JPH0820876A - Phosphate chemical conversion treatment - Google Patents
Phosphate chemical conversion treatmentInfo
- Publication number
- JPH0820876A JPH0820876A JP15990194A JP15990194A JPH0820876A JP H0820876 A JPH0820876 A JP H0820876A JP 15990194 A JP15990194 A JP 15990194A JP 15990194 A JP15990194 A JP 15990194A JP H0820876 A JPH0820876 A JP H0820876A
- Authority
- JP
- Japan
- Prior art keywords
- chemical conversion
- sludge
- phosphate
- conversion treatment
- treatment liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C23C22/36—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 phosphates
- C23C22/362—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 phosphates containing also zinc cations
-
- 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
- C23C22/73—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 characterised by the process
-
- 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
- C23C22/86—Regeneration of coating baths
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
Description
【０００１】[0001]
【産業上の利用分野】本発明は金属材料のリン酸塩化成
処理方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphate chemical conversion treatment method for metallic materials.
【０００２】本発明において、アルミニウムを含む金属
材料とは、アルミニウム板、Ｚｎ−Ａｌ合金めっき鋼
板、アルミめっき鋼板などが典型的なものとして挙げら
れ、例えば自動車ボディ外板、カラートタン等に使用さ
れる。In the present invention, the metal material containing aluminum is typically exemplified by an aluminum plate, a Zn-Al alloy plated steel plate, an aluminum plated steel plate, etc., and is used, for example, in an automobile body outer plate, a colored galvanized sheet and the like. It
【０００３】[0003]
【従来の技術】以下、主にこれらの金属材料のリン酸塩
化成処理に関して説明する。Ｚｎ−Ａｌ合金めっき鋼板
は通常のＺｎめっきよりも耐食性や耐熱性がすぐれてい
るために近年防食素材として活発に用途開発が行われて
いる。特に、塗装鋼板の素材に５％程度のアルミニウム
を含有した亜鉛めっき鋼板が多く使用されるようになっ
たが、これをリン酸塩化成処理すると処理液中にアルミ
ニウムイオンが蓄積する。アルミニウムイオンはリン酸
塩化成処理には不必要かつ有害な成分であるので反応系
外に除去されることが望ましい。2. Description of the Related Art A phosphate chemical conversion treatment of these metal materials will be mainly described below. Since Zn-Al alloy-plated steel sheets have better corrosion resistance and heat resistance than ordinary Zn plating, their applications have been actively developed in recent years as corrosion-preventing materials. In particular, a galvanized steel sheet containing about 5% aluminum has come to be often used as a material for a coated steel sheet, but when this is subjected to a phosphate chemical treatment, aluminum ions are accumulated in the treatment liquid. Since aluminum ion is an unnecessary and harmful component for the phosphate chemical conversion treatment, it is desirable to remove it outside the reaction system.
【０００４】特開昭５７−７０２８１号公報によると、
リン酸亜鉛処理溶液中に溶出して来る鋼板単位面積当り
のＡｌ溶出量が０．２×１０-3〜１．０×１０-3ｍｏｌ
／ｍ2 で且つ該溶出量に対応してＡｌイオンが５０ＰＰ
Ｍ以下になる様に溶出Ａｌと同ｍｏｌでＮａＨＦ2 ：
０．２×１０-3〜１．０×１０-3ｍｏｌ／ｍ2 及び溶出
Ａｌと２倍ｍｏｌでＫＨＦ2 ：０．４×１０-3〜２．０
×１０-3ｍｏｌ／ｍ2 を連続的に補給してＡｌを沈殿物
として除去し、リン酸亜鉛処理液中のＡｌイオン濃度を
５０ｐｐｍ以下に保持するリン酸塩化成処理方法が提案
されている。この方法ではＡｌをエルパソライト（Ｎａ
Ｋ2 ＡｌＦ6 ）として反応系外に沈降除去して所定のＡ
ｌイオン濃度を得ている。According to JP-A-57-70281,
The amount of aluminum eluted per unit area of steel sheet eluted in the zinc phosphate treatment solution is 0.2 × 10 −3 to 1.0 × 10 −3 mol
/ M 2 and the Al ion is 50 PP corresponding to the elution amount.
NaHF2 at the same mol as the eluted Al so that it becomes M or less:
0.2 * 10 <-3> to 1.0 * 10 <-3> mol / m <2> and 2 times mol of eluted Al and KHF <2>: 0.4 * 10 <-3> to 2.0.
There has been proposed a phosphate chemical conversion treatment method of continuously replenishing x10 -3 mol / m 2 to remove Al as a precipitate and keeping the Al ion concentration in the zinc phosphate treatment liquid at 50 ppm or less. In this method, Al is replaced with elpasolite (Na
K2 AlF6) is removed from the reaction system by sedimentation and removal of the desired A
l-ion concentration is obtained.
【０００５】さらに、特開昭６０−２０４８８９号公報
によると、主成分としてＺｎイオン量が０．８５〜１．
７ｇ／ｌ、Ｎｉイオン量が１．０〜２．５ｇ／ｌ、ＰＯ
4 イオン量が５．５〜１０ｇ／ｌ、ＮＯ3 イオン量が
０．８〜１．５ｇ／ｌ、Ｆイオン量が１．３〜５．５ｇ
／ｌとその他少量の添加物からなるリン酸亜鉛処理液に
対し、ＮａＨＦ2 とＫＨＦ2 若しくはＮａＨＦ2 とＫＦ
を処理液中のＡｌ量に対し等量モル量以下の量で断続的
に添加してリン酸亜鉛処理液中のＡｌをＫ2 ＮａＡｌＦ
6 として沈降除去させ処理液中のＡｌイオン量を５００
ｐｐｍを超えない量に押さえるリン酸塩化成処理方法が
提案されている。Further, according to JP-A-60-204889, the amount of Zn ions as the main component is 0.85 to 1.
7 g / l, Ni ion amount 1.0-2.5 g / l, PO
4 Ion amount 5.5 ~ 10g / l, NO3 ion amount 0.8 ~ 1.5g / l, F ion amount 1.3 ~ 5.5g
/ L and other small amounts of additives for zinc phosphate treatment solution, NaHF2 and KHF2 or NaHF2 and KF
Is intermittently added in an amount equal to or less than an equimolar amount with respect to the amount of Al in the treatment liquid so that Al in the treatment liquid of zinc phosphate is added to K2 NaAlF.
The amount of Al ions in the treatment solution is set to 500 and the amount of Al ions in the treatment solution is set to 500.
A phosphate chemical conversion treatment method has been proposed in which the amount is controlled to not exceed ppm.
【０００６】リン酸塩化成処理中に、亜鉛−アルミニウ
ム合金めっきから溶出したアルミニウムイオンをクリオ
ライト（Ｎａ3 ＡｌＦ6 ）として除去することも公知で
あり腐食防食協会誌、第３９回腐食防食討論会概要に記
載されている。It is also known to remove aluminum ions eluted from zinc-aluminum alloy plating as cryolite (Na3 AlF6) during the phosphate chemical conversion treatment. Has been described.
【０００７】金属表面のリン酸塩化成処理に際しては、
ＦｅＰＯ4 ・ｎＨ2 Ｏ，Ｚｎ3 （ＰＯ4 ）2 ・ｎＨ2 Ｏ
等のリン酸塩スラッジが生成する。一般に、リン酸塩化
成処理にあっては処理液中のスラッジの含有量を少なく
することが望まれるために、濾過や沈降分離などスラッ
ジ量低減対策が講じられている。一方、スラッジを濾過
し易くするために、特開昭５６−１０５４８５号公報に
よると、冷延鋼板をリン酸塩化成処理する際に化成処理
液に高分子凝集剤を添加することによりリン酸塩化合物
系スラッジの沈降性を高める方法が提案されている。し
かしながら、この方法はアルミニウム化合物系スラッジ
の沈降を検討したものではない。In the phosphate conversion treatment of the metal surface,
FePO4 ・ nH2 O, Zn3 (PO4) 2 ・ nH2 O
Etc. phosphate sludge is produced. Generally, in the phosphate chemical conversion treatment, it is desired to reduce the content of sludge in the treatment liquid, and therefore sludge amount reduction measures such as filtration and sedimentation are taken. On the other hand, according to Japanese Patent Application Laid-Open No. 56-105485, in order to facilitate sludge filtration, when a cold rolled steel sheet is subjected to a phosphate chemical conversion treatment, a polymer coagulant is added to the chemical conversion treatment liquid to form a phosphate salt. Methods have been proposed for increasing the sedimentation of compound sludge. However, this method does not consider sedimentation of aluminum compound-based sludge.
【０００８】Ａｌを含む金属表面の化成処理において
は、処理液中にＡｌイオンが蓄積することを妨げるため
にＡｌイオンを固形物として反応系外に除去することが
望ましい。このためにリン酸塩の他にＮａＫ2 ＡｌＦ6
，Ｎａ3 ＡｌＦ6 等のスラッジも生成される。In the chemical conversion treatment of the metal surface containing Al, it is desirable to remove Al ions as a solid substance from the reaction system in order to prevent accumulation of Al ions in the treatment liquid. For this purpose, in addition to phosphate, NaK2 AlF6
, Na3 AlF6, etc. are also generated.
【０００９】一般にリン酸塩化成処理において、皮膜の
生成や、反応に伴って発生する固形物の粒径は、発生時
には非常に小さいが、次第に凝集肥大化し濾過し易くな
る傾向がある。ところが、スラッジを構成する化合物に
よりこの傾向は著しく異なり、アルミニウムを含まない
リン酸塩スラッジは比較的凝集沈降し易く、一方Ａｌの
フッ化物ＮａＫ2 ＡｌＦ6 、Ｎａ3 ＡｌＦ6 は凝集肥大
化し難いために、リン酸塩化成処理液中に粒径が小さい
まま浮遊した状態を保っており、濾過や沈降分離が困難
であることが判明した。Generally, in the phosphate chemical conversion treatment, the particle size of the solid matter generated by the formation of the film and the reaction is very small at the time of generation, but it tends to be agglomerated and thickened gradually to facilitate filtration. However, this tendency remarkably differs depending on the compounds constituting the sludge. Phosphate sludge containing no aluminum is relatively prone to coagulation and sedimentation, while Al fluorides NaK2 AlF6 and Na3 AlF6 are not prone to coagulation and enlargement. It was found that the particles remained small in the chlorination treatment solution with a small particle size, making filtration and sedimentation separation difficult.
【００１０】本発明において「スラッジ」とは、金属材
料をリン酸塩化成処理する際に起こる反応、又はＮａＨ
Ｆ2 ，ＫＨＦ2 等の添加により生成するリン酸塩やアル
ミニウム化合物のような固形物と、上記反応によらない
少量の金属塩、及び該金属材料に付着していた汚れの持
ち込みや空中粉塵の混入物等とを指すものとする。した
がって、スラッジの典型的なものは、リン酸亜鉛、リン
酸鉄及びクリオライト（Ｎａ3 ＡｌＦ6 ）もしくはエル
パソライト（ＮａＫ2 ＡｌＦ6 ）からなるアルミニウム
化合物ならびに付着汚れ、塵などの混入物からなる。In the present invention, "sludge" is a reaction that occurs when a metal material is subjected to a phosphate conversion treatment, or NaH.
Solids such as phosphates and aluminum compounds produced by the addition of F2, KHF2, etc., a small amount of metal salts that do not depend on the above reaction, and carry-in of dirt adhering to the metal materials or contamination of airborne dust And so on. Therefore, typical sludge consists of zinc phosphate, iron phosphate and an aluminum compound consisting of cryolite (Na3 AlF6) or elpasolite (NaK2 AlF6) and contaminants such as adhered dirt and dust.
【００１１】[0011]
【発明が解決しようとする課題】本発明の目的は、アル
ミニウム化合物系スラッジに起因するリン酸塩処理に於
ける品質上及びメンテナンス上の欠点を解決することで
ある。アルミニウム化合物系スラッジは、リン酸塩化成
処理皮膜の形成を妨げるＡｌイオンを反応系外に除去す
る過程で一旦処理液中に浮遊することは避けられず、し
かも沈降性が低いために処理液中に次第に蓄積する。こ
の結果、金属表面上に形成されるリン酸塩化成処理皮膜
にはアルミニウム化合物系スラッジが取り込まれあるい
は付着して皮膜の品質、例えば耐水二次密着性を劣化す
ることが判かった。SUMMARY OF THE INVENTION It is an object of the present invention to overcome the quality and maintenance drawbacks in phosphating due to aluminum compound based sludge. Aluminum compound sludge is inevitably suspended in the treatment solution during the process of removing Al ions that interfere with the formation of the phosphate chemical conversion coating outside the reaction system, and since it has a low sedimentation property, it does not exist in the treatment solution. Gradually accumulates. As a result, it was found that the aluminum compound-based sludge was taken in or adhered to the phosphate chemical conversion coating formed on the metal surface to deteriorate the quality of the coating, for example, the water resistant secondary adhesion.
【００１２】アルミニウム化合物系スラッジに起因する
品質劣化を防止するためには、例えば処理液を強制的に
連続的又は断続的にフィルター等を通過させることによ
って、濾過を行うことが考えられるが、アルミニウム化
合物系スラッジは強制濾過が困難である。In order to prevent the quality deterioration due to the aluminum compound-based sludge, it is conceivable to perform the filtration by, for example, forcibly or continuously passing the treatment liquid through a filter or the like. Compound sludge is difficult to force filter.
【００１３】前掲特開昭５６−１０５４８５号公報によ
る鋼板又はＺｎめっき鋼板にリン酸亜鉛系化成皮膜を形
成する方法では、高分子凝集剤の添加によりリン酸亜鉛
系スラッジは沈降し易くなる。しかしながら、Ａｌを含
む金属材料表面をリン酸塩化成処理とすると、スラッジ
は沈降し易いリン酸塩と沈降し難いアルミニウム化合物
が混合しており、このような沈降性質が異なるスラッジ
が混在している処理液からスラッジを沈降させる方法の
検討は従来行われていなかった。In the method of forming a zinc phosphate-based chemical conversion coating on a steel sheet or a Zn-plated steel sheet according to the above-mentioned JP-A-56-105485, the zinc phosphate-based sludge tends to settle due to the addition of the polymer coagulant. However, when the surface of the metal material containing Al is subjected to the phosphate chemical conversion treatment, the sludge is mixed with a phosphate that easily sediments and an aluminum compound that does not easily sediment, and such sludges having different sedimentation properties are mixed. The method of settling sludge from the treated liquid has not been studied so far.
【００１４】[0014]
【課題を解決するための手段】本発明者は、上記したア
ルミニウム化合物系スラッジに起因する化成皮膜の品質
劣化の対策を鋭意検討した結果、金属材料の表面をフッ
化物を含有するリン酸塩化成処理液にて処理する方法に
おいて、アルミニウムを含む金属材料表面からアルミニ
ウムが溶出することにより生成しかつ前記フッ化物を含
有するリン酸塩化成処理液中に浮遊するアルミニウム化
合物系スラッジを、少なくとも一種のカチオン性高分子
凝集剤にて沈降、凝集することを特徴とするリン酸塩化
成処理方法を創案した。Means for Solving the Problems The inventors of the present invention have made extensive studies as a countermeasure against the deterioration of the quality of the chemical conversion coating due to the above-mentioned aluminum compound-based sludge, and as a result, the surface of the metal material is treated with a phosphate chemical containing fluoride. In the method of treating with a treatment liquid, an aluminum compound-based sludge produced by elution of aluminum from the surface of a metal material containing aluminum and floating in a phosphate chemical treatment liquid containing the fluoride is at least one kind. We devised a phosphate chemical conversion treatment method characterized by sedimentation and aggregation with a cationic polymer flocculant.
【００１５】金属材料のリン酸塩化成処理とは、該金属
材料の表面に、リン酸塩処理液をスプレー法もしくは浸
漬法により接触させ、該金属材料の表面が溶解すること
によって、該金属材料の表面に、例えばリン酸亜鉛系処
理の場合、Ｚｎ3 （ＰＯ4 ）2 ・ｍＨ2 Ｏ，Ｚｎ2 Ｆｅ
（ＰＯ4 ）2 ・ｎＨ2 Ｏ，Ｚｎ2 Ｃａ（ＰＯ4 ）2 ・ｎ
Ｈ2 Ｏに代表される皮膜を生成させ、該金属材料の防錆
や塗装密着性を向上させるものである。リン酸亜鉛系化
成処理液は、リン酸、Ｚｎ2+及び水を必須成分として含
有し、任意成分として、例えばＮｉ2+，Ｍｎ2+，Ｃａ2
+，Ｆｅ2+，Ｈ+ ，Ｎａ+ ，Ｋ+，ＮＨ4+，ＮＯ3-，ＮＯ
2 - ，フッ化物，ＳＯ4 2-，Ｃｌ- 等を含有する。これ
らリン酸塩処理液の成分は一般的なものである。Phosphate chemical conversion treatment of a metal material means that a phosphate treatment liquid is brought into contact with the surface of the metal material by a spray method or a dipping method, and the surface of the metal material is dissolved, whereby the metal material is dissolved. In the case of zinc phosphate-based treatment, for example, Zn3 (PO4) 2.mH2O, Zn2Fe
(PO4) 2 ・ nH2 O, Zn2 Ca (PO4) 2 ・ n
A film represented by H2 O is formed to improve rust prevention and coating adhesion of the metal material. The zinc phosphate-based chemical conversion treatment liquid contains phosphoric acid, Zn2 + and water as essential components, and as optional components, for example, Ni2 +, Mn2 +, Ca2.
+, Fe2 +, H +, Na +, K +, NH4 +, NO3-, NO
It contains 2-, fluoride, SO4 2-, Cl-, etc. The components of these phosphating solutions are common.
【００１６】本発明におけるリン酸塩化成処理液は、前
記リン酸、亜鉛及び水以外にフッ化物を必須成分とす
る。アルミニウム材料を含む金属表面にリン酸塩皮膜を
生成させる為にはアルミニウム材料の表面を容易にエッ
チングさせる成分としてフッ化物が必要である。The phosphate chemical conversion treatment liquid in the present invention contains a fluoride as an essential component in addition to the phosphoric acid, zinc and water. Fluoride is required as a component for easily etching the surface of the aluminum material in order to form a phosphate film on the metal surface containing the aluminum material.
【００１７】本発明者は、高分子凝集剤がスラッジの各
成分をフッ化物含有リン酸塩化成処理液中で凝集肥大化
させ、沈降させる手段につき実験に基づき考案し、次の
ような知見を得た。 （イ）アルミニウム化合物系スラッジはカチオン性高分
子凝集剤で凝集し沈降する。したがって、アルミニウム
化合物系スラッジは負に帯電しているものと推定され
る。 （ロ）アルミニウム化合物とリン酸塩の混合スラッジ浮
遊した処理液にカチオン性高分子凝集剤を添加すると、
混合スラッジ全体が凝集・沈降し、リン酸塩系スラッジ
のみが凝集・沈降することはない。 （ハ）アニオン性とカチオン性高分子凝集剤を併用する
場合は、カチオン性高分子凝集剤を先に添加することが
好ましい。たとえばアニオン性凝集剤を先に添加した場
合、凝集肥大化させるに必要なカチオン性凝集剤はアニ
オン性凝集剤の添加量以上添加することが好ましい。す
なわち、アニオン性高分子凝集剤によりアルミニウム化
合物系以外のスラッジを先ず凝集・沈降した場合、処理
液中にアルミニウム化合物系スラッジが浮遊している状
態となり、この状態の処理液にカチオン性高分子凝集剤
を添加する場合に、アニオン性凝集剤の添加量以上のカ
チオン性凝集剤を添加することが好ましい。The inventor of the present invention devised on the basis of experiments on means for causing a polymer flocculant to flocculate and enlarge each component of sludge in a fluoride-containing phosphate chemical conversion treatment solution and settle it based on experiments, and the following findings were obtained. Obtained. (A) The aluminum compound-based sludge aggregates with the cationic polymer flocculant and precipitates. Therefore, it is presumed that the aluminum compound-based sludge is negatively charged. (B) When a cationic polymer flocculant is added to a treatment liquid in which sludge containing an aluminum compound and a phosphate is suspended,
The entire mixed sludge aggregates and settles, and only the phosphate sludge does not aggregate and settle. (C) When the anionic and cationic polymer flocculants are used in combination, the cationic polymer flocculant is preferably added first. For example, when the anionic flocculant is added first, it is preferable to add the cationic flocculant required for flocculation and enlargement in an amount not less than the addition amount of the anionic flocculant. That is, when sludge other than aluminum compound-based sludge is first flocculated and settled by the anionic polymer flocculant, the aluminum compound-based sludge is suspended in the treatment liquid, and the cationic polymer flocculates in the treatment liquid in this state. When the agent is added, it is preferable to add the cationic coagulant in an amount equal to or more than the amount of the anionic coagulant added.
【００１８】本発明において、カチオン性凝集剤をリン
酸塩処理液中に含有させる方法はその処理液中にカチオ
ン性凝集剤を共存させる方法であればよく、特に限定す
るものではない。その具体的例としては、リン酸塩処
理液の主剤及び又は副剤に予めカチオン性凝集剤を含有
させて補給添加する方法、又は、リン酸塩処理液中に
カチオン性凝集剤を希釈、水溶液にして添加する方法が
好ましい。In the present invention, the method for incorporating the cationic flocculant into the phosphate treatment solution may be any method as long as the cationic flocculant coexists in the treatment solution and is not particularly limited. Specific examples thereof include a method in which the main agent and / or the auxiliary agent of the phosphate treatment liquid are preliminarily added with a cationic flocculant, or the cationic flocculant is diluted in the phosphate treatment liquid to prepare an aqueous solution. Is preferred.
【００１９】カチオン性凝集剤の添加量は一般に１〜１
００ｐｐｍ程度であり、好ましくは２〜１０ｐｐｍであ
る。添加量は概ねスラッジの含有量、粒径によって決ま
るものであり、１ｐｐｍ未満では効果が低下し、１００
ｐｐｍをこえると経済的に不利である。又、カチオン性
高分子凝集剤は限定するものではないが、ポリアクリル
エステル系、ポリアクリルアマイド系のものを好ましく
使用することができる。そのイオン強度は、強、中、弱
のものがあり、どれも効果があり、実用的である。また
カチオン性高分子凝集剤の分子量は１×１０5 〜２×１
０7 のものが好ましい。The amount of cationic flocculant added is generally 1 to 1.
It is about 00 ppm, preferably 2 to 10 ppm. The amount of addition is largely determined by the content of sludge and the particle size.
If it exceeds ppm, it is economically disadvantageous. The cationic polymer flocculant is not limited, but polyacrylic ester type and polyacrylic amide type can be preferably used. There are strong, medium and weak ionic strengths, all of which are effective and practical. The molecular weight of the cationic polymer flocculant is 1 × 10 5 to 2 × 1.
Those of 07 are preferable.
【００２０】本発Ｚ明においてカチオン性高分子凝集剤
添加前の浮遊スラッジ濃度は限定するものではないが、
現在の連続化成処理ラインにおける処理を前提とすると
１００〜１０，０００ｐｐｍが一般的である。かかる濃
度中のアルミニウム化合物系スラッジの割合は処理時間
とともに増大するが、約５０％すなわち５，０００ｐｐ
ｍに達することもある。前掲のカチオン性高分子凝集
剤含有法によると、凝集剤添加後数分で浮遊スラッジ濃
度は０．１〜１０ｐｐｍに低下する。前掲の方法の場
合でもこの範囲の浮遊スラッジ濃度が得られる。The concentration of the suspended sludge before the addition of the cationic polymer coagulant is not limited in the present invention Z, but
Assuming the treatment in the current continuous chemical conversion treatment line, 100 to 10,000 ppm is general. The proportion of aluminum compound-based sludge in such a concentration increases with the treatment time, but is about 50% or 5,000 pp.
It may reach m. According to the above-mentioned cationic polymer flocculant-containing method, the floating sludge concentration drops to 0.1 to 10 ppm within a few minutes after addition of the flocculant. Even in the case of the method described above, the concentration of suspended sludge in this range can be obtained.
【００２１】本発明において、必要によりノニオン性も
しくはアニオン性凝集剤をアルミニウム化合物系スラッ
ジ以外のスラッジを沈降させるために用いることができ
る。In the present invention, a nonionic or anionic flocculant can be used, if necessary, for precipitating sludge other than aluminum compound sludge.
【００２２】[0022]
【作用】アルミニウム化合物系スラッジはリン酸塩系ス
ラッジに比べて水に対する溶解度が大きいために塗装膜
を通過した水分により溶解しやすいと考えられる。アル
ミニウム化合物系スラッジは析出するリン酸塩化成皮膜
にからむ形で一部共析し、このことがリン酸塩化成処理
皮膜の品質劣化の原因であると考えられる。本発明のカ
チオン性高分子凝集剤の使用によりアルミニウム化合物
系スラッジと被処理材料とができ、これらの品質劣化を
防止することができる。[Function] Since aluminum compound sludge has a higher solubility in water than phosphate sludge, it is considered that aluminum compound sludge is more likely to be dissolved by water that has passed through the coating film. The aluminum compound-based sludge is partly co-deposited in the form of being entangled with the precipitated phosphate conversion coating, which is considered to be the cause of the deterioration of the quality of the phosphate conversion coating. By using the cationic polymer flocculant of the present invention, an aluminum compound-based sludge and a material to be treated can be formed and their quality deterioration can be prevented.
【００２３】[0023]
【実施例】本発明を実施例によりさらに説明する。Ａｌ
板及び冷延鋼板を、処理液中のＡｌイオン濃度が約１０
０ｐｐｍ、リン酸塩スラッジが約２０００ｐｐｍになる
様にリン酸亜鉛化成処理を行った後、添加剤を用いてア
ルミニウム化合物系スラッジを生成させたものを供試処
理液として以下の方法で評価を行った。EXAMPLES The present invention will be further described with reference to Examples. Al
Plate and cold-rolled steel plate, the Al ion concentration in the treatment liquid is about 10
After zinc phosphate chemical conversion treatment was performed so that the amount of phosphate sludge became 0 ppm and about 2000 ppm, aluminum compound-based sludge was formed using an additive, and the following treatment method was used for evaluation. It was
【００２４】確性方法 （１）凝集沈降性 供試処理液に以下に掲げる高分子凝集剤を添加し、１分
間攪拌後２分間放置しスラッジの凝集肥大化及び上澄液
の清澄状況を目視観察する。 （２）濾過性 通気度１００の不織布を用いて、供試処理液及び下記に
高分子凝集剤を添加した処理液を濾過し、濾液の清澄状
況を目視観察する。 （３）化成性 供試処理液に凝集剤を添加した処理液でアルミニウム板
を処理し、皮膜の状況を目視観察する。 （４）耐水２次密着性 供試処理液でアルミニウム板を処理し水洗、乾燥後、自
動車用相当のカチオン電着、中塗り、上塗り塗装を施
す。これを供試板として、４０℃の脱イオン水に２４０
時間浸漬後、アルミニウム板に達するゴバン目（２×２
ｍｍ，１００ケ）を刻み、テープ剥離による密着性試験
を行う。Accuracy method (1) Aggregation-sedimentation property The following polymer aggregating agents were added to the test treatment liquid, and the mixture was left stirring for 1 minute and left for 2 minutes to visually inspect the sludge for agglomeration and enlargement and the clearing state of the supernatant. To do. (2) Filterability Using a non-woven fabric having an air permeability of 100, the test treatment liquid and the treatment liquid to which the polymer flocculant is added below are filtered, and the clarification state of the filtrate is visually observed. (3) Chemical conversion The aluminum plate is treated with a treatment liquid prepared by adding an aggregating agent to the test treatment liquid, and the state of the film is visually observed. (4) Water-resistant secondary adhesion The aluminum plate is treated with the test treatment liquid, washed with water, dried, and then subjected to cationic electrodeposition, intermediate coating, and top coating suitable for automobiles. Using this as the test plate, add it to deionized water at 40 ° C for 240
After soaking for a period of time, it reaches the aluminum plate.
mm, 100 pieces), and an adhesion test is performed by peeling the tape.
【００２５】供試処理液 Ｚｎ2+ ： １．５ｇ／ｌ Ｎｉ2+ ： ０．５ｇ／ｌ ＰＯ43- ：１３．５ｇ／ｌ フッ化物 ： １．０ｇ／ｌ（フッ素として） ＮＯ3- ： ６．０ｇ／ｌ ＮＯ2- ： ０．１ｇ／ｌ Ｎａ+ ： １．５ｇ／ｌ Ｎａ3 ＡｌＦ6 ：８００ｐｐｍ（スラッジとして） ＦｅＰＯ4 ：２０００ｐｐｍ（スラッジとして） ｐＨ ： ２．９Test treatment liquid Zn2 +: 1.5 g / l Ni2 +: 0.5 g / l PO43-: 13.5 g / l Fluoride: 1.0 g / l (as fluorine) NO3-: 6.0 g / l NO2 -: 0.1 g / l Na +: 1.5 g / l Na3 AlF6: 800 ppm (as sludge) FePO4: 2000 ppm (as sludge) pH: 2.9
【００２６】 供試高分子凝集剤（三洋化成工業（株）製） 高分子凝集剤 イオン分類 Ａ サンフロックＡＭ−１７０Ｐ アニオン Ｎ サンフロックＮ−５００Ｐ ノニオン Ｃ１ サンフロックＣ−００９Ｐ 強カチオン Ｃ２ サンフロックＣＥ−６８２Ｐ 弱カチオン Test polymer coagulant (manufactured by Sanyo Kasei Co., Ltd.) Polymer coagulant Ion classification A Sunfloc AM-170P Anion N Sunfloc N-500P Nonion C1 Sunfloc C-009P Strong cation C2 Sunfloc CE -682P Weak cation
【００２７】評価方法 （１）凝集沈降性 ○：スラッジが著しく凝集肥大化する。上澄液は透明に
なるか又は若干の濁りが残る。 ×：液全体に透明感が得られない。 （２）濾過性 ○：ほとんど濾過できている。 ×：透明感が得られず、濾物も少ない。 （３）化成性 ○：皮膜は良好である。 ×：皮膜にムラ、スケがある。 （４）耐水２次密着性 ○：剥離個数なし △：剥離個数１０ケ未満 ×：剥離個数が１０ケ以上Evaluation Method (1) Aggregation and Sedimentation A: Sludge remarkably aggregates and enlarges. The supernatant becomes clear or some turbidity remains. X: The liquid is not transparent as a whole. (2) Filterability A: Almost filtered. X: A transparent feeling is not obtained and there are few filter cakes. (3) Chemical conversion A: The film is good. X: The film has unevenness and scale. (4) Water-resistant secondary adhesiveness ◯: No peeling number Δ: Peeling number less than 10 ×: Peeling number 10 or more
【００２８】[0028]
【表１】 供試凝集剤 結 果 No 種 類 添加量 凝集 濾過性 化成性 耐水２次 （ppm ） 沈降性 密着性 １ Ｃ２ ２ ○ ○ ○ ○ 実 ２ Ｃ２ １００ ○ ○ ○ ○ ３ Ｃ１ ２ ○ ○ ○ ○ 施 ４ Ｃ１ １００ ○ ○ ○ ○ ５ Ｃ２＋Ａ ６ ○ ○ ○ ○ 例 ６ Ｃ２＋Ｎ ６ ○ ○ ○ ○ ７ Ａ＋Ｃ２ ６ ○ ○ ○ ○ 比 １ なし ０ × × ○ × 較 ２ Ａ ２０ × × ○ × 例 ３ Ｎ ２０ × × ○ × [Table 1] Test flocculant Result No. Type Addition amount Flocculation Filterability Chemical conversion Water resistance Secondary (Ppm) Sedimentability Adhesion 1 C2 2 ○ ○ ○ ○ Actual 2 C2 100 ○ ○ ○ ○ 3 C1 2 ○ ○ ○ ○ Application 4 C1 100 ○ ○ ○ ○ 5 C2 + A 6 ○ ○ ○ ○ Example 6 C2 + N 6 ○ ○ ○ ○ 7 A + C2 6 ○ ○ ○ ○ Ratio 1 None 0 × × ○ × Comparison 2 A 20 × × ○ × Example 3 N 20 × × ○ ×
【００２９】実施例Ｎｏ５は凝集剤Ｃ２を先に４ｍｇ／
ｌ添加攪拌した後、凝集剤Ａを２ｍｇ／ｌ添加攪拌し
た。実施例Ｎｏ６は凝集剤Ｃ２を先に４ｍｇ／ｌ添加攪
拌した後、凝集剤Ｎを２ｍｇ／ｌ添加攪拌した。実施例
Ｎｏ７は凝集剤Ａを先に２ｍｇ／ｌ添加攪拌した後、凝
集剤Ｃ２を４ｍｇ／ｌ添加攪拌した。In Example No. 5, the coagulant C2 was added at 4 mg /
After adding 1 and stirring, 2 mg / l of flocculant A was added and stirred. In Example No. 6, 4 mg / l of the flocculant C2 was first added and stirred, and then 2 mg / l of the flocculant N was added and stirred. In Example No. 7, 2 mg / l of the flocculant A was first added and stirred, and then 4 mg / l of the flocculant C2 was added and stirred.
【００３０】比較例ではリン酸塩化成処理自体は可能で
あったが、凝集沈降性、濾過性及び耐水二次密着性が不
良となった。In the comparative example, the phosphate chemical conversion treatment itself was possible, but the coagulation-sedimentation property, the filtration property and the water-resistant secondary adhesion property became poor.
【００３１】[0031]
【発明の効果】以上説明したように、本発明法によると
アルミニウム化合物系スラッジと被処理金属材料の接触
を妨げることによりリン酸塩化成処理皮膜の品質劣化を
防止することができる。As described above, according to the method of the present invention, it is possible to prevent the deterioration of the quality of the phosphate chemical conversion coating by preventing the contact between the aluminum compound sludge and the metal material to be treated.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成７年５月２６日[Submission date] May 26, 1995
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００４[Correction target item name] 0004
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００４】特開昭５７−７０２８１号公報によると、
リン酸亜鉛処理溶液中に溶出して来る鋼板単位面積当り
のＡｌ溶出量が０．２×１０-3〜１．０×１０-3ｍｏｌ
／ｍ2 で且つ該溶出量に対応してＡｌイオンが５０ＰＰ
Ｍ以下になる様に溶出Ａｌと同ｍｏｌでＮａＨＦ2 ：
０．２×１０-3〜１．０×１０-3ｍｏｌ／ｍ2 及び溶出
Ａｌと２倍ｍｏｌでＫＨＦ2 ：０．４×１０-3〜２．０
×１０-3ｍｏｌ／ｍ2 を連続的に補給してＡｌを沈殿物
として除去し、リン酸亜鉛処理液中のＡｌイオン濃度を
５０ｐｐｍ以下に保持するリン酸塩化成処理方法が提案
されている。この方法ではＡｌをエルパソライト（Ｎａ
Ｋ2 ＡｌＦ6 ）として反応系外に沈降除去して所定のＡ
ｌイオン濃度を得ている。According to JP-A-57-70281,
Al elution amount per unit area of steel sheet eluted in the zinc phosphate treatment solution is 0.2 × 10 −3 to 1.0 × 10 −3 mol
/ M 2 and the Al ion is 50 PP corresponding to the elution amount.
NaHF 2 in the same mol as the eluted Al so as to be M or less:
0.2 × 10 −3 to 1.0 × 10 −3 mol / m 2 and KHF 2 : 0.4 × 10 −3 to 2.0 at 2 times mol with eluted Al.
A phosphate chemical conversion treatment method has been proposed in which Al is removed as a precipitate by continuously replenishing × 10 -3 mol / m 2 and the Al ion concentration in the zinc phosphate treatment liquid is maintained at 50 ppm or less. . In this method, Al is replaced with elpasolite (Na
K 2 AlF 6 ) is removed by settling out of the reaction system to obtain a predetermined A
l-ion concentration is obtained.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００５[Name of item to be corrected] 0005
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００５】さらに、特開昭６０−２０４８８９号公報
によると、主成分としてＺｎイオン量が０．８５〜１．
７ｇ／ｌ、Ｎｉイオン量が１．０〜２．５ｇ／ｌ、ＰＯ
4 イオン量が５．５〜１０ｇ／ｌ、ＮＯ3 イオン量が
０．８〜１．５ｇ／ｌ、Ｆイオン量が１．３〜５．５ｇ
／ｌとその他少量の添加物からなるリン酸亜鉛処理液に
対し、ＮａＨＦ2 とＫＨＦ2 若しくはＮａＨＦ2 とＫＦ
を処理液中のＡｌ量に対し等量モル量以下の量で断続的
に添加してリン酸亜鉛処理液中のＡｌをＫ2 ＮａＡｌＦ
6 として沈降除去させ処理液中のＡｌイオン量を５００
ｐｐｍを超えない量に押さえるリン酸塩化成処理方法が
提案されている。Further, according to JP-A-60-204889, the amount of Zn ions as the main component is 0.85 to 1.
7 g / l, Ni ion amount 1.0-2.5 g / l, PO
4 ion content is 5.5~10g / l, NO 3 ion content is 0.8 to 1.5 g / l, F ion amount 1.3~5.5g
/ L and a small amount of other additives for zinc phosphate treatment liquid, NaHF 2 and KHF 2 or NaHF 2 and KF
Is intermittently added in an amount equal to or less than an equimolar amount with respect to the amount of Al in the treatment liquid so that Al in the treatment liquid of zinc phosphate is added to K 2 NaAlF.
The amount of Al ions in the treatment liquid is set to 500 and the amount of Al ions in the treatment liquid is set to 500.
A phosphate chemical conversion treatment method has been proposed in which the amount is controlled to not exceed ppm.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００６[Correction target item name] 0006
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００６】リン酸塩化成処理中に、亜鉛−アルミニウ
ム合金めっきから溶出したアルミニウムイオンをクリオ
ライト（Ｎａ3 ＡｌＦ6 ）として除去することも公知で
あり腐食防食協会誌、第３９回腐食防食討論会概要に記
載されている。It is also known to remove aluminum ions eluted from zinc-aluminum alloy plating as cryolite (Na 3 AlF 6 ) during the phosphate chemical conversion treatment. It is described in the overview.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００７】金属表面のりん酸塩化成処理に際しては、
ＦｅＰＯ4 ・ｎＨ2 Ｏ，Ｚｎ3 （ＰＯ4 ）2 ・ｎＨ2 Ｏ
等のりん酸塩スラッジが生成する。一般に、りん酸塩化
成処理にあっては処理液中のスラッジの含有量を少なく
することが望まれるために、濾過や沈降分離等スラッジ
量低減対策が講じられている。一方、スラッジを濾過し
易くするために、特開昭５６−１０５４８５号公報によ
ると、冷延鋼板をリン酸塩化成処理する際に化成処理液
に高分子凝集剤を添加することによりリン酸塩化合物系
スラッジの沈降性を高める方法が提案されている。しか
しながら、この方法はアルミニウム化合物系スラッジの
沈降を検討したものではない。During the phosphate conversion treatment of the metal surface,
FePO 4 · nH 2 O, Zn 3 (PO 4 ) 2 · nH 2 O
Etc. phosphate sludge is produced. Generally, in the phosphate chemical conversion treatment, since it is desired to reduce the content of sludge in the treatment liquid, measures for reducing the sludge amount such as filtration and sedimentation have been taken. On the other hand, according to Japanese Patent Application Laid-Open No. 56-105485, in order to facilitate sludge filtration, when a cold rolled steel sheet is subjected to a phosphate chemical conversion treatment, a polymer coagulant is added to the chemical conversion treatment liquid to form a phosphate salt. Methods have been proposed for increasing the sedimentation of compound sludge. However, this method does not consider sedimentation of aluminum compound-based sludge.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００８】Ａｌを含む金属表面の化成処理において
は、処理液中にＡｌイオンが蓄積することを妨げるため
にＡｌイオンを固形物として反応系外に除去することが
望ましい。このためにリン酸塩の他にＮａＫ2 ＡｌＦ
6 ，Ｎａ3 ＡｌＦ6 等のスラッジも生成される。In the chemical conversion treatment of the metal surface containing Al, it is desirable to remove Al ions as a solid substance from the reaction system in order to prevent accumulation of Al ions in the treatment liquid. For this purpose, in addition to phosphate, NaK 2 AlF
6 , sludge such as Na 3 AlF 6 is also generated.
【手続補正６】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】一般にリン酸塩化成処理において、皮膜の
生成や、反応に伴って発生する固形物の粒径は、発生時
には非常に小さいが、次第に凝集肥大化し濾過し易くな
る傾向がある。ところが、スラッジを構成する化合物に
よりこの傾向は著しく異なり、アルミニウムを含まない
リン酸塩スラッジは比較的凝集沈降し易く、一方Ａｌの
フッ化物ＮａＫ2 ＡｌＦ6 、Ｎａ3 ＡｌＦ6 は凝集肥大
化し難いために、リン酸塩化成処理液中に粒径が小さい
まま浮遊した状態を保っており、濾過や沈降分離が困難
であることが判明した。Generally, in the phosphate chemical conversion treatment, the particle size of the solid matter generated by the formation of the film and the reaction is very small at the time of generation, but it tends to be agglomerated and thickened gradually to facilitate filtration. However, this tendency remarkably differs depending on the compounds that make up the sludge, and the phosphate sludge that does not contain aluminum is relatively prone to coagulation and sedimentation, while the Al fluorides NaK 2 AlF 6 and Na 3 AlF 6 are difficult to coagulate and enlarge. In addition, it was found that the phosphate conversion treatment liquid remained in a suspended state with a small particle size, and filtration and sedimentation separation were difficult.
【手続補正７】[Procedure Amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】本発明において「スラッジ」とは、金属材
料をリン酸塩化成処理する際に起こる反応、又はＮａＨ
Ｆ2 ，ＫＨＦ2 等の添加により生成するリン酸塩やアル
ミニウム化合物のような固形物と、上記反応によらない
少量の金属塩、及び該金属材料に付着していた汚れの持
ち込みや空中粉塵の混入物等とを指すものとする。した
がって、スラッジの典型的なものは、リン酸亜鉛、リン
酸鉄及びクリオライト（Ｎａ3 ＡｌＦ6 ）もしくはエル
パソライト（ＮａＫ2 ＡｌＦ6 ）からなるアルミニウム
化合物ならびに付着汚れ、塵などの混入物からなる。In the present invention, "sludge" is a reaction that occurs when a metal material is subjected to a phosphate conversion treatment, or NaH.
Solid substances such as phosphates and aluminum compounds produced by the addition of F 2 , KHF 2, etc., a small amount of metal salts that do not depend on the above reaction, and carry-on of dirt attached to the metal materials and airborne dust It refers to contaminants and the like. Therefore, typical sludge consists of zinc phosphate, iron phosphate and aluminum compound consisting of cryolite (Na 3 AlF 6 ) or elpasolite (NaK 2 AlF 6 ), and contaminants such as adhered dirt and dust. .
【手続補正８】[Procedure Amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Name of item to be corrected] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１５】金属材料のリン酸塩化成処理とは、該金属
材料の表面に、リン酸塩処理液をスプレー法もしくは浸
漬法により接触させ、該金属材料の表面が溶解すること
によって、該金属材料の表面に、例えばリン酸亜鉛系処
理の場合、Ｚｎ3 （ＰＯ4 ）2 ・ｍＨ2 Ｏ，Ｚｎ2 Ｆｅ
（ＰＯ4 ）2 ・ｎＨ2 Ｏ，Ｚｎ2 Ｃａ（ＰＯ4 ）2 ・ｎ
Ｈ2 Ｏに代表される皮膜を生成させ、該金属材料の防錆
や塗装密着性を向上させるものである。リン酸亜鉛系化
成処理液は、リン酸、Ｚｎ2+及び水を必須成分として含
有し、任意成分として、例えばＮｉ2+，Ｍｎ2+，Ｃ
ａ2+，Ｆｅ2+，Ｈ+ ，Ｎａ+ ，Ｋ+，ＮＨ4 +，ＮＯ3 -，
ＮＯ2 - ，フッ化物，ＳＯ4 2-，Ｃｌ- 等を含有する。
これらリン酸塩処理液の成分は一般的なものである。Phosphate chemical conversion treatment of a metal material means that a phosphate treatment liquid is brought into contact with the surface of the metal material by a spray method or a dipping method, and the surface of the metal material is dissolved, whereby the metal material is dissolved. In the case of zinc phosphate treatment, for example, Zn 3 (PO 4 ) 2 · mH 2 O, Zn 2 Fe
(PO 4 ) 2 · nH 2 O, Zn 2 Ca (PO 4 ) 2 · n
A film typified by H 2 O is formed to improve rust prevention and coating adhesion of the metal material. The zinc phosphate chemical conversion treatment liquid contains phosphoric acid, Zn 2+ and water as essential components, and as optional components, for example, Ni 2+ , Mn 2+ , C.
a 2+, Fe 2+, H + , Na +, K +, NH 4 +, NO 3 -,
It contains NO 2 − , fluoride, SO 4 2− , Cl − and the like.
The components of these phosphating solutions are common.
【手続補正９】[Procedure Amendment 9]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１９[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１９】カチオン性凝集剤の添加量は一般に１〜１
００ｐｐｍ程度であり、好ましくは２〜１０ｐｐｍであ
る。添加量は概ねスラッジの含有量、粒径によって決ま
るものであり、１ｐｐｍ未満では効果が低下し、１００
ｐｐｍをこえると経済的に不利である。又、カチオン性
高分子凝集剤は限定するものではないが、ポリアクリル
エステル系、ポリアクリルアマイド系のものを好ましく
使用することができる。そのイオン強度は、強、中、弱
のものがあり、どれも効果があり、実用的である。また
カチオン性高分子凝集剤の分子量は１×１０5 〜２×１
０7 のものが好ましい。The amount of cationic flocculant added is generally 1 to 1.
It is about 00 ppm, preferably 2 to 10 ppm. The amount of addition is largely determined by the content of sludge and the particle size.
If it exceeds ppm, it is economically disadvantageous. The cationic polymer flocculant is not limited, but polyacrylic ester type and polyacrylic amide type can be preferably used. There are strong, medium and weak ionic strengths, all of which are effective and practical. The molecular weight of the cationic polymer flocculant is 1 × 10 5 to 2 × 1.
Those of 0 7 are preferable.
【手続補正１０】[Procedure Amendment 10]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２５[Name of item to be corrected] 0025
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２５】供試処理液 Ｚｎ2+ ： １．５ｇ／ｌ Ｎｉ2+ ： ０．５ｇ／ｌ ＰＯ4 3- ：１３．５ｇ／ｌ フッ化物 ： １．０ｇ／ｌ（フッ素として） ＮＯ3 - ： ６．０ｇ／ｌ ＮＯ2 - ： ０．１ｇ／ｌ Ｎａ+ ： １．５ｇ／ｌ Ｎａ3 ＡｌＦ6 ：８００ｐｐｍ（スラッジとして） ＦｅＰＯ4 ：２０００ｐｐｍ（スラッジとして） ｐＨ ： ２．９The test treatment solution Zn 2+: 1.5g / l Ni 2+ : 0.5g / l PO 4 3-: 13.5g / l fluoride: 1.0 g / l (as fluorine) NO 3 - : 6.0g / l NO 2 -: 0.1g / l Na +: 1.5g / l Na 3 AlF 6: 800ppm ( as sludge) FePO 4: (as sludge) 2000 ppm pH: 2.9
Claims (2)
ン酸塩化成処理液にて処理する方法において、 アルミニウムを含む金属材料表面からアルミニウムが溶
出することにより生成しかつ前記フッ化物を含有するリ
ン酸塩化成処理液中に浮遊するアルミニウム化合物系ス
ラッジを、少なくとも一種のカチオン性高分子凝集剤に
て凝集、沈降させることを特徴とするリン酸塩化成処理
方法。1. A method for treating the surface of a metal material with a phosphate chemical conversion treatment solution containing a fluoride, which is produced by elution of aluminum from the surface of a metal material containing aluminum and contains the fluoride. A phosphate chemical conversion treatment method, characterized in that an aluminum compound-based sludge floating in a phosphate chemical conversion treatment liquid is aggregated and precipitated with at least one cationic polymer flocculant.
前記フッ化物を含有するリン酸塩化成処理液中において
１〜１００ｐｐｍの範囲内にある請求項１記載のリン酸
塩化成処理方法。2. The concentration of the cationic polymer flocculant is
The phosphate chemical conversion treatment method according to claim 1, wherein the phosphate chemical conversion treatment liquid contains the fluoride within a range of 1 to 100 ppm.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15990194A JPH0820876A (en) | 1994-07-12 | 1994-07-12 | Phosphate chemical conversion treatment |
| US08/765,934 US5904785A (en) | 1994-07-12 | 1995-07-11 | Process for forming a phosphate conversion coating |
| PCT/US1995/008228 WO1996001914A1 (en) | 1994-07-12 | 1995-07-11 | Process for forming a phosphate conversion coating |
| EP95926607A EP0765405A4 (en) | 1994-07-12 | 1995-07-11 | Process for forming a phosphate conversion coating |
| CA 2194910 CA2194910A1 (en) | 1994-07-12 | 1995-07-11 | Process for forming a phosphate conversion coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15990194A JPH0820876A (en) | 1994-07-12 | 1994-07-12 | Phosphate chemical conversion treatment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0820876A true JPH0820876A (en) | 1996-01-23 |
Family
ID=15703651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15990194A Pending JPH0820876A (en) | 1994-07-12 | 1994-07-12 | Phosphate chemical conversion treatment |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0765405A4 (en) |
| JP (1) | JPH0820876A (en) |
| CA (1) | CA2194910A1 (en) |
| WO (1) | WO1996001914A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100317680B1 (en) * | 1999-04-29 | 2001-12-22 | 이계안 | Surface treatment agent for treating aluminium alloy and steel plate simultaneously before painting |
| JP2003038982A (en) * | 2001-07-31 | 2003-02-12 | Nippon Paint Co Ltd | Sludge thickening method, thick sludge obtained by this method and sludge thickening equipment |
| US6756092B2 (en) | 2001-02-26 | 2004-06-29 | Sumitomo Metal Industries, Ltd. | Surface treated steel material, a method for its manufacture, and a chemical conversion treatment liquid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2494559C (en) * | 2002-07-10 | 2011-09-20 | Chemetall Gmbh | Method for coating metallic surfaces |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53109871A (en) * | 1977-03-07 | 1978-09-26 | Nippon Paint Co Ltd | Treating method for sludge by-product formed in chemical treatment of zinc phosphate film |
| JPS56105485A (en) * | 1980-01-24 | 1981-08-21 | Nippon Parkerizing Co Ltd | Chemical conversion process for phosphate coating |
| JPS5770281A (en) * | 1980-10-20 | 1982-04-30 | Nisshin Steel Co Ltd | Zinc phosphate treatment of zinc hot dipping steel plate |
| JPS60204889A (en) * | 1984-03-29 | 1985-10-16 | Nisshin Steel Co Ltd | Zinc phosphate treatment of steel sheet plated with zn-al alloy |
| KR100197145B1 (en) * | 1989-12-19 | 1999-06-15 | 후지이 히로시 | Method for phosphating metal surface with zinc phosphate |
-
1994
- 1994-07-12 JP JP15990194A patent/JPH0820876A/en active Pending
-
1995
- 1995-07-11 CA CA 2194910 patent/CA2194910A1/en not_active Abandoned
- 1995-07-11 WO PCT/US1995/008228 patent/WO1996001914A1/en not_active Application Discontinuation
- 1995-07-11 EP EP95926607A patent/EP0765405A4/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100317680B1 (en) * | 1999-04-29 | 2001-12-22 | 이계안 | Surface treatment agent for treating aluminium alloy and steel plate simultaneously before painting |
| US6756092B2 (en) | 2001-02-26 | 2004-06-29 | Sumitomo Metal Industries, Ltd. | Surface treated steel material, a method for its manufacture, and a chemical conversion treatment liquid |
| US7918945B2 (en) | 2001-02-26 | 2011-04-05 | Sumitomo Metal Industries, Ltd. | Method for manufacturing surface treated steel material using a chemical conversion treatment liquid |
| US8333847B2 (en) | 2001-02-26 | 2012-12-18 | Sumitomo Metal Industries, Ltd. | Chemical conversion treatment liquid |
| JP2003038982A (en) * | 2001-07-31 | 2003-02-12 | Nippon Paint Co Ltd | Sludge thickening method, thick sludge obtained by this method and sludge thickening equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0765405A1 (en) | 1997-04-02 |
| WO1996001914A1 (en) | 1996-01-25 |
| CA2194910A1 (en) | 1996-01-25 |
| EP0765405A4 (en) | 1997-06-04 |
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