JPS6179782A - Treatment of phosphate - Google Patents

Treatment of phosphate

Info

Publication number
JPS6179782A
JPS6179782A JP20255884A JP20255884A JPS6179782A JP S6179782 A JPS6179782 A JP S6179782A JP 20255884 A JP20255884 A JP 20255884A JP 20255884 A JP20255884 A JP 20255884A JP S6179782 A JPS6179782 A JP S6179782A
Authority
JP
Japan
Prior art keywords
chemical conversion
steel
zinc
phosphate
treatment
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
JP20255884A
Other languages
Japanese (ja)
Other versions
JPH0380877B2 (en
Inventor
Takashi Kawakami
隆 川上
Yoshiji Shirogane
白銀 嘉二
Shigeki Matsuda
茂樹 松田
Yukiyoshi Omi
大見 幸義
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.)
Nihon Parkerizing Co Ltd
Denso Corp
Original Assignee
Nihon Parkerizing Co Ltd
NipponDenso 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 Nihon Parkerizing Co Ltd, NipponDenso Co Ltd filed Critical Nihon Parkerizing Co Ltd
Priority to JP20255884A priority Critical patent/JPS6179782A/en
Publication of JPS6179782A publication Critical patent/JPS6179782A/en
Publication of JPH0380877B2 publication Critical patent/JPH0380877B2/ja
Granted legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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 phosphates
    • C23C22/08Orthophosphates
    • C23C22/12Orthophosphates containing zinc cations
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/78Pretreatment of the material to be coated
    • C23C22/80Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds

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 form a fine phosphate film excellent in corrosion resistance by means of a chemical conversion by treatng steel preliminarily with a prescribed aq. surface adjustor soln. and thereafter treating it with a film-chemical conversion treatment soln. consisting of a specified composition contg. Zn, PO4 and Fe<3+> in the presence of an oxidizing agent. CONSTITUTION:Steel and steel product plated with zinc and zinc alloy are preliminarily treated with the aq. surface adjustor soln. contg. 1-50ppm Ti, 200-3000ppm PO4 and 50-600ppm P2O7 and having 8.0-9.5pH at <=40 deg.C by a spray method or the like. While using a zinc phosphate film-chemical conversion treatment soln. as an essential condition contg. 0.5-1.5g/l Zn, PO4 having the ratio of PO4:Zn=(10-35):1 in the presence of an oxidizing agent such as nitrous acid ion and chloric acid ion and >=5ppm Fe<3+> as a chemical conversion promoter and controlling pH of the soln. to 3.3-4.5, steel, steel products are treated in the low-temp. region of 10-40 deg.C. By the above-mentioned treatment, the phosphate film excellent in quality is formed on the surface of the steel or the like by means of the chemical conversion.

Description

【発明の詳細な説明】 [産業上の利用分野] 本発明は塗装用の暦れた下地皮膜を低dシぐ化成させる
方法に関するものであり、更に詳しくは鉄鋼、亜鉛及び
亜鉛合金めっき鋼材を表面調整剤水溶液で処理し、次い
で低温のりん耐亜鉛系皮膜化成液で処理して、鉄鋼、亜
鉛及び亜鉛合金めっき鋼材表面に良好なりん酸塩皮膜を
一低111Mで化成させるりん酸塩処理方法に関するも
のである。
[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for converting a seasoned base film for painting into a low-d staining film, and more specifically, it relates to a method for converting a seasoned base film for painting into a low-d staining material. Phosphate treatment in which a good phosphate film is formed on the surface of steel, zinc, and zinc alloy plated steel at a low temperature of 111M by treating with an aqueous solution of a surface conditioner and then with a low-temperature phosphorus-resistant zinc-based coating conversion solution. It is about the method.

[従来の技術1 従来から第1りん酸亜鉛を主成分とし、亜Ii!!4酸
イオンを促進剤とした酸性のりん酸塩処理液にて、鉄鋼
、亜鉛及び亜鉛合金めっき鋼材を処理して結晶性りん酸
塩皮膜を化成させるりん酸塩処理法は鉄鋼、亜鉛及び亜
鉛合金めっき鋼材表面の耐食1!I及び塗料付着性の向
上にτ■要な工業的役割を果たしていることは良く知ら
れている。これらの処理方法どしでは、従来から鉄鋼、
亜鉛及び!l[鉛合金めっぎ鋼材を50℃以上のアルカ
リ脱脂液で表面を清浄にした後、水洗し、45℃以上の
りん酸什鉛系化成処理液にて処理する方法が行われてお
り、また特に皮膜化成を促進し、緻密な拮品皮嘆を1゛
7るために、脱脂、水洗後コロイドチタンを含む表面調
整液で処1!I! u、次いで化成処理する方法が(j
われている。脱脂、化或はいずれも45℃以上の高温で
処理されている。これらの化成処理方法における接液方
式は一般に浸漬法、スプレー法、間欠スプレー法、スプ
レー→浸漬法、浸漬→スプレー法、ハーフディップ法な
どの処理方式が工業的に採用されている。このように処
理された被処理物は、溶剤@装、粉体塗装、電右¥装に
用いられ、塗装塗膜の密着性、耐食性の向上に重要な役
割を宋たしてきている。りん耐亜鉛系皮膜のし成分はP
hosphophyllite(Zn 、、 Fe (
PO4) 2−4 ト1 2 0  〕  、  Ho
peite(Zn  3  (PO4)2   ”4H
7O)の結晶組成物から構成され、化学的に安定で素地
鋼材表面との結合性に優れているP host)hol
llhy l l i teを形成することが望ましく
、特に電着塗装においてはP hosphophy I
 l i teとP hO3phophl/l1itf
3+ H0peiteの比(以下rP/P + HJと
略す。)の高い化成皮膜が採用されている。P / P
 + Hの高い皮膜を形成させるためには、りんflu
塩処理液中のZ n / P O4比を従来よりも小さ
くし、亜鉛イオン濃度を0.5〜1.5g/lの範囲に
して用いられるようになってきた。
[Conventional technology 1 Conventionally, zinc monophosphate has been used as the main ingredient, and sub-Ii! ! A phosphate treatment method in which a crystalline phosphate film is formed by treating steel, zinc, and zinc alloy coated steel with an acidic phosphate treatment solution using tetraacid ions as an accelerator. Corrosion resistance of alloy plated steel surfaces 1! It is well known that τ■ plays an important industrial role in improving I and paint adhesion. These processing methods have traditionally been used to treat steel,
Zinc and! l [The method used is to clean the surface of lead alloy plated steel with an alkaline degreasing solution at a temperature of 50°C or higher, wash it with water, and treat it with a lead diphosphate-based chemical conversion treatment solution at a temperature of 45°C or higher. In addition, in order to particularly promote film formation and remove fine scratches, treat with a surface conditioning solution containing colloidal titanium after degreasing and washing with water. I! u, then the method of chemical conversion treatment is (j
It is being said. Both degreasing and chemical treatment are carried out at a high temperature of 45°C or higher. As the liquid contact method in these chemical conversion treatment methods, treatment methods such as a dipping method, a spray method, an intermittent spray method, a spray->immersion method, an immersion->spray method, and a half-dip method are generally adopted industrially. The treated objects thus treated are used for solvent coating, powder coating, and electric coating, and have been playing an important role in improving the adhesion and corrosion resistance of paint films. The component of the phosphorus-resistant zinc coating is P.
phosphophyllite (Zn,, Fe (
PO4) 2-4 To1 2 0], Ho
peite(Zn 3 (PO4)2 ”4H
P host) hol is composed of a crystalline composition of 7O), is chemically stable, and has excellent bonding properties with the surface of the base steel material.
It is desirable to form Phosphophy I, especially in electrodeposition coating.
l ite and P hO3phophl/l1itf
A chemical conversion film with a high ratio of 3+ H0peite (hereinafter abbreviated as rP/P + HJ) is employed. P/P
In order to form a film with high +H, phosphorus flu
It has come to be used by lowering the Z n /P O4 ratio in the salt treatment solution than before and setting the zinc ion concentration in the range of 0.5 to 1.5 g/l.

しかし前記のようなりん酸1n処理液中の亜鉛イオンが
0.5〜1.5g、lという低濃度の場合は、そのとき
の条件により、例えば化成しにくい鋼材であったり、り
ん酸塩処理液の前処理として強アルカリ脱脂液を用いた
場合などには、化成後被処理物表面にM錆が発生する場
合があった。すなわち均一かつ緻密で耐食性に優れた皮
膜が形成できないことがあった。特に化成処理液が40
℃以下の低温領域で処理した場合、均一かつ緻密で耐食
性に浸れた皮膜が形成できず、塗装下地として好ましい
皮膜を提供することは困難であった。また高温化成処理
液では、遊離酸度を高く、すなわらpHを2.0〜3.
0の範囲にすることで処1’N造成分のバランスを維持
しているが、高温領域では被処理物のエツチング■が多
く、すなわち反応1!1が畠く、処理液の流動拡散が活
発であるため、スラッジを発生する。これらのスラッジ
は被処理物への付着、加熱装置への固着、スプレー装d
りの配管の閉塞などの不具合を生じさせている。
However, if the concentration of zinc ions in the phosphoric acid 1N treatment solution is as low as 0.5 to 1.5 g, 1, as mentioned above, depending on the conditions, for example, the steel material may be difficult to chemically form, or the phosphate treatment When a strong alkaline degreasing solution is used as a pretreatment solution, M rust may occur on the surface of the treated object after chemical conversion. In other words, it may not be possible to form a uniform, dense film with excellent corrosion resistance. Especially the chemical conversion treatment liquid is 40
When treated at low temperatures below 0.degree. C., a uniform, dense, and corrosion-resistant film cannot be formed, making it difficult to provide a film suitable as a base for painting. In addition, high-temperature chemical conversion treatment liquids have a high free acidity, that is, a pH of 2.0 to 3.
By keeping the temperature within the range of 0, the balance of the processing 1'N forming components is maintained, but in the high temperature range, there is a lot of etching of the processed material, that is, the reaction 1!1 is prevalent, and the flow and diffusion of the processing solution is active. Therefore, sludge is generated. These sludges adhere to objects to be treated, stick to heating equipment, and spray equipment.
This is causing problems such as blockage of pipes.

[本発明が解決しようとする問題点] 本発明は、10〜40℃の低温領域で化成するに当って
、化成処理液が安定で、スラッジの生成が(参めて少な
い化成処理液を提供し、かつ鉄鋼、亜鉛及び亜鉛合金め
っき鋼材表面の性状に影響されることなく、fa密で耐
食性が優れたP/P+Hが0.5以上の皮膜を形成させ
ることのでざる化成処理方法を提供することを目的とし
ているもので6ウリ、また工業的処理ラインにおける省
エネルギー、省資源を追求した処理方法であり、110
熱装置などをほとんど必要とセずに、皮膜を形成させる
ことができ、薬剤消費量が少ない化成処理方法を提供す
ることを目的としている。
[Problems to be Solved by the Present Invention] The present invention provides a chemical conversion treatment solution that is stable and produces less sludge during chemical conversion at a low temperature range of 10 to 40°C. To provide a chemical conversion treatment method that does not form a film with a P/P+H ratio of 0.5 or more, which is fa-dense and has excellent corrosion resistance, without being affected by the surface properties of steel, zinc, or zinc alloy-plated steel. It is a processing method that pursues energy saving and resource saving in industrial processing lines, and has 110
The purpose of the present invention is to provide a chemical conversion treatment method that can form a film with almost no need for a heating device or the like and consumes a small amount of chemicals.

[問題を解決するための手段] 本発明者らは、りんM塩処理液及びその処理方法につい
て研究した結末、亜鉛イオン0.5〜1.57/!J、
PO4:Zn =10〜35:1の比率のりlvRイオ
ンと硝酸イオン、Ni 、 Mn 。
[Means for Solving the Problem] The present inventors researched a phosphorus M salt treatment solution and its treatment method and found that the zinc ion was 0.5 to 1.57/! J.
PO4:Zn = 10-35:1 ratio of lvR ions and nitrate ions, Ni, Mn.

COなどのC[金属イオン、ふつ化物イオンなどのエツ
チング剤を適宜配合し、史に亜1i1’1Mイオン、塩
素酸イオンなどの酸化剤を含有、した処理液に33+ 1illi鉄イオン(Fe  )を51)11111以
上含有する化成処理液により、10〜40℃の低温領域
でも化成反応が促進されることを見い出した。更にこの
処理液を用いて化成処理するに当たり、あらかじめ40
℃以下のチタンイオン1〜5Qppm、りん酸イオン2
00〜30001)l)m、ピロリん酸イオン50〜6
00ppmを含有し、pH8,0〜9.5からなる表面
調整剤水溶液で処理し、次いで化成することによって、
化成処理条件、被迅埋物表面の性状に左右されずに均一
かつ緻密でP / P + Hが0.5以上を有する皮
膜を形成させる方法を見い出し本発明を完成した。
33+ 1illi iron ions (Fe) are added to the treatment solution containing CO and other C [etching agents such as metal ions and common ions, and oxidizing agents such as submers ions and chlorate ions. 51) It has been found that a chemical conversion treatment solution containing 11111 or more promotes chemical conversion reactions even in the low temperature range of 10 to 40°C. Furthermore, when performing chemical conversion treatment using this treatment solution, 40%
Titanium ion 1-5Qppm below ℃, phosphate ion 2
00-30001)l)m, pyrophosphate ion 50-6
By treating with an aqueous surface conditioner solution containing 00 ppm and having a pH of 8.0 to 9.5, and then chemical conversion,
The present invention was accomplished by discovering a method for forming a uniform and dense film having a P/P+H ratio of 0.5 or more, regardless of the chemical conversion treatment conditions or the surface properties of the object to be buried.

亜硝酸イオン、In ! ll!2イオンなどの酸化剤
を含有する一般のりん酸亜鉛処理液で鋼材等を処理する
場合、低湿領域での鋼材の溶解反応、酸化還元反応、皮
膜析出反応は基本的に高64領域に比べて緩慢であり、
酸化還元反応を促進し化成皮膜を円滑に生成させるため
には一定で以上のFe3+イオンを含有させることが4
効であることが分かった。
Nitrite ion, In! ll! When treating steel materials with a general zinc phosphate treatment solution containing oxidizing agents such as 2 ions, the dissolution reaction, redox reaction, and film deposition reaction of steel materials in the low humidity region are basically lower than in the high 64 region. It is slow;
In order to promote the redox reaction and smoothly generate a chemical conversion film, it is necessary to contain a certain amount of Fe3+ ions.
It turned out to be effective.

これらのFe”4オンを5 CDl11〜飽和状態に維
持することにより、化成反応の酸化λマ元反応を促進す
る亜硝酸イオンなどの酸化剤の添加補給量が少なくなり
、その温度も高温領域に比較して低濃度に維持すること
ができることを見い出した。
By maintaining these Fe"4 ons in a saturated state of 5 CDl11~, the amount of addition and replenishment of oxidizing agents such as nitrite ions that promote the oxidation lambda element reaction of the chemical reaction is reduced, and the temperature is also in the high temperature range. It has been found that the concentration can be maintained at a comparatively low level.

1:03+イオンは5 ppm〜飽和状態の範囲で良好
な化成皮膜が生成できるが好ましくは101111m以
上である。Fe”#オンが5 ppm未満では皮膜化成
の促進効果が低く、良好な皮膜を形成することができな
い。りん酸亜鉛系皮膜化成処理液にFe3+イオンを8
有させるには、スチールウールヤ他の鉄鋼材料を処理液
に浸漬してFe3”−+’オンを生成させるか、又は易
溶性の3価鉄塩、例えばFe  (NO)   −91
−120,Fe C13−61−10,Fe  (So
  )  −xl−120などの処理液に添加してFe
”宥オンを生成させても良い。史に、低温のりん耐亜鉛
系皮膜化成液で鉄鋼材料を処理する工程によって溶出し
てくる鉄イオンもFe”イオンとして使用される。要す
るに鉄鋼材料を処理するに当って、りんR塩処し![!
液中にFe”#オンが含まれることが重要なのである。
A good chemical conversion film can be formed with 1:03+ ions in the range of 5 ppm to saturation, but preferably 101111 m or more. If Fe''#on is less than 5 ppm, the effect of promoting film formation is low and a good film cannot be formed.
This can be achieved by immersing steel wool or other steel materials in a treatment solution to generate Fe3''-+', or by adding a readily soluble trivalent iron salt, such as Fe(NO)-91.
-120,Fe C13-61-10,Fe (So
)-xl-120 etc. to treat Fe.
Iron ions may also be generated.Historically, iron ions eluted during the process of treating steel materials with a low-temperature phosphorus-resistant zinc-based coating solution have also been used as Fe ions. In short, when processing steel materials, treat them with phosphorus and salt! [!
It is important that the liquid contains Fe''#on.

りん酸塩処理液の亜鉛イオンcJj東としては0.5f
f/J)未満の低い濃度では化成性が悪くなり、皮膜外
観、皮膜品質上満足な化成皮膜が得られない。
Zinc ion cJj east of phosphate treatment solution is 0.5f
If the concentration is lower than f/J), the chemical conversion property will be poor and a chemical conversion film that is satisfactory in terms of film appearance and film quality cannot be obtained.

また1、!M/41より多い場合はP/P+Hの高い皮
膜が得られず、処理液の安定性が悪く、スラッジも発生
し好ましくない。PO4/Znは1゜/1〜35/1の
範囲が好ましく 10/1より低い値では形成されるり
ん酸塩皮膜が均一でなく、不満足な皮膜となり、優れた
耐食性を得ることができない。またPO/Znが35/
1より高い場合は、化成不良が生じやすいとともに、化
成処理液として経済上不利である。硝酸、亜硝酸、塩素
酸などの酸化剤、Ni、co、Mnなどの重金属イオン
、ふっ化物などのエツチング剤、ふっ化物、オキシカル
ボン酸、EDTAなとのキレート剤は処理加工条件によ
ってそれらの種類及びその濃度を適宜選択して配合する
ことができる。リン酸塩処理液にキレート化合物を添加
しない場合はFe3〉オンを50 ppm位までしか含
有させることが出来ないが、キレート剤を配合すること
により、i o o ppm位まで含有させることが出
来る。
Another one! When the amount is more than M/41, a film with a high P/P+H cannot be obtained, the stability of the treatment liquid is poor, and sludge is generated, which is not preferable. The PO4/Zn ratio is preferably in the range of 1°/1 to 35/1. If the ratio is lower than 10/1, the phosphate film formed will not be uniform and will be unsatisfactory, making it impossible to obtain excellent corrosion resistance. Also, PO/Zn is 35/
When it is higher than 1, chemical conversion defects are likely to occur and it is economically disadvantageous as a chemical conversion treatment liquid. The types of oxidizing agents such as nitric acid, nitrous acid, and chloric acid, heavy metal ions such as Ni, co, and Mn, etching agents such as fluoride, and chelating agents such as fluoride, oxycarboxylic acid, and EDTA depend on the processing conditions. and its concentration can be appropriately selected and blended. If no chelate compound is added to the phosphate treatment solution, Fe3>one can be contained up to about 50 ppm, but by blending a chelating agent, it can be contained up to about IO ppm.

しかし余り5最に含有させるとスラッジが増加するので
、10〜601)D11含有させるのが好ましい。
However, if the excess 5 is contained, sludge will increase, so it is preferable to contain 10 to 601) D11.

硝酸イオン濃度は2〜2o9/ρの範囲が好ましい。処
し!!!液のpHは3.3〜4.5であり、好ましくは
3.5〜4.0である。このpH値は温度、処理条件、
処理液組成によって変化させることが可能であり、pH
3,3より低い場合は本発明の化成温度(10〜40℃
)においては化成性が低下し、良好な皮膜が形成できな
くなる。従ってD I−1が3.3よりも低下したとき
は、力性ソーダ等のアルカリを含む溶液を補給し、D 
Hが4.5をこえたときは、りん酸イオン、硝酸イオン
、亜1irl酸イΔン簀を含むりんM塩処理剤(主剤)
を処理液に補給することによって処理液のpHを3.3
〜4.5に制陣するのである。またpHが4.5よりb
高い場合は処理液が不安定となりJ化成化が低下し、良
好な皮膜を形成できない。処理温度は10〜40℃で処
理するものであるが、本発明の化成処理においては、処
理液温度は環境温度によって左右されるが、10〜40
’Cの範囲のある一定温度に維持管理することが望まし
い。
The nitrate ion concentration is preferably in the range of 2 to 2o9/ρ. Punishment! ! ! The pH of the liquid is 3.3 to 4.5, preferably 3.5 to 4.0. This pH value depends on temperature, processing conditions,
It can be changed depending on the treatment liquid composition, and the pH
If it is lower than 3.3, the chemical formation temperature of the present invention (10 to 40℃
), the chemical conversion property decreases and it becomes impossible to form a good film. Therefore, when DI-1 drops below 3.3, replenish the solution containing an alkali such as diluted soda, and
When H exceeds 4.5, use a phosphorus M salt treatment agent (main agent) containing phosphate ions, nitrate ions, and 1irl acid ion filter.
By replenishing the processing solution with
They will take control at ~4.5. Also, the pH is higher than 4.5.
If it is high, the treatment solution becomes unstable, J chemical conversion is reduced, and a good film cannot be formed. The treatment temperature is 10 to 40°C, but in the chemical conversion treatment of the present invention, the treatment liquid temperature varies depending on the environmental temperature, but is 10 to 40°C.
It is desirable to maintain the temperature at a constant temperature in the range of 'C.

処理温度が10℃未満では化成性が低下する傾向がある
If the treatment temperature is less than 10° C., the chemical conversion property tends to decrease.

亜鉛イオン0.5〜1.5g/fJ 、PO4/Zn 
=10/1〜35/1.Fe3”(オン5DDm〜飽和
状態のりん酸亜鉛処理液を用い、低温領域で化成処理す
ることにより、処理液が安定で、がつP/P+H比の高
いりん酸亜鉛皮膜を形成することができるが、不動態皮
膜、醇化物などで不動態化された鋼材表面や、強アルカ
リ脱脂液を用いて洗浄された表面では化成不良が発生し
、処理表面に黄精が発生したり、不均一な皮膜を形成す
る現象が発生する。これらを解決するために、本発明者
らは、鋼材表面を清浄にした後、あらかじめチタンイオ
ン1〜50ppm、りん酸イオン200〜300011
E1m 、 ヒロil:)ん酸イオン50〜6o。
Zinc ion 0.5-1.5g/fJ, PO4/Zn
=10/1~35/1. By performing chemical conversion treatment in a low temperature range using a saturated zinc phosphate treatment solution, the treatment solution is stable and a zinc phosphate film with a high P/P+H ratio can be formed. However, poor chemical conversion occurs on steel surfaces that have been passivated with a passive film or infusion, or on surfaces that have been cleaned using a strong alkaline degreasing solution, resulting in yellowing or uneven film formation on the treated surface. In order to solve these problems, the present inventors cleaned the surface of the steel material and added 1 to 50 ppm of titanium ions and 200 to 300011 of phosphate ions in advance.
E1m, Hiroil:) Phosphate ion 50-6o.

ppmを含有し、pI−18,0〜9.5からなる40
℃以下の表面調整剤水溶液で処理し、次いで本発明の低
温型りん酸塩処理液で化成処理することにより、相乗的
に化成反応が促進され、均一かつ緻密な皮膜を形成させ
ることができ、耐食性の優れた塗装下地皮膜を形成する
ことができた。また表面調整液の温度を40’C以下に
規制する理由は、被処理物の鋼種により、処理液中の組
成成分が鋼材表面と反応して不働態化し、その後の化成
反応を阻害するためである。特に本発明の低温領域での
化成では、反応が緩慢であるため表面調整液の処理温度
を化成処理液温度と同等又はそれ以下に管理することが
必要である。前記表面調整剤の必須イオン洪給源として
は各種のものが使用されるが、例えばチタンイオンとし
ては硫酸チタン、硫酸チタニル、酸化チタン、りん酸イ
オンとしてはりん酸、りん酸のアルカリ金属塩又はアン
モニウム塩、ピロりん酸イオンとしては、ピロりん酸、
ピロりん酸のアルカリ金属又はアンモニウム塩が挙げら
れる。上記各成分供給源と水を混合加熱し、次いで水分
を除去し、残留物に所定o l−11+fiを与える吊
の炭酸ソーダなどを均一混合し、該混合物を適量の水に
溶解して表面調整剤を調整すればよい。
40 containing ppm and consisting of pI-18.0 to 9.5
By treating with an aqueous surface conditioner solution at a temperature of ℃ or below, and then chemical conversion treatment with the low-temperature phosphate treatment solution of the present invention, the chemical conversion reaction is synergistically promoted and a uniform and dense film can be formed. It was possible to form a coating base film with excellent corrosion resistance. Also, the reason why the temperature of the surface conditioning liquid is regulated to 40'C or less is that, depending on the steel type of the object to be treated, the compositional components in the treatment liquid may react with the steel surface and become passivated, inhibiting the subsequent chemical conversion reaction. be. In particular, in the chemical conversion in the low temperature range of the present invention, since the reaction is slow, it is necessary to control the treatment temperature of the surface conditioning liquid to be equal to or lower than the temperature of the chemical conversion treatment liquid. Various types of ion sources are used as the essential ion source for the surface conditioning agent. For example, titanium ions include titanium sulfate, titanyl sulfate, and titanium oxide, and phosphate ions include phosphoric acid, alkali metal salts of phosphoric acid, and ammonium ions. Salts and pyrophosphate ions include pyrophosphate,
Alkali metal or ammonium salts of pyrophosphoric acid may be mentioned. Mix and heat each of the above component sources and water, then remove the moisture, uniformly mix with soda carbonate, etc. that gives the residue a predetermined o l-11+fi, and dissolve the mixture in an appropriate amount of water to adjust the surface. Just adjust the agent.

表面調整剤は鉄鋼、1IIi鉛及び亜鉛合金めっき鋼材
表面にチタン化合物のコロイドを付着させて、化成性を
向上させ、良好な皮膜を得るものである。
The surface conditioner is used to attach a colloid of a titanium compound to the surface of steel, 1IIIi lead and zinc alloy plated steel to improve chemical conversion properties and obtain a good film.

したがってチタンイオン濃度が規定1iffより低いと
化成性が悪く、逆に規定値より高くなってもそれ以上の
実質的な2Il果は望めない。りん酸イオンも上記と同
様に機能する。ピOりん酸イオンは化成皮膜の化成性を
良好にする効果があり、そのイオン濃度が規定値より低
いとその効果が認められず、逆に高くなると素材と反応
してピロりん酸化合物を形成し、化成皮膜の形成を阻害
する。表面調整剤水溶液のρ1」が規定1直より低いと
、ピロりん酸と素材の反応が起こり、以後の化成皮膜の
形成を阻害し、逆に高すぎても化成皮膜の形成を阻害り
゛る。    ゛ 本発明のりん酸塩処理方法における接液り式は表面調整
剤水溶液及びりん酸伊鉛系皮膜化成処理液共に限定する
ものではなく、一般的に行われている浸心法、スプレー
法、間欠スプレー法、スプレー→トΩ漬法、浸漬→スプ
レー法、ハーフディップ法などのいずれの方法でも適用
できる。特にこれらの方法の中で1表面流層による浸漬
法とスプレー→浸漬法が効果的である。またこのように
処理された被処理物の塗装方法も一般的に行われている
溶剤系又は水系塗料のスプレー塗装・浸漬塗装・静電塗
装など、粉体塗装、電着塗装などのいずれの方法でもよ
い。
Therefore, if the titanium ion concentration is lower than the specified 1iff, the chemical formation property will be poor, and conversely, even if it is higher than the specified value, no further substantial 2I effect can be expected. Phosphate ions function similarly as above. Piophosphate ions have the effect of improving the chemical conversion properties of chemical conversion coatings, and if the ion concentration is lower than the specified value, the effect will not be recognized, and if it is higher, it will react with the material and form a pyrophosphate compound. and inhibits the formation of chemical conversion films. If the ρ1 of the surface conditioner aqueous solution is lower than the specified value of 1, a reaction between pyrophosphoric acid and the material will occur, inhibiting the subsequent formation of a chemical conversion film, and conversely, if it is too high, the formation of a chemical conversion film will be inhibited. .゛The wetted method in the phosphate treatment method of the present invention is not limited to the surface conditioner aqueous solution and the lead phosphate-based film conversion treatment solution, and may be any of the commonly used immersion methods, spray methods, Any of the following methods can be applied: intermittent spray method, spray → dip method, dipping → spray method, half-dip method, etc. Particularly effective among these methods are the 1-surface flow layer immersion method and the spray->immersion method. In addition, the method of painting the treated object in this way can be any of the commonly used methods such as spray painting, dipping painting, electrostatic painting, etc. using solvent-based or water-based paints, powder painting, electrodeposition painting, etc. But that's fine.

[実施例1 冷延鋼板を強アルカリ脱脂剤(ファインクリーナー43
57日本バー力うイジング@製)を用いて55〜60℃
で脱脂、水洗し表1に記載する表面調整剤水溶液で20
〜25℃で30秒間スプレーした後、直ちに表1に記載
する亜鉛イオン。
[Example 1] A cold rolled steel plate was treated with a strong alkaline degreaser (Fine Cleaner 43).
55-60℃ using 57 Nippon Bar Power Ising@)
Degreased with water, washed with water, and treated with a surface conditioner aqueous solution listed in Table 1 for 20 minutes.
Zinc ions listed in Table 1 immediately after spraying for 30 seconds at ~25°C.

PO/Zn比、Fe3+イオン濃度を含有し、硝酸イオ
ン6.7’J/f)、亜IirJMイt>0.1 g/
、0.Niイオン0.69/j 、BF  −イオン0
.1g/ρからなる化成処理液を用い表1記載の温度で
1分間スプレー処理し水洗、乾燥して、一部は皮膜特性
用の試料とし、他の被処理鋼板はアミラックL−52(
関西ペイント社製)を乾燥膜厚として19〜22μm塗
布し、180’CF5分間焼付乾燥し、塗面にカッター
大イフでスクラッチを入れ、JIS  Z2371によ
る3g水噴霧試験を384時間行い、セロハンデーブで
塗面を圧着剥離し、スクラッチ部からの塗膜剥卯巾を測
定した。これらの結果を表1に記載する。
PO/Zn ratio, Fe3+ ion concentration, nitrate ion 6.7'J/f), NiirJMt>0.1 g/
,0. Ni ion 0.69/j, BF - ion 0
.. Using a chemical conversion treatment solution of 1 g/ρ, spray treatment was performed for 1 minute at the temperature listed in Table 1, washed with water, and dried. Some of the steel sheets were used as samples for film properties, and the other steel sheets were treated with Amirac L-52 (
Kansai Paint Co., Ltd.) was applied to a dry film thickness of 19 to 22 μm, baked at 180'CF for 5 minutes, scratched on the coated surface with a cutter, and subjected to a 3g water spray test according to JIS Z2371 for 384 hours. The coated surface was peeled off by pressure, and the width of the coated film peeled off from the scratched area was measured. These results are listed in Table 1.

なお実施例4は電気亜鉛めっき鋼板(亜鉛めっき吊29
g/Ir/、)を用いた以外は他の実施例と同様な方法
で試験した。
In addition, Example 4 is an electrogalvanized steel sheet (galvanized steel plate 29
The test was carried out in the same manner as in the other Examples except that 100 g/Ir/) was used.

[発明の効果] 実施例から分かるように本発明により低温の化成領域に
おいて処理液中のスラッジの発生も少なく均一かつ緻密
な皮膜が形成でき、塗装竣の耐食性に優れた皮膜が形成
できる。本発明における亜1り冒オン0.5〜1 、5
 g/’J 、 POa Zn I Q/1〜35/1
.Fe3+イオン5ppI11〜飽和状態。
[Effects of the Invention] As can be seen from the examples, according to the present invention, a uniform and dense film can be formed in a low-temperature chemical conversion region with little generation of sludge in the treatment solution, and a film with excellent corrosion resistance can be formed after painting. In the present invention, the concentration of chloride in the present invention is 0.5 to 1,5
g/'J, POa Zn I Q/1~35/1
.. Fe3+ ion 5ppI11 ~ saturated state.

DH3,3〜4.5の範囲の低温りんWli塩処理液で
あっても、あらかじめ表面調整剤水溶液で処理すること
により、黄精などの発生もなく相乗的に浸れた化成皮膜
を形成することができる。
Even with a low-temperature phosphorus Wli salt treatment solution in the range of DH3.3 to 4.5, by treating it with an aqueous surface conditioner solution in advance, it is possible to form a synergistically immersed chemical conversion film without generating yellowing particles. can.

特許出願人 日本パー力ライジング株式会社同  日本
電装株式会社 手続補正舌 昭和59年11月シ日
Patent Applicant Nippon Pariki Rising Co., Ltd. Nippon Denso Co., Ltd. Procedural Amendment Date November 1982

Claims (1)

【特許請求の範囲】[Claims] 鉄鋼、亜鉛及び亜鉛合金めっき鋼材を、予めチタンイオ
ン1〜50ppm、りん酸イオン200〜3000pp
m、ピロりん酸イオン50〜600ppmを含有し、p
H8.0〜9.5からなる40℃以下の表面調整剤水溶
液で処理し、次いで亜鉛イオン0.5〜1.5g/l、
りん酸イオン(PO_4:g/l):亜鉛イオン(Zn
:g/l)=10〜35:1の比率のりん酸イオン及び
3価鉄イオン(Fe^3^+)5ppm以上を含有する
りん酸亜鉛系皮膜化成処理液を用い、その液のpHを3
.3〜4.5に制御しながら処理温度10〜40℃の低
温領域で処理することを特徴とするりん酸塩処理方法。
Steel, zinc and zinc alloy plated steel materials are pre-treated with 1 to 50 ppm of titanium ions and 200 to 3000 ppm of phosphate ions.
m, contains 50 to 600 ppm of pyrophosphate ions, and p
Treated with a surface conditioner aqueous solution at 40°C or lower consisting of H8.0-9.5, and then treated with zinc ion 0.5-1.5 g/l,
Phosphate ion (PO_4: g/l): Zinc ion (Zn
:g/l) = 10 to 35:1 using a zinc phosphate-based film conversion treatment solution containing 5 ppm or more of phosphate ions and trivalent iron ions (Fe^3^+), and adjusting the pH of the solution. 3
.. A phosphate treatment method characterized by carrying out treatment at a low temperature range of 10 to 40°C while controlling the temperature to 3 to 4.5°C.
JP20255884A 1984-09-27 1984-09-27 Treatment of phosphate Granted JPS6179782A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP20255884A JPS6179782A (en) 1984-09-27 1984-09-27 Treatment of phosphate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP20255884A JPS6179782A (en) 1984-09-27 1984-09-27 Treatment of phosphate

Publications (2)

Publication Number Publication Date
JPS6179782A true JPS6179782A (en) 1986-04-23
JPH0380877B2 JPH0380877B2 (en) 1991-12-26

Family

ID=16459484

Family Applications (1)

Application Number Title Priority Date Filing Date
JP20255884A Granted JPS6179782A (en) 1984-09-27 1984-09-27 Treatment of phosphate

Country Status (1)

Country Link
JP (1) JPS6179782A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63100185A (en) * 1986-10-16 1988-05-02 Nippon Parkerizing Co Ltd Phosphating method
JPH02101174A (en) * 1988-10-06 1990-04-12 Nippon Paint Co Ltd Treatment with zinc phosphate for cold working
US8062435B2 (en) 2001-06-18 2011-11-22 Henkel Kommanditgesellschaft Auf Aktien Phosphating operation
CN102776498A (en) * 2012-07-23 2012-11-14 宁波市鸿博机械制造有限公司 Method for reducing negative camber abrasion of stator of automobile steering vane pump
RU2510431C2 (en) * 2008-10-31 2014-03-27 Хенкель Аг Унд Ко. Кгаа Liquid for chemical conversion treatment of metallic material and treatment method
JP2018016835A (en) * 2016-07-27 2018-02-01 Jfeスチール株式会社 Method for manufacturing zinc phosphate treated steel sheet

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63100185A (en) * 1986-10-16 1988-05-02 Nippon Parkerizing Co Ltd Phosphating method
JPH055899B2 (en) * 1986-10-16 1993-01-25 Nippon Packaging Kk
JPH02101174A (en) * 1988-10-06 1990-04-12 Nippon Paint Co Ltd Treatment with zinc phosphate for cold working
US8062435B2 (en) 2001-06-18 2011-11-22 Henkel Kommanditgesellschaft Auf Aktien Phosphating operation
RU2510431C2 (en) * 2008-10-31 2014-03-27 Хенкель Аг Унд Ко. Кгаа Liquid for chemical conversion treatment of metallic material and treatment method
CN102776498A (en) * 2012-07-23 2012-11-14 宁波市鸿博机械制造有限公司 Method for reducing negative camber abrasion of stator of automobile steering vane pump
JP2018016835A (en) * 2016-07-27 2018-02-01 Jfeスチール株式会社 Method for manufacturing zinc phosphate treated steel sheet

Also Published As

Publication number Publication date
JPH0380877B2 (en) 1991-12-26

Similar Documents

Publication Publication Date Title
JP2806531B2 (en) Zinc phosphate aqueous solution for surface treatment of iron or iron alloy material and treatment method
KR910003722B1 (en) Phosphate coating composition and method of applying a zinc-nickel phosphate coating
JP3267979B2 (en) Zinc phosphate coating composition containing oxime accelerator
JP3063920B2 (en) How to treat metal surfaces with phosphate
US5976272A (en) No-rinse phosphating process
JP5462467B2 (en) Chemical treatment solution for metal material and treatment method
JP2680618B2 (en) Metal phosphate treatment method
US4486241A (en) Composition and process for treating steel
JPS6136588B2 (en)
JPS6056429B2 (en) Phosphate film treatment method for metals
JPH0394074A (en) Improved composition and method for imparting coating to metal surface
JPH11335865A (en) Processing agent for forming protective coating film on metal and its formation
JPS63190178A (en) Formation of phosphate film
JP3137535B2 (en) Zinc-containing metal-coated steel sheet composite excellent in coatability and method for producing the same
JPH10500452A (en) Iron phosphate treatment with substituted monocarboxylic acids
JPH03267378A (en) Method for phosphating metal surface and phosphating solution
JPH09217180A (en) Middle-temperature manganese phosphate chemical conversion treating liquid and chemical conversion treatment
US4596607A (en) Alkaline resistant manganese-nickel-zinc phosphate conversion coatings and method of application
US6179934B1 (en) Aqueous phosphating composition and process for metal surfaces
JP3088623B2 (en) Method for forming zinc phosphate film on metal surface
JPS6179782A (en) Treatment of phosphate
JPH06228766A (en) Method of forming phosphate film
JP3737168B2 (en) Manufacturing method of electrogalvanized steel sheet with high whiteness and excellent paintability
JPH04341574A (en) Treatment of zinc phosphate onto metal surface
US3459600A (en) Novel zinc coating composition and method

Legal Events

Date Code Title Description
LAPS Cancellation because of no payment of annual fees