JPS58189377A - Surface treating agent for aluminum and its alloy - Google Patents

Surface treating agent for aluminum and its alloy

Info

Publication number
JPS58189377A
JPS58189377A JP7157782A JP7157782A JPS58189377A JP S58189377 A JPS58189377 A JP S58189377A JP 7157782 A JP7157782 A JP 7157782A JP 7157782 A JP7157782 A JP 7157782A JP S58189377 A JPS58189377 A JP S58189377A
Authority
JP
Japan
Prior art keywords
ions
chromium
surface treatment
treatment agent
sexivalent
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
Application number
JP7157782A
Other languages
Japanese (ja)
Other versions
JPS621476B2 (en
Inventor
Toru Ishii
透 石井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Light Metal Co Ltd
Original Assignee
Nippon Light Metal Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Light Metal Co Ltd filed Critical Nippon Light Metal Co Ltd
Priority to JP7157782A priority Critical patent/JPS58189377A/en
Publication of JPS58189377A publication Critical patent/JPS58189377A/en
Publication of JPS621476B2 publication Critical patent/JPS621476B2/ja
Granted legal-status Critical Current

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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/37—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 fluorides or complex fluorides containing also hexavalent chromium compounds
    • C23C22/38—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 fluorides or complex fluorides containing also hexavalent chromium compounds containing also phosphates
    • 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
    • C23C22/24—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 hexavalent chromium compounds
    • C23C22/33—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 hexavalent chromium compounds containing also phosphates

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

PURPOSE:To obtain a surface treating agent for Al causing no coloring and leaving no sexivalent Cr, by preparing an aqueous soln. contg. tervalent Cr ions, sexivalent Cr ions, phosphate ions and a water soluble acrylic polymer at specified concns. CONSTITUTION:A surface treating agent for Al and its alloys is obtd. by blending 1l water with 0.8-1.5g tervalent Cr ions, about 0.1-0.6g sexivalent Cr ions, 1.5-15g phosphate ions and 0.5-15g water soluble acrylic polymer. The ratio of the sexivalent Cr ions to the total Cr ions is 0.05-0.35. The tervalent Cr ions are ions from chromium hydroxide, chromium nitrate or the like, and the sexivalent Cr ions are ions from chromium trixoide or the like. The phosphate ions are ions from phosphoric acid or the lile. ''Acryzole A-1'' or the like is used as the water soluble acrylic polymer.

Description

【発明の詳細な説明】[Detailed description of the invention]

本光明は、アルミニウム及びその８　’？　ｔｏ表間の
防食処理あるいは塗装の下地処理に用いられる表面処理
４１１に関するものである。 従来から、アルミ、＝ラム及びそし、合金材（以ド。 アルミニウム伊という）の表面の肋員処理あるいは塗装
の下地処理用として各檀Ｖ衣聞処理剤が知ら第１ている
。これらのうち、クロム系の表′面処理剤は、皮膜形ｆ
ＪＳｊ、の機構上から、いわゆるリンス型と呼ばれる変
換皮膜形成型と、ツノリンス型と呼ばれる塗布型とに分
類できる。 しかして、リンス型の表面処理剤（ハウアルミニウム衣
而に広範・な用途に対応できる良好な性能を有する皮Ｉ
Ｎ’に形成するので長く使用されている。 しかしながら、この型の表面処理剤は１表向処理剤を使
用して竹なうアルミニウム表面の化成’ＩＪＬ理のイ友
に水洗をする必要がある。このために、多情（・て排出
される洗浄水中に表面処理剤に含有される６１曲クロム
や〕、化物などの有害物質が含有さ才することｉｌＣな
り、洗浄水を排棄するためには、こねらの有害物質を除
かねばならず、美大な除去設備投資、除去費などを必要
とするといった欠点がある。 また１、ツノリンス型と呼ばれる塗布型の表向処理剤は
、衣ｌ処理剤を塗布した紋に水洗が不安であるためにリ
ンス型の表向処理剤のような排水処理ｒ必要とぜず、衣
■処理剤を塗布したアルミニラム材は、乾燥体、ぞのま
ま防貢皮膜処理材として、あるいは、ざらに準装を行な
った後に１史出し得るという利点かめる。 しかして、この型の表面処理剤にも含有する主要成分で
あるクロムの原子価によって、　　Ｃｒ（ｔｉｌｌ型Ｃ
ｒ（Ｖｌ）型、　　Ｃｒ（１）　＋　Ｃ直■）型の三つ
に分ｚ＋：Ｉｌｌされるすなわち、Ｃｒ（■）型（・ま
　ｃｒ３＋　、　　ｐ請を主要成分とし、と）１に壱機
吻とかコロイダルシリカ＋　　Ｆ’。 ＮＯｉなどを添加した組成を廟している。（たとえは、
特開昭５３−；１（７３５０，特開昭５３−１１５６２
５など）　この型の表面７＋１理剤で処理して生成され
る皮膜は無色であり、びらに皮膜中に６前のクロムが有
在し斤い利点が二（５るので広範な分計への応用が考え
られる。ことに、わが国においてはアルミニウム素地の
廟する片しい金属感を表門処理においても績喰的に生か
し７たものが好壕れるので、生成する。皮膜力旬、１す
、色でちることの夾際囲でのメリットは犬さｌものがあ
る。しかしながらｌ　　Ｃｒ１ｌｌｌｌ型の皮脂は、と
＜This light is aluminum and its 8'? The present invention relates to surface treatment 411 used for anticorrosion treatment between surfaces or surface treatment for painting. BACKGROUND OF THE INVENTION Hitherto, various varnish coating agents have been well-known for treating the surfaces of aluminum, laminate, and alloy materials (hereinafter referred to as aluminum) or as a base treatment for painting. Among these, chromium-based surface treatment agents have a film type f
Based on the mechanism of JSj, it can be classified into a conversion film forming type called a rinse type and a coating type called a tsunorinse type. Therefore, a rinse-type surface treatment agent (a coating with good performance that can be used in a wide range of applications for aluminum coatings) has been developed.
It has been used for a long time because it is formed into N'. However, this type of surface treatment agent requires washing with water before chemical formation of the aluminum surface using the surface treatment agent. For this reason, harmful substances such as 61% chromium contained in surface treatment agents and other chemicals may be contained in the cleaning water that is discharged. However, there are drawbacks such as the need to remove harmful substances from the dough, requiring large investment in removal equipment, and removal costs.1. Since it is difficult to wash the pattern coated with a treatment agent with water, there is no need for drainage treatment such as a rinse-type surface treatment agent. This type of surface treatment agent has the advantage of being able to be used as a coating treatment material or after being coated with rough coating. Type C
It is divided into three types: r (Vl) type, Cr (1) + C direct ■) type, that is, Cr (■) type (・Ma cr3+, with p as the main component, and) 1 to 1. Mechanical nose or colloidal silica + F'. The composition is composed of additives such as NOi. (example is,
JP-A-53-1 (7350, JP-A-53-11562)
5, etc.) The film produced by treating this type of surface with a 7+1 chemical agent is colorless, and has the advantage of having chromium 6 before being present in the film on the leaf. In particular, in Japan, it is preferable to take advantage of the dull metallic feel of the aluminum substrate in the front gate treatment, so it is produced. The extreme benefits of coloring are similar to those of dogs.However, Cr1llll type sebum is

【１゛−の下地処理皮膜としての性能はト塗り塗料の
硬化温度によって大きく変化する。すなわち、ｍ化を通
常１４０〜１９０℃（被塗物の１ｍ　！ｆｆ　＋　リド
＋”ｌ　休）で行なわれるが、このものを高温ＩＪｊ雰
囲気下に放置するとブリスターあるいは準膜丁価食とい
う形の欠陥を呈するように防貢１住の点で満足し侍ない
。そして、この欠陥は、ガ囲気の鴨食性が増すにつれ一
層顕著になってくる。 このためにＣｒ　（［）型の表面処理剤は、その用途を
コイル塗装ラインのような塗膜硬化時の温度が２００℃
を超える条件で処理される場合に限定せざるを得ない欠
点がある。 次に、　　Ｃｒ（Ｖｌ）型の表面処理剤は、　　Ｃｒ”
　、　　ＰＯ”２　ｉ−主要５９分とし、各種成分が添
加された組成ヲ櫓する。（・−と、えは、特開昭５４−
３１０４３など）１゜かして、この池の表面処理剤によ
って形成さ、ｆｌる皮８ｖの防良性あるい（１塗装の下
地としての性能（・１゜広い谷す１理条件に亘って良好
ではある力・、侍られる支保が淡褐色の見苦しい色に層
色している。このために、クリ−グー準科は勿論、隠蔽
力の低い見料のド進込埋としても１ψえないし、さらに
、生成反ｍ−Ｐにり側クロムが残照しているなどの欠点
がある。 さらに、　Ｃｒ（ｌｌｌｌ　＋Ｃｒ（Ｖｌ）型の表面処
理剤は、Ｃｒ。 ３＋ 及びＣｒを主要成分とし、これにＰＯ４、５ｉ０２ある
いはポリアクリル酸などが添加された組成を有する。 （たとえば２％開昭ｂ４−１１０１４９．米国特許第溶
液の安定性が搦なわれるとされているし、　　Ｃｒ（■
１）型と同様に皮１１＝ｊがｒ・ｋ褐色に着色され、ま
た皮１％、中ｖ（６１１１Ｉ］クロムが残留しているな
どの欠点が、苛められる。 本弁明者らは、こｔｌらの欠点のない表面処理剤を得べ
く多くの研死を重ねた結末＋　　Ｃｒ（ｉｎ！型の表面
処理剤に６１１ｔｌＩのクロムを少量添加した衣■処理
剤にすることによって、宥芭もなく、６１曲クロムが残
宙していない皮膜が侍られることを死出して杢兄明をな
したものでのる。すなわち２本発明は。 （５） 水ｌｌ中に、３価クロムイオン０，８〜１．５ｙ、６価
クロムと酸クロムイオンの比が００５〜０３５の範囲の
６Ｉｌｌｈクロムイオン、リン酸イオン１．５〜１５ｙ
＆び水浴性アクリルボ、リマ−０，５〜１５ｙを配合し
てなるアルミニウム及びその合金の次面処理剤である。 水酸化クロム、硝酸クロム、リン酸クロム、酢酸クロム
あるいはマレイン酸クロムその他適宜Ｊ）クロム塩・′
ノ形で供給でき、　　Ｃｒ　　の濃度は、０．８〜１５
７々の部間が好ましい。 ６ＩｌｌＩ！クロムイオン（Ｃｒ）は、たとえば三酔什
クロムあるいは東りロム酸塩、クロム酸地などの’ｊ’
ｃ　ｌｅｒ　ｌ＋６１１ｔ＋＋クロム化は物の形で供給
される。Ｃｒｔ１′の一層は、６１＋１１ニクロムイオ
ンと総クロムイオンとの比、すなわち、Ｃｒ／Ｃｒ３９
士Ｃｒ０＋　の比が０．０５〜Ｕ、３５．好ましくμ、
０．２〜０３３の範囲であり。 かつ、　Ｃｒ　　の龜度が０．１〜０．６ノｈの範囲で
あり。 ０．４〜ｔＪ５ｙ／ｈの範囲が好ましい。しかして、６
（６） １曲クロムイオンのｒｑｒ、合割合が、Ｃｒ６ンＣｒ３
”＋　Ｃｒ６＋＝　’００５〜０３５における下限値以
下では、６価クロム添加の効果が激減し、−Ｆ限値を超
えると得られる皮膜が着色し、クリヤー塗装は勿論、淡
色の塗料の塗装下地として便…し得ないので用途が大巾
に限定されるものである。 °　リン酸イオン（Ｐ０４　）は９通常、リン酸、リン
編塩として供給さね、　　ＰＯ４の濃度は、０．１〜０
．６勘の範囲で配合さね、０．４〜０．５　Ｐ／１−の
範囲が好１〜い。 水溶性アクリルポリマーは、たとえば、アクリ７’　−
／Ｌ、　Ａ　−１（１ｔｊ６　名、　（’−ムアンドハ
ース社。 アクリル酸固形分２５ＦＩ、ｌ［％を含む水浴久、のよ
うなポリアクリル酸またはそのエステルが用いられ、０
５〜１５　Ｆ／、　、好ましくは、３〜８ｙ／Ｊ・の範
囲で用いる。 なよ・、この他、不玲１庄コロイダルシリカを０．１〜
Ｉ　５１／７．好ましくは、５λ１０４）の範囲で省く
り［１し、りるいば、）、仕切をフッ酸ないしはでの鉛
化合物の形でＰ゛−とじて０．１〜２　Ｐ／ｌの範囲で
（７） 添ｔｙｕ−ｔろことｒよ支＞ｉｔで二ない。 本発明の表面処理剤は、このような各原料の所定量をと
り水に汀ｍ混台することによって調製することができる
。なお、使用する水は、紛イオノ水であることが好まし
い。 ること（こよって調製することもできる。 剤の的如ル分子ｄ、２〜３５〃えである。なお２表面処
理剤の安定性がより、Ｃｒ　　の−賄は、調製体約３　
、ｌ＝１間変化がぜめられなかった。 このようにして侍だ本発明の金属処理剤は２通常のよう
に、ロール塗り、リバースロール塗り。 階偵、ぴしし堕り、吹き付け、ぼたはミスト塗装なとに
よって塗料することかでさ、金属表凹に液膜の膜摩刀４
５〜２０μｍ、好１しくに１５μｍ〕１削抜の厚σにな
るように壁布する。表面処理剤を塗布恢、　７Ｊ１熱乾
脈するた、板処理叛の温度か１７０℃以（８） 下で乾燥することが１勺了しい。しかして、乾魚体の水
洗は不要であり、そのままの状態で、あるいは、さらに
塗料を塗装して使用する。 このようにして９本発明の表面処理剤を使用して得られ
た金属表面の皮膜は、無色であって、湿」Ｃ法によって
分析した結果は、　　Ｃｒ　　は検出されなった。さら
に、皮膜を施行した皮膜材を２ｇ度は明確ではないが、
　　Ｃｒ　　は検出されなかった。 本発明は、３仙】クロムイオン、及び６１曲クロムイオ
ンと総クロムイオンとの比を００５〜０３５となるよう
な６価クロムイオンを主要成分として配合したりで２表
面処理４１１の安定性がよく、アルミニウム及びその合
金の衣用１処理に使用した場合、逝常通りの塗布操作が
行ない得、水洗をする必要がないので排水処理の必要が
なく、皮膜自身の防賞性は勿論、塗装の下地反映として
の性質も向上し侍、無色の皮膜で反朕中に６価クロムが
残留していない皮ＢＶが祷られ、広範囲の用途に用い侍
るな（９） どすぐれた効果がａαめられる。 次に、実施例を述べる。 実施例　１ １）表面処理剤の調製 リン酸クロム三水和物を３．９　’／ｌ、　＋　　三酸
化クロムｆ１１．８ｊ’／ｚ　、　　リン酸ｆ　８．３
Ｆ／／　　＋　　フッ化水素酸０ｒ／Ｃｒ””　十Ｃｒ
”−０，２９，ＰＣｆ４　８．ＯＰ／１．　　Ｆ−１，
１’／ｚ＋水溶性アクリルポリマー９．０Ｐ７１　、　
’ＰＨ１，７のような組成を有する表面処理剤が得らｔ
また。 ２）次面Ｉ７ムＬ理粕果 アルミニウム板（１１００Ｈ２４，１ｍｍ厚）を通常の
非工、チンダ性りリーナーヲ快用して仲脂洗浄し、１）
により調製した表面処理剤をｆＪ　１５μｍの液膜とし
てΦり広けた。その挨＋１３ｔ１℃（機高９０℃）の、
＃ｌ＆Ｖ風で１分間加熱乾燥した。処理後の無色の皮膜
を有する＆を室温まで放冷した後、熱硬（１０） 化型の塗料を用いてＣｆ装し、塗料の焼付けを＋５０℃
で３０分間行なった。得られた乾燥Ｃヂ族厚は２０μｍ
　であった。 被竿物は、基板目テープ剥離試験による芦膜の付漸性試
験、塗面に十字の傷を入れた一後キヤス試ｋＷ　ｅ　７
２　時間ｔ　及ヒ、ＪＩＳ　　Ｚ　　２３７１の方法に
基価クロムは認められなかった。 実施ｊｕｌ＋　２ 実施沙！１１−１＞で調装した表面処理液を用い、アル
ミニウムｉ　（１１００−）（２４，１ｍｍ厚）に対し
約１５μｍの厚さに塗り広けたｉ、１７０℃で５分＋’
＋４１皮膜不浴化処理を付なった。生成された鉦色の皮
膜の耐食性を塩水噴霧試験を１００時間行なって調べた
。結果を第１六に小す。 なお、皮膜材を３５℃に保持した脱イオン水中にＩＡＩ
間浸漬（比ｇ　’ｇ　９５ｍ４．１ｍ２　）　Ｌ、　Ｌ
：ｒ　　Ｏ）抽出を試みたが使用されなかった。また、
皮膜の湿比斡ｖ１１１ 実施１＋１１１−１　）で調製した表面処理剤からＣｒ
　　を除いた組ｂｙのいわゆるＣｒ（副型の表面処理剤
を使用して、実施例１と同様な条件下で処理した後。 同体な試験を行なった。結果を第１表に下す。 ’（ｉ−１１７用して、実施例２と同様な条件下で処理
したＩＺ２．同けな試９を行なった。結果を第１衣に示
す。 のい１つゆるＣｒ　（ｍｌ　＋　Ｃｒ　（■）型のべ囲
処理剤を調製し。 実姉例２と同体に条件下に処理した俊、同様な試験を行
なった。結果を第１表に示す。 なお、実施例２と同様に皮膜のＣｒ　　抽出私、１ｖと
１雇式か＋７ｒケ何なった轄釆は、いずれもＣｒ　　が
十・ｐ出さ　第１　た。　　　　　　　　′ 第　　１　　表 特許出願人　　日本軽金属株式会社[1゛- Performance as a base treatment film varies greatly depending on the curing temperature of the paint. In other words, m-coating is normally carried out at 140 to 190°C (1m of object to be coated), but if this material is left in a high-temperature IJj atmosphere, blisters or quasi-membrane corrosion occur. However, as the moths become more and more phagocytic, these defects become more noticeable.For this reason, Cr ([) type surface treatment agents are used. The application is for coil painting lines where the temperature during coating film curing is 200℃.
There is a drawback that it must be limited to cases where processing is performed under conditions exceeding . Next, the Cr(Vl) type surface treatment agent is Cr”
, PO"2 i-Main 59 minutes, and the composition in which various ingredients were added.
31043, etc.), the surface treatment agent of this pond is formed by the surface treatment agent. However, the support that can be served is layered with an unsightly light brown color.For this reason, it is impossible to bury not only Kriegu subfamily, but also a sight with low concealment power. Furthermore, there are drawbacks such as the afterglow of chromium on the side of the generated anti-m-P.Furthermore, the Cr(llll+Cr(Vl) type surface treatment agent has Cr.3+ and Cr as its main components, and It has a composition in which PO4, 5i02 or polyacrylic acid is added.
1) Similar to the mold, the skin 11=j is colored r/k brown, and the skin has 1%, medium v (6111I) chromium, remaining. The result of many efforts to obtain a surface treatment agent that does not have the drawbacks of tl et al. + Cr(in!) type surface treatment agent with a small amount of 611tlI chromium added to the surface treatment agent has been improved. (5) Zero trivalent chromium ions in 1 liter of water. , 8-1.5y, 6Illh chromium ion, phosphate ion 1.5-15y with a ratio of hexavalent chromium and acid chromium ion in the range of 005-035
This is a secondary surface treatment agent for aluminum and its alloys, which contains water-bathable acrylic rubber and Limar-0.5-15y. Chromium hydroxide, chromium nitrate, chromium phosphate, chromium acetate or chromium maleate and other appropriate J) Chromium salts
It can be supplied in the form of Cr with a concentration of 0.8 to 15
Seven parts are preferred. 6IllI! Chromium ion (Cr) is a chromium ion (Cr), for example, 'j' of chromate, chromate, chromate, etc.
cler l+611t++ chromation is supplied in physical form. One layer of Crt1' has a ratio of 61+11 nichrome ions to total chromium ions, i.e., Cr/Cr39
The ratio of Cr0+ is 0.05 to U, 35. Preferably μ,
It ranges from 0.2 to 033. and the degree of tarnishing of Cr is in the range of 0.1 to 0.6h. The range of 0.4 to tJ5y/h is preferable. However, 6
(6) The rqr of the first chromium ion, the combined ratio is Cr6 - Cr3
``+Cr6+='' Below the lower limit value of '005 to 035, the effect of hexavalent chromium addition is drastically reduced, and when it exceeds the -F limit value, the resulting film becomes colored and cannot be used as a coating base for light-colored paints as well as clear coatings. Since it cannot be excreted, its use is largely limited. ° Phosphate ion (P04) is usually supplied as phosphoric acid or phosphorus salt, and the concentration of PO4 is 0.1 to 0.
．． Please mix it within the range of 6 intuition, preferably the range of 0.4 to 0.5 P/1-. The water-soluble acrylic polymer is, for example, acrylic 7'-
/L, A-1 (1tj6 names, ('-M&Haas Co., Ltd.) Polyacrylic acid or its esters are used, such as acrylic acid solids containing 25 FI, l[%, 0
It is used in the range of 5 to 15 F/, preferably 3 to 8 y/J. Nayo, in addition to this, Furei 1 Sho colloidal silica is 0.1 ~
I 51/7. Preferably, it is omitted in the range of 5λ104) and the partition is closed with P in the form of a lead compound in hydrofluoric acid or in the range of 0.1 to 2 P/l (7 ) It's not two. The surface treatment agent of the present invention can be prepared by taking a predetermined amount of each of these raw materials and mixing it with water. Note that the water used is preferably powdered ionized water. (It can also be prepared in this way. The target molecule d of the agent is 2 to 35. Furthermore, depending on the stability of the surface treatment agent, the amount of Cr used in the preparation is approximately 3.
, no change was observed between l=1. In this way, the metal treatment agent of the present invention can be used in two conventional ways: roll coating and reverse roll coating. The paint is applied by spraying, spraying, and mist painting, and a liquid film is applied to the concave metal surface.
5 to 20 μm, preferably 15 μm] The wall cloth is made to have a thickness of 1 cutout σ. After applying the surface treatment agent and drying it under 7J1 heat, it is recommended to dry it at a temperature of 170°C or lower (8), which is the temperature of the plate treatment. Therefore, it is not necessary to wash the dried fish body with water, and it can be used as is or after being coated with paint. The film on the metal surface thus obtained using the surface treatment agent of the present invention was colorless, and as a result of analysis by the wet C method, no Cr was detected. Furthermore, although it is not clear that the coating material on which the coating was applied is 2g,
Cr was not detected. The present invention improves the stability of 2-surface treatment 411 by blending chromium ions as main components and hexavalent chromium ions such that the ratio of chromium ions to total chromium ions is 005 to 035. When used for the coating treatment of aluminum and its alloys, the coating operation can be carried out as usual, and there is no need to wash with water, so there is no need for drainage treatment. It also improves its properties as a reflection of the substrate, and the colorless film with no residual hexavalent chromium is desired, making it useful for a wide range of applications (9). It will be done. Next, an example will be described. Example 1 1) Preparation of surface treatment agent Chromium phosphate trihydrate 3.9'/l, + chromium trioxide f11.8j'/z, phosphoric acid f8.3
F// + Hydrofluoric acid 0r/Cr"" 10Cr
”-0,29,PCf4 8.OP/1.F-1,
1'/z + water-soluble acrylic polymer 9.0P71,
'A surface treatment agent with a composition such as PH1.7 can be obtained.
Also. 2) The next surface I7mm L grain aluminum plate (1100H24, 1mm thickness) was cleaned using a regular non-working, tinkering and leaner, and 1)
The surface treatment agent prepared by the method was spread as a liquid film with an fJ of 15 μm. The dust +13t1℃ (machine height 90℃),
It was dried by heating with #1&V wind for 1 minute. After treatment, the colorless film was allowed to cool to room temperature, and then coated with Cf using a thermosetting (10) type paint, and the paint was baked at +50°C.
This was done for 30 minutes. The thickness of the dried C group obtained was 20 μm.
Met. The rods to be tested were a reed film deposition test using a tape stripping test on the substrate, and a cross-shaped scratch on the painted surface, followed by a cross-shaped scratch test.kW e 7
After 2 hours and 2 hours, no basic chromium was found in the method of JIS Z 2371. Implementation jul + 2 Implementation Sha! Using the surface treatment solution prepared in step 11-1>, it was spread on aluminum i (1100-) (24.1 mm thick) to a thickness of about 15 μm, and heated at 170°C for 5 minutes+'.
+41 film anti-bath treatment. The corrosion resistance of the produced dark-colored film was investigated by conducting a salt spray test for 100 hours. Reduce the result to the 16th. In addition, IAI was added to the coating material in deionized water kept at 35°C.
Intermittent immersion (ratio g'g 95m4.1m2) L, L
:r O) Attempted extraction but not used. Also,
Cr from the surface treatment agent prepared in 111-1)
After treatment under the same conditions as in Example 1 using a so-called Cr (subtype) surface treatment agent of the group with the exception of . IZ2 treated under the same conditions as Example 2 using I-117.A similar test 9 was conducted.The results are shown in Figure 1. A mold coating treatment agent was prepared, and the same test was conducted under the same conditions as in Example 2. The results are shown in Table 1. In addition, in the same manner as in Example 2, Cr extraction from the film was carried out. For me, 1v and 1 employment ceremony, +7r, etc., both had Cr of 10.p.' Table 1 Patent Applicant Nippon Light Metal Co., Ltd.

Claims (1)

【特許請求の範囲】 １）水ｌｌ中に、３１曲クロムイオン０．８〜１．５ｇ
。 ６価クロムイオンと総クロムイオンの比が０．０５〜＋
１３５の範囲の６　ｆＸクロムイオン、リン酸イオン１
．５〜１５ｇ及び水抽性アクリルホリマー０．５〜１５
ｇを自己合し・てなることを特徴とするアルミニウム及
びその合金の表面処理剤。[Claims] 1) 0.8 to 1.5 g of 31-benigned chromium ion in 1 liter of water
. The ratio of hexavalent chromium ions to total chromium ions is 0.05 to +
6 fX chromium ion, phosphate ion 1 in the range of 135
．． 5-15g and water-extractable acrylic polymer 0.5-15g
A surface treatment agent for aluminum and its alloys, which is characterized by self-combining and forming g.
JP7157782A 1982-04-30 1982-04-30 Surface treating agent for aluminum and its alloy Granted JPS58189377A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7157782A JPS58189377A (en) 1982-04-30 1982-04-30 Surface treating agent for aluminum and its alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7157782A JPS58189377A (en) 1982-04-30 1982-04-30 Surface treating agent for aluminum and its alloy

Publications (2)

Publication Number Publication Date
JPS58189377A true JPS58189377A (en) 1983-11-05
JPS621476B2 JPS621476B2 (en) 1987-01-13

Family

ID=13464688

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7157782A Granted JPS58189377A (en) 1982-04-30 1982-04-30 Surface treating agent for aluminum and its alloy

Country Status (1)

Country Link
JP (1) JPS58189377A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4650527A (en) * 1983-08-12 1987-03-17 Nippon Light Metal Company Limited Hydrophilic surface-treating process for an aluminum article

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50158535A (en) * 1974-06-12 1975-12-22
JPS5230235A (en) * 1975-09-02 1977-03-07 Nippon Paint Co Ltd Chromating process
JPS5230230A (en) * 1975-09-03 1977-03-07 Toyota Motor Co Ltd Method of cutting off gate and runner during material melting
JPS542231A (en) * 1977-06-07 1979-01-09 Nippon Paint Co Ltd Metal surface treating method
JPS54110145A (en) * 1978-01-30 1979-08-29 Amchem Prod Metal surface coating composition* preparation thereof* and application using same
JPS54133440A (en) * 1978-03-31 1979-10-17 Amchem Prod Aluminum coating composition and method for coating
JPS5631877A (en) * 1979-08-10 1981-03-31 Isao Minagawa Loading bed connected to tractor

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50158535A (en) * 1974-06-12 1975-12-22
JPS5230235A (en) * 1975-09-02 1977-03-07 Nippon Paint Co Ltd Chromating process
JPS5230230A (en) * 1975-09-03 1977-03-07 Toyota Motor Co Ltd Method of cutting off gate and runner during material melting
JPS542231A (en) * 1977-06-07 1979-01-09 Nippon Paint Co Ltd Metal surface treating method
JPS54110145A (en) * 1978-01-30 1979-08-29 Amchem Prod Metal surface coating composition* preparation thereof* and application using same
JPS54133440A (en) * 1978-03-31 1979-10-17 Amchem Prod Aluminum coating composition and method for coating
JPS5631877A (en) * 1979-08-10 1981-03-31 Isao Minagawa Loading bed connected to tractor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4650527A (en) * 1983-08-12 1987-03-17 Nippon Light Metal Company Limited Hydrophilic surface-treating process for an aluminum article

Also Published As

Publication number Publication date
JPS621476B2 (en) 1987-01-13

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