preferable range,
50 to 80 ° C. for 3 to 5 minutes), and the resistance to blackening by boiling water of the formed film and the adhesion to the coating film are insufficient. Further, since the formed film is gray, it is unsuitable for application to aluminum or aluminum alloy for beverage can applications.
本発明の目的は、かかる従来技術の問題点を解消し、低
温、短時間での処理が可能であり、耐沸水黒変性、塗膜
との密着性及び滑り性に優れた皮膜を形成することので
きるアルミニウム又はその合金の表面処理剤及び処理浴
を提供することにある。An object of the present invention is to solve the problems of the prior art, to form a film which can be treated at a low temperature for a short time, and which has excellent resistance to blackening by boiling water, excellent adhesion to a coating film, and slipperiness. It is to provide a surface treatment agent and a treatment bath of aluminum or an alloy thereof which can be used.
〔課題を解決するための手段〕 上記問題点を解決するために鋭意研究の結果、本発明者
はバナジウムイオン、ジルコニウムイオン、リン酸イオ
ン及び有効フッ素イオンを特定割合で配合させればよい
ことを発見し、本発明に想到した。[Means for Solving the Problems] As a result of intensive research to solve the above problems, the present inventor may mix vanadium ions, zirconium ions, phosphate ions and effective fluorine ions in specific proportions. Discovered and invented the present invention.
すなわち、本発明のアルミニウムまたはその合金の表面
処理剤は、バナジウムイオン10〜1000重量部に対して、
ジルコニウムイオンを10〜500重量部、リン酸イオンを1
0〜500重量部、及び遊離フッ素イオンを１〜50重量部の
割合で含有することを特徴とする。That is, the surface treating agent of the present invention aluminum or its alloy, with respect to vanadium ions 10 to 1000 parts by weight,
Zirconium ion 10 to 500 parts by weight, phosphate ion 1
It is characterized by containing 0 to 500 parts by weight and 1 to 50 parts by weight of free fluorine ion.
また、本発明のアルミニウムまたはその合金の表面処理
浴は、バナジウムイオンを10〜1000ppm、ジルコニウム
イオンを10〜500ppm、リン酸イオンを10〜500ppm、遊離
フッ素イオンを１〜50ppm含み、pHが2.0〜4.0であるこ
とを特徴とする。Further, the surface treatment bath of the aluminum or its alloy of the present invention, vanadium ions 10 ~ 1000 ppm, zirconium ions 10 ~ 500 ppm, phosphate ions 10 ~ 500 ppm, containing free fluorine ions 1 ~ 50 ppm, pH 2.0 ~. It is characterized by being 4.0.
以下本発明を詳細に説明する。The present invention will be described in detail below.
本発明の表面処理剤はアルミニウム又はその合金の表面
処理に用いる物質を所定の割合で含有するもので、適当
な濃度となるように薄めて処理浴とする。その中に含ま
れているバナジウムイオンは10〜1000重量部（表面処理
浴中の濃度としてはバナジウムイオン10〜1000ppm、以
下同じ）である。バナジウムイオン含有量が10重量部
（10ppm）未満では、殺菌のために沸とう水で処理した
際に、生成皮膜が黒変し、対沸水黒変性が劣ったものと
なり、更には、ペイント等の塗膜との密着性、滑り性が
悪化する。バナジウムイオンを1000重量部1000ppmを越
えて添加しても、バナジウムイオン添加の効果はそれ以
上向上しないので、経済性を考慮すると1000重量部（10
00ppm）で十分である。好ましいバナジウムイオン含有
量は、25〜500重量部（25〜500ppm）、特に25〜200重量
部（25〜200pm）である。バナジウムイオンの供給源と
しては、HVO3、NH4VO3、NHVO3等のバナジン酸及びその
塩、硫酸バナジル、シュウ酸バナジル等のバナジル塩、
VF5のようなハロゲン化物等が好適であり、特にNH4VO3
が好ましい。The surface treatment agent of the present invention contains a substance used for surface treatment of aluminum or its alloy in a predetermined ratio, and is diluted to a suitable concentration to prepare a treatment bath. The vanadium ion contained therein is 10 to 1000 parts by weight (as the concentration in the surface treatment bath, vanadium ion is 10 to 1000 ppm, the same applies hereinafter). When the vanadium ion content is less than 10 parts by weight (10 ppm), when treated with boiling water for sterilization, the resulting film turns black and the black denaturation against boiling water is inferior. Adhesion to the coating film and slipperiness deteriorate. Even if vanadium ion is added in excess of 1000 ppm by weight, the effect of vanadium ion addition will not be further improved.
00ppm) is sufficient. The preferred vanadium ion content is 25 to 500 parts by weight (25 to 500 ppm), especially 25 to 200 parts by weight (25 to 200 pm). As a source of vanadium ions, HVO 3 , NH 4 VO 3 , vanadic acid such as NHVO 3 and salts thereof, vanadyl sulfate, vanadyl salts such as vanadyl oxalate,
Halides such as VF 5 are preferred, especially NH 4 VO 3
Is preferred.
また、本発明の表面処理剤（表面処理浴）は、10〜500
重量部（10〜500ppm）、好ましくは20〜100重量部（20
〜100ppm）のジルコニウムイオンを含んでいる。ジルコ
ニウムイオン含有量が10重量部（10ppm）未満では、皮
膜生成速度が極端に低くなり、満足な皮膜が形成されな
い。しかしジルコニウムイオンを500重量部（500ppm）
を越えて添加しても、ジルコニウム添加の効果はそれほ
ど向上せず、経済性を考慮すると500重量（500ppm）で
十分である。ジルコニウムイオンの供給源としては、H2
ZrF6、（NH4）2ZrF6、Na2ZrF6、K2ZrF6、Zr（NO3）４、
ZrO（NO3）２、Zr（SO4）２、ZrOSO4などを挙げること
ができ、特に（NH4）2ZrF6が好ましい。Further, the surface treatment agent (surface treatment bath) of the present invention is 10 to 500
Parts by weight (10 to 500 ppm), preferably 20 to 100 parts by weight (20
~ 100ppm) zirconium ion. If the zirconium ion content is less than 10 parts by weight (10 ppm), the rate of film formation is extremely low, and a satisfactory film cannot be formed. However, 500 parts by weight of zirconium ion (500 ppm)
The effect of adding zirconium does not improve so much even if it is added in excess of 500 wt.%, And 500 wt.% (500 ppm) is sufficient in consideration of economic efficiency. As a source of zirconium ions, H 2
ZrF 6 , (NH 4 ) 2 ZrF 6 , Na 2 ZrF 6 , K 2 ZrF 6 , Zr (NO 3 ) 4 ,
Examples thereof include ZrO (NO 3 ) 2 , Zr (SO 4 ) 2 and ZrOSO 4 , and (NH 4 ) 2 ZrF 6 is particularly preferable.
更に、本発明の表面処理剤（表面処理浴）は、10〜500
重量部（10〜500ppm）、好ましくは25〜200重量部（25
〜200ppm）のリン酸イオンを含んでいる。リン酸イオン
の含有量が10重量部（10ppm）未満では、塗膜との密着
性が悪化し、また500重量部（500ppm）を越えると耐沸
水黒変性、塗膜との密着性が悪化するうえ、Zr・Ｖ・Al
−PO4の沈澱が生成する恐れが生じてくる。リン酸イオ
ンの供給源としては、H3PO4、NaH2PO4、（NH4）H2PO4な
どを挙げることができ、なかでもH3PO4が好適である。Further, the surface treatment agent (surface treatment bath) of the present invention is 10 to 500
Parts by weight (10 to 500 ppm), preferably 25 to 200 parts by weight (25
~ 200ppm) containing phosphate ions. If the content of phosphate ions is less than 10 parts by weight (10 ppm), the adhesion to the coating film will deteriorate, and if it exceeds 500 parts by weight (500 ppm), boiling water black resistance and adhesion to the coating film will deteriorate. Above, Zr ・ V ・ Al
There is a risk that a precipitate of PO 4 will form. Sources of phosphate ion, H 3 PO 4, NaH 2 PO 4, (NH 4) H 2 PO 4 , etc. can be mentioned, with preference given H 3 PO 4.
本発明の表面処理剤（表面処理浴）は、１〜50重量部
（１〜50ppm）、好ましくは３〜20重量部（３〜20ppm）
の有効フッ素イオンを含んでいる。有効フッ素イオンの
含有量が１重量部（1ppm）未満では、アルミニウムのエ
ッチング反応がほとんど起こらず、皮膜が生成しない。
一方、50重量部（50ppm）を越えると、皮膜生成速度よ
りもアルミニウムのエッチング速度の方が大きくなっ
て、皮膜が生成し難くなる。また皮膜が生成したとして
も、耐沸水黒変性、塗膜との密着性が悪化する。ここ
で、有効フッ素イオンとは遊離のフッ素イオンを意味
し、その濃度はフッ素イオン電極を有するメータで処理
液を測定することにより求められる。有効フッ素イオン
の供給源としては、HF、NH4F、NH4HF2、NaF、NaHF2など
を挙げることができ、特にHFが好ましい。The surface treatment agent (surface treatment bath) of the present invention is 1 to 50 parts by weight (1 to 50 ppm), preferably 3 to 20 parts by weight (3 to 20 ppm).
It contains effective fluorine ions. When the content of effective fluorine ions is less than 1 part by weight (1 ppm), the etching reaction of aluminum hardly occurs and a film is not formed.
On the other hand, when it exceeds 50 parts by weight (50 ppm), the etching rate of aluminum is higher than the rate of film formation, and it becomes difficult to form a film. Even if a film is formed, boiling water resistance to blackening and adhesion to the coating film deteriorate. Here, the effective fluorine ion means a free fluorine ion, and the concentration thereof is obtained by measuring the treatment liquid with a meter having a fluorine ion electrode. Examples of the source of effective fluorine ions include HF, NH 4 F, NH 4 HF 2 , NaF, and NaHF 2 , and HF is particularly preferable.
尚、表面処理剤中で遊離せず、フッ素イオンを放出しな
いフッ素化合物は、有効フッ素イオンの供給源として不
適である。A fluorine compound that does not release in the surface treatment agent and does not release fluorine ions is not suitable as a source of effective fluorine ions.
また、本発明の表面処理浴はpHが2.0〜4.0、好ましくは
2.7〜3.3、であることが必要である。pHが2.0未満で
は、アルミニウムのエッチング反応が大きくなりすぎ
て、皮膜が生成し難くなり、また4.0を越えると、Zr・
Ｖ・Al−PO4の沈澱が生じ易くなる。The surface treatment bath of the present invention has a pH of 2.0 to 4.0, preferably
It should be 2.7 to 3.3. When the pH is less than 2.0, the etching reaction of aluminum becomes too large, which makes it difficult to form a film.
Precipitation of V · Al-PO 4 is likely to occur.
pHの調整は、硝酸、硫酸を用いて行うことができ、ま
た、10ppm〜500ppmの範囲を超えない限りリン酸により
行ってもよい。The pH can be adjusted using nitric acid or sulfuric acid, and phosphoric acid may be used as long as it does not exceed the range of 10 ppm to 500 ppm.
本発明の表面処理剤（表面処理浴）には、必要に応じ
て、グルコン酸（塩）、ヘプトン酸（塩）などのような
アルミニウムの有機キレート剤を添加してもよい。An organic organic chelating agent such as gluconic acid (salt) and heptonic acid (salt) may be added to the surface treatment agent (surface treatment bath) of the present invention, if necessary.
本発明の表面処理剤は、上述の各成分を水に添加混合し
て水性濃厚溶液にすることにより調製されるが、これを
適量の水で所定濃度に希釈後、必要に応じてpHを調整し
て本発明の表面処理浴とする。The surface treatment agent of the present invention is prepared by adding and mixing the above-mentioned components to water to form an aqueous concentrated solution, which is diluted with an appropriate amount of water to a predetermined concentration, and then the pH is adjusted if necessary. And used as the surface treatment bath of the present invention.
本発明の表面処理浴をアルミニウム又はその合金に適用
するには、浸漬法、スプレー法、絞りロール法などの任
意の処理方法を用いることができ、一般に室温〜50℃、
好ましくは30〜40℃の温度で適用処理する。また、処理
時間は、処理方法、処理温度によっても異なるが、通
常、５〜60秒という極めて短い時間で処理が完了する。To apply the surface treatment bath of the present invention to aluminum or its alloys, any treatment method such as dipping method, spraying method, squeezing roll method can be used, generally room temperature to 50 ° C.,
It is preferably applied at a temperature of 30 to 40 ° C. Although the treatment time varies depending on the treatment method and the treatment temperature, the treatment is usually completed in an extremely short time of 5 to 60 seconds.
本発明の表面処理浴が適用されるアルミニウム又はその
合金としては、アルミニウム、アルミニウム−銅合金、
アルミニウム−マンガン合金、アルミニウム−ケイ素合
金、アルミニウム−マグネシウム合金、アルミニウム−
マグネシウム−ケイ素合金、アルミニウム−亜鉛合金、
アルミニウム−亜鉛−マグネシウム合金などをを挙げる
ことができ、板、棒、線、管などの任意の形で処理する
ことができる。特に、アルミニウム製飲料缶を処理する
のが適している。Aluminum or its alloy to which the surface treatment bath of the present invention is applied, aluminum, aluminum-copper alloy,
Aluminum-manganese alloy, aluminum-silicon alloy, aluminum-magnesium alloy, aluminum-
Magnesium-silicon alloy, aluminum-zinc alloy,
Aluminum-zinc-magnesium alloy and the like can be mentioned, and it can be processed in any shape such as a plate, a bar, a wire and a tube. In particular, it is suitable to treat aluminum beverage cans.
本発明の表面処理浴でアルミニウム又はその合金を処理
すると、アルミニウムが有効フッ素イオンによりエッチ
ングされ、処理浴中に存在するバナジウム、ジルコニウ
ム、リン酸、フッ素とで複塩を形成し、皮膜が形成す
る。ジルコニウムはバナジウムの析出促進剤として作用
すると推定され、その結果バナジウムは相対的に皮膜表
層に多く存在し、このバナジウムの耐食性のために皮膜
面が非常に耐食性を示し、沸とう水に30分間浸漬した後
でも全く黒色化しないものと考えられる。また皮膜面に
塗装印刷を施すと皮膜と塗膜との密着性が著しく大きい
が、これはバナジウムと塗膜との相互作用によるものと
考えられる。このように本発明においては、バナジウム
イオン、ジルコニウムイオン、リン酸イオン及び有効フ
ッ素イオンの相互作用により、良好な耐食性、耐沸水黒
変性、滑り性等を有する皮膜が得られる。When aluminum or its alloy is treated in the surface treatment bath of the present invention, aluminum is etched by effective fluorine ions, and vanadium, zirconium, phosphoric acid, and fluorine present in the treatment bath form a double salt to form a film. . It is presumed that zirconium acts as a precipitation promoter for vanadium, and as a result, vanadium is relatively present in the surface layer of the film, and the corrosion resistance of vanadium makes the film surface highly corrosion resistant. It is considered that blackening does not occur even after the process. Further, when the film surface is coated and printed, the adhesion between the film and the coating film is remarkably large, which is considered to be due to the interaction between vanadium and the coating film. As described above, in the present invention, a film having good corrosion resistance, boiling water black denaturation, slipperiness, etc. can be obtained by the interaction of vanadium ion, zirconium ion, phosphate ion and effective fluorine ion.
以下、実施例及び比較例により本発明を更に詳細に説明
する。Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
なお、以下の実施例及び比較例における（１）耐沸水黒
変性、（２）塗膜密着性、（３）滑り性は、下記のよう
に評価した。In addition, (1) boiling water black resistance, (2) coating film adhesion, and (3) slipperiness in the following Examples and Comparative Examples were evaluated as follows.
（１）耐沸水黒変性 表面処理浴で処理したアルミニウム缶を乾燥し、その缶
から底部を切り出して、100℃の水道水に30分間浸漬し
た後の黒変度を下記の５段階で評価する。(1) Black water resistance against boiling water Drying an aluminum can treated with a surface treatment bath, cutting out the bottom from the can, and immersing it in tap water at 100 ° C for 30 minutes to evaluate the degree of blackness according to the following five grades. .
◎ ：まったく黒変なし ○ ：ごくわずかに黒変 △ ：わずかに黒変 × ：かなり黒変 ××：完全に黒変 （２）塗膜密着性 表面処理浴で処理したアルミニウム缶を乾燥し、その缶
の外面にエポキシ−フェノール系塗料（東洋インキ
（株）製フィニシーズＡ）を塗布、焼付硬化する。この
塗装板２枚の間に、厚さ40μｍのポリアミド系フィルム
（ダイセル化学工業（株）製ダイアミドフィルム＃700
0）をはさんで加熱圧着後、幅5mmの試験片を切り出し、
Ｔ型ピール法及び180゜ピール法で剥離強度を測定す
る。単位はkgf/5mmで表わす。なお、そのまま測定した
ものを一次密着性、90℃の水道水に7.5時間浸漬した後
測定したものを二次密着性とする。◎: No blackening at all ○: Slightly blackening △: Slightly blackening ×: Quite blackening × ×: Completely blackening (2) Adhesion of coating film Drying the aluminum can treated with the surface treatment bath, An epoxy-phenolic coating (Finishes A manufactured by Toyo Ink Co., Ltd.) is applied to the outer surface of the can and baked and cured. Between these two coated plates, a 40 μm thick polyamide film (Daicel Chemical Industries Ltd., Daiamide film # 700)
After heat-pressing with 0) sandwiched between them, a test piece with a width of 5 mm is cut out,
Peel strength is measured by the T-peel method and 180 ° peel method. The unit is kgf / 5mm. In addition, what is measured as it is is the primary adhesiveness, and what is measured after being immersed in tap water at 90 ° C for 7.5 hours is the secondary adhesiveness.
（３）滑り性 第１図に示すように、傾斜角θを変更できるようにした
滑り板１に、２つの表面処理アルミニウム缶２、２′
を、底部３、３′が下を向き、圧延目が水平方向となる
ように両面テープで固定し、その缶２、２′の上に、缶
２、２′と直交するように２つの表面処理アルミニウム
缶４、４′を載置する。その際、缶４、４′の底部５、
５′を互いに逆向きに配置し、圧延目は垂直方向になる
ようにする。また、上の２つの缶４、４′は、下の缶
２、２′と接触しない側面部で両面テープにより互いに
固定されている。(3) Sliding property As shown in FIG. 1, two surface-treated aluminum cans 2 and 2'are attached to a sliding plate 1 whose tilt angle θ can be changed.
Are fixed with a double-sided tape so that the bottoms 3 and 3 ′ face downward and the rolled eyes are in the horizontal direction, and two surfaces are placed on the cans 2 and 2 ′ so as to be orthogonal to the cans 2 and 2 ′. Place the treated aluminum cans 4 and 4 '. At that time, the bottom portion 5 of the cans 4, 4 ',
The 5'are arranged opposite to each other so that the rolling mesh is vertical. Further, the upper two cans 4 and 4'are fixed to each other by a double-sided tape at a side surface portion which does not contact the lower cans 2 and 2 '.
滑り板１をおこして、傾斜角θを大きくしていき、上の
２つの缶４、４′が滑り始めたときの角度θを測定し、
tanθから摩擦係数を算出する。摩擦係数の値から、次
の５段階評価を行う。Raise the sliding plate 1 to increase the inclination angle θ, and measure the angle θ when the two upper cans 4 and 4 ′ start sliding,
Calculate the friction coefficient from tan θ. The following five-level evaluation is performed from the value of the friction coefficient.
◎ :0.7未満 ○ :0.7以上0.8未満 △ :0.8以上0.9未満 × :0.9以上1.0未満 ××:1.0以上 実施例１〜10、比較例１〜８ アルミニウム板（JISA3004）に絞り−しごき加工を施し
て得られた缶本体を、酸性クリーナー（日本ペイント株
式会社製、商品名リドリンNHC100）でスプレー脱脂し、
水洗後、第１表に示した組成及びpHの表面処理浴で40℃
にて30秒間スプレー処理した。次いで、水洗及び脱イオ
ン水による洗浄を行い、オーブン中で200℃で乾燥し
た。乾燥後の缶について、耐沸水黒変性、塗膜密着性及
び滑り性を測定、評価した。結果は第２表に示す通りで
あった。◎: Less than 0.7 ○: 0.7 or more and less than 0.8 △: 0.8 or more and less than 0.9 ×: 0.9 or more and less than 1.0 XX: 1.0 or more Examples 1 to 10 and Comparative Examples 1 to 8 Aluminum plate (JISA3004) is drawn and ironed. The can body obtained by spray degreasing with an acid cleaner (Nippon Paint Co., Ltd., trade name Rydrin NHC100),
After washing with water, use a surface treatment bath with the composition and pH shown in Table 1 at 40 ℃
It was sprayed for 30 seconds. Then, it was washed with water and washed with deionized water, and dried in an oven at 200 ° C. The cans after drying were measured and evaluated for boiling water blackening resistance, coating film adhesion and slipperiness. The results are shown in Table 2.
第１表 注：（１）NH4VO3として添加 （２）（NH4）2ZrF6として添加 （３）H3PO4として添加 （４）HFとして添加 （５）pHの調整はHNO3及びアンモニア水 により行った。 Table 1 Note: (1) Add as NH 4 VO 3 (2) Add as (NH 4 ) 2 ZrF 6 (3) Add as H 3 PO 4 (4) Add as HF (5) Adjust pH to HNO 3 And aqueous ammonia.
（６）白濁 以上の結果から明らかなように、本発明の表面処理浴で
処理した場合（実施例１〜10）は、耐沸水黒変性、塗膜
との密着性、滑り性共に良好な結果が得られるが、バナ
ジウムイオンが10ppm（10重量部）未満の場合（比較例
１及び７）は、耐沸水黒変性、塗膜密着性、滑り性がい
ずれも不良である。また、ジルコニウムイオンが10ppm
（10重量部）未満の場合（比較例２及び８）及び有効フ
ッ素イオンが1ppm（１重量部）未満の場合は（比較例
４）は、満足な皮膜が形成されず、耐沸水黒変性、塗膜
密着性、滑り性のいずれもが不良である。なお、比較例
４では、処理浴に沈澱が生じ、白濁していた。更に、リ
ン酸イオンが10ppm（10重量部）未満の場合（比較例
３）は、耐沸水黒変性、塗膜密着性が劣ったものとな
る。pHが2.0未満の場合（比較例５）は、皮膜が形成し
難いため、わずかに黒変が生じ、塗膜密着性も悪い。一
方、pHが4.0を越える場合（比較例６）は、処理浴に沈
澱が生じ、白濁して耐沸水黒変性がやや劣り、塗膜密着
性も悪くなる。(6) White turbidity As is clear from the above results, when treated with the surface treatment bath of the present invention (Examples 1 to 10), good results were obtained with respect to blackening resistance to boiling water, adhesion to coating film, and slipperiness. However, when vanadium ions are less than 10 ppm (10 parts by weight) (Comparative Examples 1 and 7), boiling water black resistance, coating adhesion, and slipperiness are all poor. Also, zirconium ion is 10ppm
When it is less than (10 parts by weight) (Comparative Examples 2 and 8) and when the effective fluorine ion is less than 1 ppm (1 part by weight) (Comparative Example 4), a satisfactory film is not formed and boiling water black resistance, Both coating adhesion and slipperiness are poor. In addition, in Comparative Example 4, precipitation occurred in the treatment bath and it was cloudy. Furthermore, when the phosphate ion content is less than 10 ppm (10 parts by weight) (Comparative Example 3), boiling water resistance to blackening and coating film adhesion are poor. When the pH is less than 2.0 (Comparative Example 5), it is difficult to form a film, so a slight blackening occurs and the coating film adhesion is poor. On the other hand, when the pH exceeds 4.0 (Comparative Example 6), precipitation occurs in the treatment bath, it becomes cloudy and boiling water resistance to blackening resistance is slightly inferior, and coating film adhesion is poor.
本発明の表面処理剤（表面処理浴）によれば、低温、短
時間で極めて耐食性の高い皮膜をアルミニウム又はその
合金の表面に形成することができる。この皮膜は沸とう
水中に浸漬しても黒色化せず、低皮膜量でも優れた耐沸
水黒変性を示す。また、皮膜上に塗装印刷を施す場合、
非常に強固な塗膜密着性を得ることができる。更に、皮
膜面が良好な滑り性を有しているため、缶の搬送を行う
うえで極めて有利である。According to the surface treatment agent (surface treatment bath) of the present invention, a film having extremely high corrosion resistance can be formed on the surface of aluminum or its alloy at low temperature in a short time. This film does not blacken even when immersed in boiling water, and exhibits excellent blackening resistance against boiling water even with a small amount of film. In addition, when applying paint printing on the film,
Very strong coating adhesion can be obtained. Further, since the coating surface has a good slip property, it is extremely advantageous for carrying the can.
本発明の表面処理剤（表面処理浴）は処理液の濃度が多
少変動しても十分な性能を得ることができるので、処理
液の管理が容易になるという利点も有している。The surface-treating agent (surface-treating bath) of the present invention can obtain sufficient performance even if the concentration of the treatment liquid varies to some extent, and thus has an advantage of facilitating management of the treatment liquid.
以上のような特徴を有する本発明の処理剤は特にアルミ
ニウム製缶の表面処理に好適である。The treating agent of the present invention having the above characteristics is particularly suitable for surface treatment of aluminum cans.
第１図は、滑り性の測定方法を説明するための斜視図で
ある。 １……滑り板 ２、２′、４、４′……アルミニウム缶FIG. 1 is a perspective view for explaining a method of measuring slipperiness. 1 ... Sliding plate 2, 2 ', 4, 4' ... Aluminum can
Claims (4)
て、ジルコニウムイオンを10〜500重量部、リン酸イオ
ンを10〜500重量部、及び遊離フッ素イオンを１〜50重
量部の割合で含有することを特徴とするアルミニウムま
たはその合金の表面処理剤。1. A zirconium ion in an amount of 10 to 500 parts by weight, a phosphate ion in an amount of 10 to 500 parts by weight, and a free fluorine ion in an amount of 1 to 50 parts by weight with respect to 10 to 1000 parts by weight of vanadium ion. A surface treatment agent for aluminum or an alloy thereof, which is characterized in that
記遊離フッ素イオンがHF、NH4F、NH4HF2、NaF及びNaHF2
からなる群から選ばれたフッ素化合物から得られたもの
であることを特徴とする表面処理剤。2. The surface treatment agent according to claim 1, wherein the free fluorine ions are HF, NH 4 F, NH 4 HF 2 , NaF and NaHF 2.
A surface treatment agent, which is obtained from a fluorine compound selected from the group consisting of:
ニウムイオンを10〜500ppm、リン酸イオンを10〜500pp
m、遊離フッ素イオンを１〜50ppm含み、pHが2.0〜4.0で
あることを特徴とするアルミニウムまたはその合金の表
面処理浴。3. Vanadium ions are 10 to 1000 ppm, zirconium ions are 10 to 500 ppm, and phosphate ions are 10 to 500 pp.
A surface treatment bath of aluminum or its alloy, characterized in that it contains m, 1 to 50 ppm of free fluorine ions, and has a pH of 2.0 to 4.0.
記遊離フッ素イオンがHF、NH4F、NH4HF2、NaF及びNaHF2
からなる群から選ばれたフッ素化合物から得られたもの
であることを特徴とする表面処理浴。4. The surface treatment bath according to claim 3, wherein the free fluorine ions are HF, NH 4 F, NH 4 HF 2 , NaF and NaHF 2.
A surface treatment bath, which is obtained from a fluorine compound selected from the group consisting of:
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63033755A JPH0788588B2 (en) | 1988-02-15 | 1988-02-15 | Surface treatment agent and treatment bath for aluminum or its alloys |
| CA000591030A CA1333043C (en) | 1988-02-15 | 1989-02-14 | Surface treatment chemical and bath for aluminium and its alloy |
| DE89102575T DE68907112T2 (en) | 1988-02-15 | 1989-02-15 | Composition and bath for surface treatment of aluminum and aluminum alloys. |
| US07/310,569 US4992115A (en) | 1988-02-15 | 1989-02-15 | Surface treatment chemical and bath for aluminum and its alloy |
| EP89102575A EP0337075B1 (en) | 1988-02-15 | 1989-02-15 | Surface treatment composition and surface treatment bath for aluminium and aluminium alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63033755A JPH0788588B2 (en) | 1988-02-15 | 1988-02-15 | Surface treatment agent and treatment bath for aluminum or its alloys |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01208477A JPH01208477A (en) | 1989-08-22 |
| JPH0788588B2 true JPH0788588B2 (en) | 1995-09-27 |
Family
ID=12395243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63033755A Expired - Lifetime JPH0788588B2 (en) | 1988-02-15 | 1988-02-15 | Surface treatment agent and treatment bath for aluminum or its alloys |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788588B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101783A (en) * | 1996-06-14 | 1998-01-06 | Nippon Paint Co Ltd | Aluminum surface treating agent, treatment therefor and treated aluminum material |
| JP4008620B2 (en) * | 1999-06-04 | 2007-11-14 | カルソニックカンセイ株式会社 | Aluminum alloy heat exchanger |
| JP4615807B2 (en) * | 1999-12-13 | 2011-01-19 | 東洋鋼鈑株式会社 | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet |
| JP4778769B2 (en) * | 2005-10-24 | 2011-09-21 | 昭和アルミニウム缶株式会社 | Aluminum can manufacturing method and aluminum can manufactured by the method |
| JP6184051B2 (en) | 2011-09-21 | 2017-08-23 | 日本ペイント・サーフケミカルズ株式会社 | Surface treatment method for aluminum heat exchanger |
| JP6146954B2 (en) | 2012-03-09 | 2017-06-14 | 日本ペイント・サーフケミカルズ株式会社 | Chemical conversion treatment agent and chemical conversion treatment film |
| JP6105979B2 (en) | 2012-03-09 | 2017-03-29 | 日本ペイント・サーフケミカルズ株式会社 | Surface treatment method for aluminum heat exchanger |
| JP6055085B2 (en) | 2013-04-03 | 2016-12-27 | 日本ペイント・サーフケミカルズ株式会社 | Chemical conversion treatment agent and metal surface treatment method |
| CN105143512B (en) * | 2013-04-03 | 2018-01-12 | 日涂表面处理化工有限公司 | The surface treatment method of aluminum-made heat exchanger |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56136978A (en) * | 1980-03-26 | 1981-10-26 | Showa Alum Ind Kk | Chemically treating solution for aluminum or aluminum alloy |
-
1988
- 1988-02-15 JP JP63033755A patent/JPH0788588B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56136978A (en) * | 1980-03-26 | 1981-10-26 | Showa Alum Ind Kk | Chemically treating solution for aluminum or aluminum alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01208477A (en) | 1989-08-22 |
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