JPS5848678A - Pretreating agent for coating steel products and pretreatment for coating - Google Patents
Pretreating agent for coating steel products and pretreatment for coatingInfo
- Publication number
- JPS5848678A JPS5848678A JP14596681A JP14596681A JPS5848678A JP S5848678 A JPS5848678 A JP S5848678A JP 14596681 A JP14596681 A JP 14596681A JP 14596681 A JP14596681 A JP 14596681A JP S5848678 A JPS5848678 A JP S5848678A
- Authority
- JP
- Japan
- Prior art keywords
- treated
- treatment
- oxalate
- cooling
- experimental example
- 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
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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/088—Iron or steel solutions containing organic acids
-
- 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
- C23C22/46—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 oxalates
- C23C22/47—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 oxalates 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)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は鋼材表面に塗装を施す場合の前処埋却１及び前
処理方法に関［７、特に炉中ろう付のクロ＜無酸化雰囲
気において高熱処理された鋼材の塗装前処理剤及び前処
理方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to pretreatment burial 1 and pretreatment method for coating the surface of steel materials [7, particularly for furnace brazing black coating, etc. The present invention relates to a painting pretreatment agent and a pretreatment method.
一般に鋼材表面に塗装を施す場合には、鋼材表面に直接
塗料を吹付けると付着性、耐蝕性等において劣るため、
鋼材表面に塗装下地としてのリン酸亜鉛などの化成皮膜
を形成し、この化成皮膜表面に塗膜を形成するようにし
ている。Generally, when painting steel surfaces, spraying the paint directly onto the steel surface will result in poor adhesion and corrosion resistance.
A chemical conversion film such as zinc phosphate is formed on the surface of the steel material as a base for painting, and a paint film is formed on the surface of this chemical conversion film.
一方鋼材を炉中ろう付等の高温処理をする場合には、鋼
材の機械的性質を向上せしめ部材の薄肉化、軽量化を図
るべく、加熱後の鋼材を約５７０〜７２０Ｃの変態点付
近まで炉冷し、次いでこれを急冷するようにしている。On the other hand, when steel materials are subjected to high-temperature treatment such as furnace brazing, the heated steel materials are heated to around the transformation point of about 570 to 720 C in order to improve the mechanical properties of the steel materials and make the parts thinner and lighter. It is cooled in a furnace and then rapidly cooled.
しかしながら上記の如く処理した場合には下記の表１に
示す如き酸化膜（酸化スケール）が鋼材表面に生じる。However, when treated as described above, an oxide film (oxide scale) as shown in Table 1 below is formed on the surface of the steel material.
〔表 １〕
そして上記の如き酸化スケールを除去し２ない捷ま鋼材
の表面に化成皮膜を形成すると、化成皮膜と鋼材との密
着性及び化成皮膜表面への塗料の付着性、或いは化成皮
膜表面に形成される塗膜の耐蝕性等の化成皮膜性が極め
て劣るものとなる。[Table 1] When a chemical conversion film is formed on the surface of a rolled steel material without removing the oxidized scale as described above, the adhesion between the chemical conversion film and the steel material, the adhesion of paint to the surface of the chemical conversion film, or the surface of the chemical conversion film. The chemical conversion film properties such as the corrosion resistance of the coating film formed on this surface are extremely poor.
したがって塗装下地皮膜を形成するに先って鋼材表面の
酸化スケールを除去する必要があるが、従来においては
、この手段として、ショツトブラスト、サンドブラスト
或いはパフ掛は等の物理的な手段、または、塩酸、硫酸
、リン酸などの無機酸、シュウ酸、酒石酸、リンゴ酸な
どの有機酸による化学的な手段を用いている。Therefore, it is necessary to remove the oxidized scale on the surface of the steel material before forming a coating base film. Conventionally, this has been done by physical means such as shot blasting, sandblasting, or puffing, or by using hydrochloric acid. , chemical means using inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as oxalic acid, tartaric acid, and malic acid.
斯る従来手段によって酸化スケールを除去する場合には
以下の如き不利がある。即ち、ショツトブラスト等の物
理的手段による場合には鋼材の表面粗度が荒くなり、ま
たショット等の困難な部位においては酸化スケールを除
去することができず、更にショツト粒子等を完全に掃除
しに＜＜、ゴミも付着しやすいので均一な化成皮膜を形
成することができない。また塩酸、硫酸を用いた場合に
は水素脆弱による鋼材表面の劣化、及び水洗不良による
黄銅の発生による化成皮膜性の悪化が著しく、またリン
酸等を用いた場合にも塩酸、硫酸はどではないが同様の
問題がある。When removing oxide scale by such conventional means, there are the following disadvantages. In other words, when using physical means such as shot blasting, the surface roughness of the steel material becomes rough, and oxidized scale cannot be removed from difficult areas such as shot blasting, and it is difficult to completely clean shot particles. Also, dirt tends to adhere to it, making it impossible to form a uniform chemical conversion film. In addition, when hydrochloric acid or sulfuric acid is used, the steel surface deteriorates due to hydrogen brittleness, and the chemical conversion coating property deteriorates significantly due to the generation of brass due to poor washing. No, but I have a similar problem.
以上の如き品質上の問題の他に従・来手段による場合に
は前処理工程数の増加と設備の増大等の問題がある。二
・、即ち、例えばショツトブラストを行なう場合には、
吊掛け、吹付（ブラスト）、ワークの回転、吹付及びエ
アブロ−という多数の工程を必要とし、そのための装置
を必要とするとともに、該装置を設置する場所も確保し
なければならない。In addition to the above-mentioned quality problems, when conventional methods are used, there are problems such as an increase in the number of pretreatment steps and an increase in equipment. 2. For example, when performing shot blasting,
It requires a number of steps such as hanging, blasting, rotating the workpiece, spraying, and air blowing, and requires equipment for these steps, as well as a place to install the equipment.
また化学的手段においても、酸洗ζ水洗、中和及び防錆
等の各処理を行なわなければならず、上記同様工程数と
設備の増加を来たし７、且つ工場内における占有面積の
問題がある。そして処理工程が増加することはそれだけ
処理時間が長くなるという不利にもつながる。In addition, with chemical means, various treatments such as pickling, water washing, neutralization, and rust prevention must be performed, which increases the number of steps and equipment as described above7, and there is also the problem of occupying space within the factory. . The increase in the number of processing steps also leads to a disadvantage in that the processing time becomes longer.
本発明者等は上述の如き従来技術の課題を解決すべく本
発明を成したものであり、その目的とする処は炉中ろう
付などの如く無酸化雰囲気において高熱処理された鋼材
の表面に、均−且つ高品質の塗装下地を形成し得るとと
もに、処理工程数及び処理設備の削減を図９、もって工
場内の占有面積の減少と処理時間の短縮を達成し得る鋼
材の塗装前処理剤及び塗装前処理方法を提供するにある
。The present inventors have developed the present invention in order to solve the problems of the prior art as described above, and the purpose is to apply heat treatment to the surface of steel materials that have been subjected to high heat treatment in a non-oxidizing atmosphere, such as during furnace brazing. A pre-painting treatment agent for steel materials that can form a uniform and high-quality paint base, reduce the number of treatment steps and treatment equipment, and thereby reduce the area occupied in the factory and shorten the treatment time. and a painting pretreatment method.
斯る目的を達成すべく第１発明に係る鋼材の塗装前処理
剤は、リン酸、水溶性溶剤及びキレート剤を主体とし且
つ該リン酸の濃度を０．０５〜５．Ｑｗｔ係とした酸組
成物溶液に、シュウ酸塩を３〜１０００ｍｇ／−ｇ添加
したことを要旨としており、また第２発明に係る鋼材の
塗装前処理方法は、無酸化雰囲気の加熱炉において高熱
処理した鋼材を炉冷室で炉冷した後、リン酸、水溶性溶
剤及びキレート剤を主体とし該リン酸の濃度を０．０５
〜５．Ｑｗｔ％とじた酸組成物溶液にシュウ酸塩を添加
してなる処理液によって上記鋼材を急冷し２、次いでこ
の鋼材表面に塗装下地としての化成皮膜を形成するよう
にしたことをその要旨としている。In order to achieve this object, a pre-painting treatment agent for steel materials according to the first invention mainly contains phosphoric acid, a water-soluble solvent, and a chelating agent, and the concentration of the phosphoric acid is set to 0.05 to 5. The gist of the invention is that 3 to 1000 mg/-g of oxalate is added to an acid composition solution with a Qwt ratio, and the method for pre-painting steel materials according to the second invention involves high temperature treatment in a heating furnace in a non-oxidizing atmosphere. After the heat-treated steel material is cooled in a furnace cooling chamber, phosphoric acid, a water-soluble solvent, and a chelating agent are mainly used, and the concentration of the phosphoric acid is 0.05.
~5. The gist of this method is to rapidly cool the above steel material using a treatment solution made by adding oxalate to a Qwt% acid composition solution2, and then form a chemical conversion film on the surface of the steel material as a base for painting. .
以下に本発明の好適一実施例を添付図面に基いて詳述す
る。A preferred embodiment of the present invention will be described in detail below with reference to the accompanying drawings.
第１図は本発明に係る塗装前処理剤を冷却液として用い
た炉中ろう付装置を示すものである。FIG. 1 shows a furnace brazing apparatus using the paint pretreatment agent according to the present invention as a cooling liquid.
図中１はブツシャ−であり、このプッシャー１によって
鋼材を載置したトレイ２がコンベア３上を図中右方向へ
間欠的に移送される。そして図中右端まで移送されたト
レイ２は下降装置４によつて下方のコンベア３上に位置
せしめられ、プッシャー５ Ｋよって図中左方向へ間欠
的に移送される。Reference numeral 1 in the figure is a pusher, and the pusher 1 intermittently transports a tray 2 on which steel materials are placed on a conveyor 3 in the right direction in the figure. The tray 2 that has been transferred to the right end in the figure is positioned on the lower conveyor 3 by the lowering device 4, and is intermittently transferred to the left in the figure by the pusher 5K.
更に図中左端まで移送されたトレイ２は上昇装置６によ
ってもとの状態まで上昇せしめられ、再び鋼材を載置し
て右方へ移動する。Further, the tray 2 that has been transferred to the left end in the figure is raised to its original state by the lifting device 6, and the steel material is placed thereon again and the tray 2 is moved to the right.
そして炉中ろう付装置のコンベア３に沿って上流側（図
中左側）には予備加熱室７を設け、この予備加熱室７に
連続し７て加熱室８を設け、更にこ、の加熱室８の下流
側に連続してウォータジャケット式の炉冷室９及び冷却
室１０を設けている。A preheating chamber 7 is provided on the upstream side (left side in the figure) along the conveyor 3 of the furnace brazing device, and a heating chamber 8 is provided continuously to this preheating chamber 7. A water jacket type furnace cooling chamber 9 and a cooling chamber 10 are provided continuously on the downstream side of the furnace 8.
また上記予備加熱室７の入口部、炉冷室９と冷却室１０
との境界部、及び冷却室１０の出口部の夫々にシャッタ
ー１１・・・を堰り付・け各室を気密に区画し得るよう
にし、更に加熱炉８、炉冷室９及び冷却室１０の夫々の
天井部に分解アンモニア等の変性ガス、チッ素ガス、還
元ガス等の導管１２・・・を連結するとともに、予備加
熱室７の入口近傍、炉冷室９と冷却室１０の境界部近傍
及び冷却室１０の出口近傍の夫々にガス排出管１３・・
・を取シ付け、炉内を無酸化雰囲気に保つようにしてい
る。Also, the entrance of the preheating chamber 7, the furnace cooling chamber 9 and the cooling chamber 10.
A shutter 11 is provided at each of the boundary between the heating furnace 8, the furnace cooling chamber 9, and the cooling chamber 10, so that each chamber can be partitioned airtight. Conduit pipes 12 for denatured gas such as decomposed ammonia, nitrogen gas, reducing gas, etc. are connected to the ceilings of each of the pipes, and a pipe 12 for carrying modified gas such as decomposed ammonia, nitrogen gas, reducing gas, etc. is connected to the ceiling of each of Gas exhaust pipes 13 are installed near the outlet of the cooling chamber 10 and near the outlet of the cooling chamber 10, respectively.
- is installed to maintain a non-oxidizing atmosphere inside the furnace.
また冷却室１０の下方には冷却槽１４を設け、この中に
トレイ２を昇降せしめる昇降装置１５を配置し、更に上
記冷却槽１４の下方には冷却液の供給タンク１６を配設
し、この供給タンク１６と冷却槽１４とをパイプ１７．
１７で連結するとともにポンプ１８によって冷却液１９
を冷却槽１４内に送り込むようにしている。Further, a cooling tank 14 is provided below the cooling chamber 10, in which a lifting device 15 for raising and lowering the tray 2 is arranged, and further below the cooling tank 14, a cooling liquid supply tank 16 is arranged. The supply tank 16 and the cooling tank 14 are connected by a pipe 17.
17 and coolant 19 is connected by a pump 18.
is fed into the cooling tank 14.
そして上記冷却液１９は鋼材表面の酸化スケールを除去
する処理剤としてめ効果も有し、その成分はリン酸、水
溶性溶剤及びキレート剤を含み、且つ該リン酸の濃度を
０．０５〜５．０ｗｔ％とじた酸組成物溶液に、３〜１
０００ ｍｇ／Ｊ！のシュウ酸塩を添加したもので、そ
の温度は５〜４５ｃとしている。The cooling liquid 19 also has the effect of acting as a treatment agent for removing oxidized scale on the surface of steel materials, and its components include phosphoric acid, a water-soluble solvent, and a chelating agent, and the concentration of the phosphoric acid is 0.05 to 5. 3 to 1 to the acid composition solution containing .0 wt%
000 mg/J! of oxalate is added, and the temperature is set at 5 to 45 degrees centigrade.
以上の如き構成からなる装置において、各接合部にろう
材をセットした鋼材をトレイ２上に載せ、予備加熱室７
に送シ、ここで予熱した後、加熱室８に搬送し、この加
熱室８において例えば１１００Ｃ〜１１５０Ｃまで加熱
してろう付を行なう。In the apparatus configured as described above, the steel material with brazing filler metal set at each joint is placed on the tray 2, and the preheating chamber 7
After being preheated there, it is transported to a heating chamber 8, where it is heated to, for example, 1100C to 1150C to perform brazing.
次いで鋼材を炉冷室９に送り、ここで後に急冷しても熱
による変形が小さい変態点以下の温度、即ち５７０−１
”７２ ｏＣ程度捷で冷却する。そして炉冷が終った鋼
材を次の冷却室１０に導き、この冷却室１０の下部に設
けた冷却槽１４内の冷却液１９中に浸漬して急冷する。Next, the steel material is sent to the furnace cooling chamber 9, where it is heated to a temperature below the transformation point where deformation due to heat is small even if it is rapidly cooled later, that is, 570-1.
The steel material is cooled down to approximately 72 oC.Then, the steel material that has been furnace cooled is led to the next cooling chamber 10, and is immersed in the cooling liquid 19 in the cooling tank 14 provided at the bottom of this cooling chamber 10 to be rapidly cooled.
この後鋼材を冷却槽１４から引き上げ、冷却室１０から
取り出し、次工程へ搬送する。After this, the steel material is pulled up from the cooling tank 14, taken out from the cooling chamber 10, and transported to the next process.
次工程においては上記鋼材をリン酸亜鉛等の化成皮膜処
理剤を満した処理槽に浸漬し、塗装下地を形成する。そ
して下地を形成した鋼材表面に塗料を吹付け、焼付乾燥
せしめて製品とする。In the next step, the steel material is immersed in a treatment tank filled with a chemical conversion coating treatment agent such as zinc phosphate to form a base for painting. Paint is then sprayed onto the surface of the steel material that has formed the base, and the product is baked and dried.
第２図は上記酸組成物溶液のリン酸濃度と化成皮膜性と
の関係を示したもので８シ、化成皮膜の優劣を５点法で
示し、３点以上であることが従来以上の効果を発揮する
のに必要である。また上記酸組成物溶液に添加するシュ
ウ酸塩はシュウ酸ニッケルとし、且つその濃度は０．０
１ｗｔ％とじている。Figure 2 shows the relationship between the phosphoric acid concentration of the acid composition solution and the chemical conversion coating properties. It is necessary to demonstrate the Further, the oxalate added to the acid composition solution is nickel oxalate, and its concentration is 0.0.
It is bound to 1wt%.
この第２図からも明らかな如く、酸組成物溶液中のリン
酸濃度ｉｊ ｏ、 ０５ ｗｔ％以上であることが好ま
しく、またリン酸濃度が５． Ｏｗｔ％を超えると鋼材
表面がエツチングされる不利があるため、リン酸濃度は
０．０５〜５．０ｗｔ％であることが好ましい。As is clear from FIG. 2, it is preferable that the phosphoric acid concentration in the acid composition solution is at least 5.05 wt%. If it exceeds Owt%, there is a disadvantage that the surface of the steel material will be etched, so the phosphoric acid concentration is preferably 0.05 to 5.0wt%.
第３図は上記酸組成物溶液に添加するシュウ酸塩の濃度
と化成皮膜性との関係を第２図と同様の５点法で示した
ものであシ、酸組成物溶液中のリン酸濃度は０，５ｗｔ
％とじている。Figure 3 shows the relationship between the concentration of oxalate added to the acid composition solution and the chemical conversion film properties using the same five-point method as in Figure 2. Concentration is 0.5wt
% is closed.
この第３図からも明らかな如く、添加するシュウ酸塩の
濃度は３ ｍｇ／−８以上であることが好ましく−ｘ
＊１ｏ ｏ ｏｍｖ’−ｅ 以上となると酸組成物溶−
液の温度との関係で溶解しにくくなるので、シュウ酸塩
の濃度は３〜１０００ ｍｙ７’Ａの範囲が適当である
。尚、添加するシュウ酸塩の種類は任意であシ、また二
種以上のシュウ酸煙を混合して添加してもよい。As is clear from Fig. 3, the concentration of oxalate to be added is preferably 3 mg/-8 or more -x
*1o o omv'-e or more, the acid composition dissolves.
Since it becomes difficult to dissolve depending on the temperature of the liquid, the appropriate concentration of oxalate is in the range of 3 to 1000 my7'A. The type of oxalate to be added is arbitrary, and two or more types of oxalate fumes may be mixed and added.
下記の表２に各種シュウ酸塩の具体例を挙げる。Specific examples of various oxalates are listed in Table 2 below.
〔表 ２〕
次に本発明の効果を具体的々実験例と比較例を挙げて説
明する。[Table 2] Next, the effects of the present invention will be specifically explained by giving experimental examples and comparative examples.
実験例１
リン酸２５ｗｔ％、水溶性溶剤としてのブチルセロソル
ブ５Ｑｗｔ９１）、非イオン界面活性剤ＩＱｗｔ％、キ
レート剤５ｗｔ％及び水］Ｑｗｔ％からなる酸組成物溶
液（以下単に酸組成物Ａとする）を用意し、この酸組成
物Ａを１ｗｔ ％ 、シュウ酸ニッケル１ｗｔ係、残部
を水道水とした溶液をよく攪拌して液温を２５±５Ｃと
したものを、前記炉中ろう付装置の冷却室下部に設けた
急冷用冷却槽内に満しておく。Experimental Example 1 An acid composition solution (hereinafter simply referred to as acid composition A) consisting of 25 wt% phosphoric acid, 5 Qwt% butyl cellosolve as a water-soluble solvent, IQwt% nonionic surfactant, 5 wt% chelating agent, and Qwt% water (hereinafter simply referred to as acid composition A). A solution containing 1 wt % of this acid composition A, 1 wt % of nickel oxalate, and the balance of tap water was stirred well to bring the liquid temperature to 25 ± 5 C. Fill the cooling tank for rapid cooling installed in the lower part of the room.
そして炭素含有率０．０２〜０８５％の鋼材からなる被
処理材であるリヤフォークの各終合部間に銅ろう材をセ
ットし、この被処理材を変性ガス等によって無酸化雰囲
気とされた予備加熱室に送入し予備加熱を行なう。その
後被処理材を加熱炉本体内に移行せしめ１１００〜１１
５０ｒの温度で２〜３分間加熱し、ろう材を上記各結合
部間に溶融して流入充填せしめる。Copper brazing filler metal was then set between each end of the rear fork, which is a material to be treated made of steel with a carbon content of 0.02 to 085%, and the material to be treated was made into a non-oxidizing atmosphere using modified gas, etc. It is sent to a preheating chamber and preheated. After that, the material to be treated is transferred into the heating furnace main body 1100-11
Heating is carried out at a temperature of 50 r for 2 to 3 minutes, and the brazing filler metal is melted and filled between the above-mentioned joints.
次いでこの被処理材をウォータジャケット式の炉冷室に
導き、炉冷を行なって約７００Ｃとし、更にこの炉冷後
の被処理材を上記急冷用兼表面処理用の溶液を満だ【−
た冷却槽内に約１分間浸漬せしめる。その後被処理材を
冷却槽から取り出し、エアブロ−して水切り乾燥を行な
う。Next, this material to be treated was introduced into a water jacket-type furnace cooling chamber, where it was cooled to approximately 700C, and the material to be treated after being cooled in the furnace was filled with the above-mentioned solution for quenching and surface treatment.
immerse it in a cooling bath for about 1 minute. Thereafter, the material to be treated is taken out of the cooling tank and dried by air blowing.
このように処理した被処理材の表面には酸化スケールの
発生けみられず、且つ面粗度も良好であった。No oxide scale was observed on the surface of the treated material treated in this manner, and the surface roughness was also good.
この後、被処理材を脱脂処理剤（リドリン＃５３：日本
ペイント製）を５ ｗｔ％に調整し、且つ５５Ｕに保っ
た脱脂槽に約２分間浸漬し７て洗浄し、次いで脱脂槽か
ら取り出して約３０秒間水洗゛を行なう。After this, the material to be treated was cleaned by immersing it in a degreasing tank containing a degreasing agent (Ridrin #53: manufactured by Nippon Paint Co., Ltd.) adjusted to 5 wt% and maintained at 55 U for about 2 minutes, and then taking it out from the degreasing tank. Wash with water for about 30 seconds.
次いで被処理材を、リン酸亜鉛化成処理剤（グラノジン
…Ｃ８１０００：日本ペイント製）を３ｗｔ％に調整す
るとともに、液温を５０±５℃とした溶液を満した化成
皮膜処理槽に約３分間浸漬し、その後水切乾燥を行なう
。Next, the material to be treated was placed in a chemical conversion coating treatment tank filled with a solution containing a zinc phosphate chemical conversion treatment agent (Granodine C81000 manufactured by Nippon Paint Co., Ltd.) adjusted to 3 wt% and at a temperature of 50 ± 5°C for about 3 minutes. Soak, then drain and dry.
次に被処理材の表面に、水溶性アクリル上塗り塗料（ア
クア＃７１００：日本油脂製）を２５〜３０μの厚さに
吹付塗装し、約１７０Ｃで３０分間程度熱風炉内で焼付
を行々い、次いで炉より取り出し室温まで冷却する。Next, a water-soluble acrylic top coat (Aqua #7100, manufactured by Nippon Oil & Fats Co., Ltd.) was spray-coated to a thickness of 25 to 30 μm on the surface of the material to be treated, and baked in a hot air oven at about 170 C for about 30 minutes. Then, it is taken out of the oven and cooled to room temperature.
以上のように処理した被処理材であるリヤフォークの表
面に形成された塗膜の外観性、密着性及び耐蝕性等の塗
膜物性は、従来方法によって酸化スケールを除去したも
のに比べ大巾に良好であった。The appearance, adhesion, corrosion resistance, and other physical properties of the paint film formed on the surface of the rear fork, which is the material to be treated as described above, are significantly greater than those from which oxide scale has been removed by conventional methods. It was in good condition.
実験例２
酸組成物Ａを１ｗｔ％、シュウ酸亜鉛Ｑ、５ｗｔ％、残
部を水道水とした溶液をよく攪拌して液温を２５±５℃
としたものを急冷用の冷却槽内に満す一方、前記実験例
１の被処理材に前記と同様の無酸化雰囲気における加熱
及び炉冷処理を行なって被処理材の温度を７００Ｃとす
る。Experimental Example 2 A solution containing 1 wt% of acid composition A, 5 wt% of zinc oxalate Q, and the balance of tap water was stirred well and the liquid temperature was adjusted to 25±5°C.
While filling a cooling tank for rapid cooling, the material to be treated in Experimental Example 1 was subjected to the same heating and furnace cooling treatment in a non-oxidizing atmosphere as described above to bring the temperature of the material to 700C.
そして炉冷後の被処理材を冷却槽内に約３０秒間浸漬し
、次いで冷却槽から取り出し、エアブロ−によって水切
りを行なう。After cooling in the furnace, the material to be treated is immersed in a cooling tank for about 30 seconds, then taken out from the cooling tank and drained by air blowing.
このように処理した被処理材の表面には酸化スケールの
発生はみられず、外観も良好であった。No oxide scale was observed on the surface of the treated material treated in this way, and the appearance was good.
この後、被処理材に前記実験例１と同様の化成皮膜処理
を施し７、更に前記実験例１と同様の塗装処理を施す。Thereafter, the material to be treated is subjected to the same chemical conversion coating treatment as in Experimental Example 1 7, and is further subjected to the same painting treatment as in Experimental Example 1.
以上によって得られた被処理材の表面に形成された塗膜
の外観性、密着性及び耐参性等の塗膜物性は極めて良好
であった。The physical properties of the coating film formed on the surface of the treated material obtained above, such as appearance, adhesion, and resistance to dust, were extremely good.
実験例３
酸組成物ＡをＱ、５ｗｔ％、シュウ酸銅１ｗｔ％、残部
を水道水とした溶液をよく攪拌して液温を２５±５Ｃと
したものを急冷用の冷却槽内に満す一方、前記実験例１
の被処理材に前記と同様の無酸化雰囲気における熱処理
を行ない、被処理材の温度を７０００とする。Experimental Example 3 A solution containing acid composition A as Q, 5 wt%, copper oxalate 1 wt%, and the balance tap water was stirred well to bring the liquid temperature to 25 ± 5 C, and a cooling tank for rapid cooling was filled. On the other hand, the experimental example 1
The material to be treated is subjected to heat treatment in the same non-oxidizing atmosphere as described above, and the temperature of the material to be treated is set to 7000.
そして上記被処理材を急冷用の冷却槽内に約３０秒間浸
漬し、次いで冷却槽から取り出し、エアブロ−によって
水切りを行なう。The material to be treated is immersed in a cooling tank for rapid cooling for about 30 seconds, then taken out from the cooling tank and drained by air blowing.
このように処理した被処理材の表面には酸化スケールの
発生はみられず、且つ外観も良好であった。No oxide scale was observed on the surface of the treated material treated in this way, and the appearance was good.
この後、被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施す。Thereafter, the treated material was subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1 above.
以上によって得られた被処理材の表面に形成された塗膜
の外観性、密着性及び耐蝕性等の塗膜物性は従来方法に
よる場合に比べ極めて良好であつｔ（。The physical properties of the coating film formed on the surface of the treated material obtained by the above method, such as appearance, adhesion, and corrosion resistance, are extremely good compared to those obtained by conventional methods.
実験例４
酸組成物Ａを５，９ｗｔ％、シュウ酸バリウム０．５ｗ
ｔ％、残部を水道水とした溶液をよく攪拌して液温を２
５±５Ｃとしたものを急冷用の冷却槽内に満す一方、前
記実験例１の被処理材を無酸化雰囲気において予備加熱
を行なうとともに加熱炉本体に移行して９００Ｃで５分
間加熱する。Experimental Example 4 5.9 wt% of acid composition A, 0.5 w of barium oxalate
t% and the remainder was tap water, stir well and bring the liquid temperature to 2.
While the cooling tank for rapid cooling was filled with 5±5C, the material to be treated from Experimental Example 1 was preheated in a non-oxidizing atmosphere, transferred to the heating furnace body, and heated at 900C for 5 minutes.
次いで被処理材を６５０′ｃまで炉冷し、この被処理材
を上記急冷用の冷却槽内に約３０秒間浸漬し、次いで冷
却槽から取り出し、エアブローによって水切りを行なう
。Next, the material to be treated is furnace-cooled to 650'c, immersed in the cooling tank for quenching for about 30 seconds, then taken out from the cooling tank, and drained by air blowing.
このように処理した被処理材の表面には酸化スケールの
発生はみられず、且つ外観も良好であった。No oxide scale was observed on the surface of the treated material treated in this way, and the appearance was good.
この後、被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施す。Thereafter, the treated material was subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1 above.
以−ヒによって得られた被処理材の表面に形成された塗
膜の外観性、密着性及び耐蝕性等の塗膜物性は従来方法
による場合に比べ極めて良好であった。The physical properties of the coating film formed on the surface of the treated material obtained by this method, such as appearance, adhesion, and corrosion resistance, were extremely good compared to those obtained by the conventional method.
実験例５
酸組成物Ａを３． Ｑ ｗｔ％、シュウ酸ニッケル０．
０１ｗｔ％、残部を水道水とした溶液をよく攪拌して液
温を２５±５Ｃとしたものを急冷用の冷却槽に満す一方
、前記実験例１の被処理材を無酸化雰囲気において、予
備加熱を行なうとともに加熱炉本体に移行して９００Ｃ
で５分間加熱する。Experimental Example 5 Acid composition A was mixed with 3. Q wt%, nickel oxalate 0.
A cooling tank for quenching was filled with a solution containing 0.01 wt% and the balance being tap water and the temperature was brought to 25 ± 5 C. As well as heating, it moves to the heating furnace main body and reaches 900C.
Heat for 5 minutes.
次いで被処理材を７００Ｃまで炉冷し、この被処理材を
上記急冷用の冷却槽に約３０秒間浸漬し、その後冷却槽
から取り出し、エアブロ−によって水切りを行なう。Next, the material to be treated is furnace-cooled to 700C, immersed in the cooling tank for rapid cooling for about 30 seconds, and then taken out from the cooling tank and drained by air blowing.
このように処理した被処理材の表面には酸化スケールの
発生はなく、且つ外観も良好であった。There was no oxide scale on the surface of the treated material treated in this way, and the appearance was good.
この後、被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施す。Thereafter, the treated material was subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1 above.
以上によって得られた被処理材の表面に形成された塗膜
の外観性、密着性及び耐蝕性等の塗膜物性は椿めて良好
であった。The physical properties of the coating film formed on the surface of the treated material obtained above, such as appearance, adhesion, and corrosion resistance, were all excellent.
実験例６
酸組成物Ａを０．５ｗｔ％、シュウ酸鉄１，９ｗｔ％、
残部を水道水とした溶液をよく攪拌して液温を２５±５
Ｃとしたものを急冷用の冷却槽に満す一方、前記実験例
１の被処理材を無酸化雰囲気において、予備加熱を行な
った後加熱炉本体に移行して９０００で５分間加熱する
。Experimental Example 6 0.5 wt% of acid composition A, 1.9 wt% of iron oxalate,
Stir the solution with tap water in the balance and bring the temperature to 25±5.
While filling the cooling tank for rapid cooling with C, the material to be treated from Experimental Example 1 was preheated in a non-oxidizing atmosphere, transferred to the heating furnace body, and heated at 9000 for 5 minutes.
次いで被処理材を７５０Ｃまで炉冷した後、上記急冷用
の冷却槽に約３０秒間浸漬し、その後冷却槽から取り出
し、エアブロ−によって水切りを行なう。Next, the material to be treated is furnace-cooled to 750 C, and then immersed in the cooling tank for quenching for about 30 seconds, and then taken out from the cooling tank and drained by air blowing.
このように処理した被処理材の表面には酸化スケールの
発生はなく、且つ外観も良好であった。There was no oxide scale on the surface of the treated material treated in this way, and the appearance was good.
この後、被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施す。Thereafter, the treated material was subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1 above.
以上によって得られた被処理材の表面に形成された塗膜
の外観性、密着性及び耐蝕性は極めて良好であった。The appearance, adhesion, and corrosion resistance of the coating film formed on the surface of the treated material obtained above were extremely good.
実験例７
酸組成物Ａを］、Ｑｗｔ％、シュウ酸ニッケルｏ５ｗｔ
４ ％防錆油（ＮＰオイルＡＲ−５：日本ペイント製）
Ｑ、５ｗｔ％、残部を水道水とした溶液をよく攪拌して
液温を２５±５Ｃとしたものを急冷用の冷却槽に満す一
方、前記実験例１の被処理材を無酸化雰囲気において、
予備加熱を行なった後加熱炉本体に移行して９００Ｃで
５分間加熱する。Experimental Example 7 Acid composition A], Qwt%, nickel oxalate o5wt
4% Rust preventive oil (NP oil AR-5: manufactured by Nippon Paint)
A cooling tank for rapid cooling was filled with a solution containing 5 wt% of Q, the balance being tap water and the liquid temperature was 25 ± 5 C, while the material to be treated from Experimental Example 1 was placed in a non-oxidizing atmosphere. ,
After preheating, it is transferred to the heating furnace main body and heated at 900C for 5 minutes.
次いで被処理材を７００Ｃまで炉冷した後、上記急冷用
の冷却槽に約３０秒間浸漬し、その後冷却槽から取り出
し、エアブローによって水切りを行なう。Next, the material to be treated is furnace-cooled to 700 C, then immersed in the cooling tank for quenching for about 30 seconds, and then taken out from the cooling tank and drained by air blowing.
このように処理した被処理材の表面に、ｔｄ、酸化スケ
ールの発生はみられず、且つ外観も良好＋あった。No td or oxide scale was observed on the surface of the treated material treated in this manner, and the appearance was also good.
この後、被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施す。Thereafter, the treated material was subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1 above.
以上によって得られた被処理材の表面に形成された塗膜
の外観性、密着性及び耐蝕性は極めて良好であった。The appearance, adhesion, and corrosion resistance of the coating film formed on the surface of the treated material obtained above were extremely good.
実験例８
リン酸８Ｑｗｔ％、ブチルセロソルブ９ｗｔ％、キレー
ト剤２ｗｔ％及び水９ｗｔ％からなる酸組成物溶液（以
下単に酸組成物Ｂとする）を用意し、この酸組成物Ｂを
１ｗｔ％、シュウ酸ニッケル１ｗｔ％、残部を水道水と
した溶液をよく攪拌して液温を２５±５Ｃとしたものを
急冷用の冷却槽に満す。Experimental Example 8 An acid composition solution (hereinafter simply referred to as acid composition B) consisting of 8Qwt% phosphoric acid, 9wt% butyl cellosolve, 2wt% chelating agent, and 9wt% water was prepared, and 1wt% of this acid composition B was A solution containing 1 wt % of nickel oxide and the balance being tap water was stirred well to bring the temperature to 25±5 C, and a cooling tank for rapid cooling was filled.
その一方、前記実験例１の被処理材を無酸化雰囲気にお
いて、予備加熱を行なった後加熱炉本体内に移行して９
００Ｃで５分間加熱する。On the other hand, the material to be treated in Experimental Example 1 was preheated in a non-oxidizing atmosphere and then transferred into the heating furnace main body.
Heat at 00C for 5 minutes.
次いで被処理材を７０Ｏｒまで炉冷した後、上記急冷用
の冷却槽に約３０秒間浸漬し、その後冷却槽から取り出
し、エアブロ−によって水切りを行なう。Next, the material to be treated is furnace-cooled to 70 Or, immersed in the cooling tank for quenching for about 30 seconds, then taken out from the cooling tank, and drained by air blowing.
このように処理した被処理材の表面には酸化スケールの
発生はみられず、且つ外観も良好であった。No oxide scale was observed on the surface of the treated material treated in this way, and the appearance was good.
この後、被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施す。Thereafter, the treated material was subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1 above.
以上によって得られた被処理材の表面に形成された塗膜
の外観性、密着性及び耐蝕性等の塗膜物性は極めて良好
であった。The physical properties of the coating film formed on the surface of the treated material thus obtained, such as appearance, adhesion, and corrosion resistance, were extremely good.
実験例９
酸組成物Ｂを０．５ｗｔ％、シュウ酸亜鉛０，５ｗｔ％
残部を水とした溶液をよく攪拌して液温を２５±５℃と
したものを急冷用の冷却槽に満す一方、前記実験例１の
被処理材を無酸化雰囲気において、予備加熱を行なった
後加熱炉本体に移行して１１２０〜１１５０Ｃで３分間
加熱する。Experimental Example 9 Acid composition B: 0.5 wt%, zinc oxalate: 0.5 wt%
A cooling tank for rapid cooling was filled with a solution in which the remainder was water and the solution was stirred well to bring the temperature to 25±5°C, while the material to be treated from Experimental Example 1 was preheated in a non-oxidizing atmosphere. After that, it is transferred to the heating furnace main body and heated at 1120 to 1150 C for 3 minutes.
次いで被処理材を７００Ｃまで炉冷した後、上記急冷用
の冷却槽に約３０秒間浸漬し、その後冷却槽から取り出
し、エアブロ−によって水切シを行なう。Next, the material to be treated is furnace-cooled to 700 C, and then immersed in the cooling tank for quenching for about 30 seconds, and then taken out from the cooling tank and drained by air blowing.
このように処理した被処理材の表面には酸化スケールの
発生はみられず、且つ外観も良好であった。No oxide scale was observed on the surface of the treated material treated in this way, and the appearance was good.
この後被処理材に前記実験例１と同様の化成皮膜処理及
び塗装処理を施す。Thereafter, the treated material was subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1.
以上によって得られた被処理材の表面に形成された塗膜
の外観性、密着性及び耐蝕性等の塗膜物性は極めて良好
であった。The physical properties of the coating film formed on the surface of the treated material thus obtained, such as appearance, adhesion, and corrosion resistance, were extremely good.
次に本発明によらない例を以下に比較例として示し、本
発明の効果をより明確にする。Next, examples not based on the present invention will be shown below as comparative examples to further clarify the effects of the present invention.
比較例１
前記実験例１の被処理材を無酸化雰囲気において、予備
加熱を行なった後加熱炉本体に移行して１１２０〜１１
５０Ｃで３分間加熱してろう付を行なう。Comparative Example 1 The material to be treated from Experimental Example 1 was preheated in a non-oxidizing atmosphere and then transferred to the heating furnace main body to a temperature of 1120 to 11
Brazing is performed by heating at 50C for 3 minutes.
次いで上記被処理材を７０００まで炉冷した後、２５±
５０の水を張った急冷用の冷却槽に約３０秒間浸漬１−
１その後冷却槽がら取シ出し、エアブロ−によって水切
シを行なう。Next, after cooling the above-mentioned material to be treated in a furnace to 7000℃,
Immerse for about 30 seconds in a cooling tank filled with 50% water.1-
1. After that, take out the cooling tank and drain it by air blowing.
このように処理した被処理材の表面ＫＦｉ全面に酸化ス
ケールが発生しており、ブルー及びテンパーカラーを呈
していた。Oxidized scale was generated on the entire surface of the KFi surface of the treated material treated in this manner, and the material had a blue and tempered color.
更に、上記被処理材に前記実験例１と同様の化成皮膜処
理及び塗装処理を施す。Furthermore, the above treated material is subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1.
以上の如くして得られた被処理材表面に形成された塗膜
は、外観性、密着性及び耐蝕性等の全ての面において上
記各実験例のものに比べ大きく劣つていた。The coating film formed on the surface of the treated material obtained as described above was significantly inferior to those of the above-mentioned experimental examples in all aspects such as appearance, adhesion, and corrosion resistance.
比較例２
酸組成物Ａを１，０ｗ１％、残部を水とし、これをよく
攪拌して液温を２５±５０とした溶液を急冷用の冷却槽
に満し、この一方、前記実験例１の被処理材を無酸化雰
囲気において、予備加熱を行なった後、加熱炉本体に移
行して９００Ｃで５分間加熱しろう付を行なう、
その後、被処理材を７００Ｃまで炉冷し、次いでこの被
処理材を上記急冷用の冷却槽に約３０秒間浸漬し、その
後冷却槽から取り出し、エアブローによって水切りを行
々う。Comparative Example 2 A cooling tank for rapid cooling was filled with a solution containing 1.0w1% of acid composition A and the balance being water, and the solution was stirred well to bring the liquid temperature to 25±50. After preheating the material to be treated in a non-oxidizing atmosphere, it is transferred to the heating furnace main body and heated at 900C for 5 minutes to perform brazing.The material to be treated is then cooled to 700C in the furnace, and then the material to be treated is heated to 700C. The treated material is immersed in the cooling tank for rapid cooling for about 30 seconds, then taken out from the cooling tank and drained by air blowing.
このように処理した被処理材の表面の全面に酸化スケー
ルが発生しており、ブルー及びテンパーカラーを呈して
いた。Oxidized scale was generated on the entire surface of the treated material treated in this way, and the material had a blue and tempered color.
更に上記被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施す。Furthermore, the above treated material is subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1.
以上の如くして得られた被処理材表面に形成された塗膜
は、外観性密着性及び耐蝕性等の全ての面において、上
記各実験例のものに比べ大巾に劣つていた。The coating film formed on the surface of the treated material thus obtained was significantly inferior to those of the above-mentioned experimental examples in all aspects such as appearance, adhesion, and corrosion resistance.
比較例３
酸組成物Ｂをｌ、９ｗｔ％、残部を水とし、これをよく
攪拌して液温を２５±５Ｃとした溶液を急冷用の冷却槽
に満す。Comparative Example 3 A cooling tank for rapid cooling is filled with a solution containing 1 of acid composition B, 9 wt %, and the balance being water, and stirring the solution well to bring the liquid temperature to 25±5 C.
そして前記実験例１の被処理材に前記比較例１と同様の
無酸化雰囲気における熱処理を行ない、且つ急冷処理を
施す。Then, the treated material of Experimental Example 1 is subjected to heat treatment in the same non-oxidizing atmosphere as in Comparative Example 1, and is also subjected to rapid cooling treatment.
このように処理した被処理材の表面には全面に酸化スケ
ールが生じており、ブルー及びテンパーカラーを呈して
いた。Oxide scale was formed on the entire surface of the treated material treated in this way, and the material had a blue and tempered color.
更に上記被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施す。Furthermore, the above treated material is subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1.
以上の如くして得られた被処理材の表面に形成された塗
膜は前記比較例と同様に塗膜物性に劣ったものであった
。The coating film formed on the surface of the treated material obtained as described above was inferior in coating film physical properties as in the comparative example.
比較例４
シュウ酸ニッケル１． Ｏｗｔ％、残部を水とし、これ
をよく攪拌して青味がかった乳白色の溶液とし、更に液
温を２５±５Ｃとしたものを急冷用の冷却槽に満す。一
方前記実験例１の被処理材を前記比較例２と同様の無酸
化雰囲気における熱処理を施す。Comparative Example 4 Nickel oxalate 1. Owt%, the remainder being water, stir well to obtain a bluish milky white solution, and then bring the liquid temperature to 25±5C, which is then filled into a cooling tank for rapid cooling. On the other hand, the material to be treated in Experimental Example 1 is subjected to heat treatment in the same non-oxidizing atmosphere as in Comparative Example 2.
その後被処理材を上記急冷用の冷却槽に°３０秒間浸漬
し、これを取り出し、エアブロ−にて水切りを行なう。Thereafter, the material to be treated is immersed in the cooling bath for rapid cooling for 30 seconds, taken out, and drained with air blow.
このように処理した被処理材の表面は黒味の強いテンパ
ーカラーを呈し、且つ酸化スケールが全面に生じていた
。The surface of the treated material treated in this manner had a strong blackish temper color, and oxidized scale had formed on the entire surface.
更に上記被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施す。Furthermore, the above treated material is subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1.
このようにして得られた被処理材の表面に形成された塗
膜にはムラがあり、且つ密着性等の塗膜物性も前記各実
験例に比べ大巾に劣っていた。The coating film formed on the surface of the treated material thus obtained was uneven, and the physical properties of the coating film, such as adhesion, were also significantly inferior to those of the experimental examples described above.
比較例５
シュウ酸亜鉛１．Ｑｗｔ％、残部を水とし、これを前記
比較例と同一の条件で冷却槽内に満す一方、前記実験例
１の被処理材に前記比較例２と同様の無酸化雰囲気にお
ける熱処理を施し、更にこれを上記冷却槽内において、
約３０秒間浸漬し、その後槽から取り出してエアブロ−
によって水切りを行なう。Comparative Example 5 Zinc oxalate 1. Qwt%, the remainder being water, and filling the cooling tank with this under the same conditions as in the comparative example, while subjecting the treated material of Experimental Example 1 to heat treatment in the same non-oxidizing atmosphere as in Comparative Example 2, Furthermore, this is placed in the cooling tank,
Immerse it for about 30 seconds, then remove it from the bath and blow it with air.
Drain the water.
この被処理材の表面もテンパーカラーを呈し、且つ酸化
スケールが全面に生じていた。The surface of this material to be treated also exhibited a temper color, and oxidized scale was formed on the entire surface.
更に上記被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施した場合にも、塗膜物性は大巾に低下
したものであった。Furthermore, even when the above-mentioned treated material was subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1, the physical properties of the coating film were significantly reduced.
比較例６
シュウ酸５．Ｑｗｔ％、残部を水とした溶液を前記比較
例と同一の条件で冷却槽内に満す一方、前記実験例１の
被処理材に前記比較例２と同様の無酸化雰囲気における
熱処理を施し、更にこれを上記冷却槽内において約３０
秒間浸漬した後、冷却槽かう取す出し、エアブロ−に・
よって水切りを行なう。Comparative Example 6 Oxalic acid 5. Qwt%, the balance being water, was filled in the cooling tank under the same conditions as in the comparative example, while the material to be treated in Experimental Example 1 was subjected to heat treatment in the same non-oxidizing atmosphere as in Comparative Example 2, Furthermore, this was heated in the cooling tank for about 30 minutes.
After immersing for a second, take it out of the cooling tank and put it in an air blower.
Therefore, drain the water.
この被処理材の表面はブルーテンパーカラーが強く、酸
化スケールが全面に生じていた。The surface of this treated material had a strong blue tempered color, and oxide scale was present on the entire surface.
更にこの被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施した場合にも、塗膜物性は前記各実験
例と比べ大巾に低下していた。Furthermore, even when this treated material was subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1, the physical properties of the coating film were significantly lower than those in the experimental examples described above.
比較例７
３５％塩酸を２．９ｗｔ％、シュウ酸ニッケル１．Ｑｗ
ｔ係、残部を水とした溶液を前記比較例と同一条件で冷
却槽内に満す一方、前記実験例１の被処理材に前記比較
例２と同様の無酸化雰囲気における熱処理を施し、更に
この被処理材を上記冷却槽内において約３０秒間浸漬し
た後、冷却槽から取り出し、エアブロ−によって水切り
を行なう。Comparative Example 7 2.9 wt% of 35% hydrochloric acid, 1.9 wt% of nickel oxalate. Qw
Section t, while filling the cooling tank with a solution in which the remainder was water under the same conditions as in the comparative example, the material to be treated in Experimental Example 1 was subjected to heat treatment in the same non-oxidizing atmosphere as in Comparative Example 2, and After the material to be treated is immersed in the cooling tank for about 30 seconds, it is taken out from the cooling tank and water is drained by air blowing.
この被処理材の表面はブルーテンパーカラーを呈し、且
つ部分的に黄精が発生していた。The surface of the material to be treated had a blue tempered color and yellowing was partially generated.
更にこの被処理材に前記実験例１と同様の化成皮膜処理
及び塗装処理を施した場合には、塗膜物性は前記実験例
と比べ大巾に低下していた。Furthermore, when this treated material was subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1, the physical properties of the coating film were significantly reduced compared to those in Experimental Example 1.
比較例８
９８％硫酸を１０ｗｔ％、シュウ酸亜鉛１゜０ｗｔ％、
残部を水とした溶液を前記比較例と同一条件で冷却槽内
に満す。この一方、前記実験例１の被処理材を無酸化雰
囲気において、予備加熱を行なった後、加熱炉本体に移
行して９００Ｃで５分間加熱し、ろう付を行なう。その
後被処理材を６００Ｃまで炉冷する。Comparative Example 8 10 wt% of 98% sulfuric acid, 1°0 wt% of zinc oxalate,
A solution with the remainder being water is filled into the cooling tank under the same conditions as in the comparative example. On the other hand, the material to be treated in Experimental Example 1 was preheated in a non-oxidizing atmosphere, then transferred to the heating furnace body and heated at 900C for 5 minutes to perform brazing. Thereafter, the material to be treated is furnace cooled to 600C.
次いで被処理材を上記冷却槽内に約３０秒間浸漬して取
シ出し、エアブロ−によって水切りを行なう。Next, the material to be treated is immersed in the cooling tank for about 30 seconds, taken out, and drained by air blowing.
斯る処理を行４つだ被処理材の表面には酸イヒスケール
と、部分的な黄精が発生していた。After four such treatments, acidic scale and yellow pigment were found on the surface of the treated material.
そして更に、上記被処理材に前記実験伊１１と同様の化
成皮膜処理及び塗装処理を施す。その結果被処理材の表
面に形成された塗膜の物性は前言己実験例と比べ大巾に
低下したものであった。Further, the treated material is subjected to the same chemical conversion coating treatment and painting treatment as in Experiment I11. As a result, the physical properties of the coating film formed on the surface of the treated material were significantly lower than in the previous experimental example.
以上の実験例及び比較例をまとめて表３に示した。The above experimental examples and comparative examples are summarized in Table 3.
前記した実験例、比較例及び表３から明らかな如く、シ
ュウ酸塩を添加した処理液と、シュウ酸を添加しない処
理液とでは、被処理材の表面にも成される塗装下地であ
る化成皮膜の良否に顕著な差異が生じる。即ち、比較例
からも明らかな如く、リン酸を含む酸成分単独の場合、
或いはシュウ酸塩単独の場合いずれも効果が薄く、また
シュウ酸塩を混合しても、酸成分が塩酸又は硫酸の場合
は効果がない。これは−塩酸等の無機酸は鋼材表面の酸
化スケールを溶解して除去するが、空気中に放出した場
合の酸化が極めて早く、シュウ酸塩の防錆効果が低下す
るものと考えられる。As is clear from the experimental examples, comparative examples, and Table 3, the treatment solution containing oxalate and the treatment solution without oxalic acid have a significant effect on chemical conversion, which is a coating base that is also formed on the surface of the treated material. There is a noticeable difference in the quality of the film. That is, as is clear from the comparative example, when the acid component containing phosphoric acid is used alone,
Alternatively, oxalate alone has little effect, and even if oxalate is mixed, there is no effect when the acid component is hydrochloric acid or sulfuric acid. This is because - Although inorganic acids such as hydrochloric acid dissolve and remove oxidized scale on the surface of steel materials, oxidation is extremely rapid when released into the air, and it is thought that the antirust effect of oxalate is reduced.
また比較例６に示すように、シュウ酸の如く酸化スケー
ルを溶解せしめる速度の遅い有機酸を用いて急冷処理を
行なうと酸化スケールの除去性が良くないことが分かる
。Furthermore, as shown in Comparative Example 6, it can be seen that when the rapid cooling treatment is performed using an organic acid such as oxalic acid, which has a slow rate of dissolving oxide scale, the oxide scale removal performance is not good.
次に二種以上のシュウ酸塩を酸組成物に添加した実験例
を示す。Next, an experimental example in which two or more types of oxalates were added to the acid composition will be shown.
実験例１０
前記実験例１に示した酸組成物Ａをｌ、Ｑｗｔ％、シュ
ウ酸ニッケル０． Ｏ，，２５ｗｔ％、シュウ酸亜鉛０
．０２５ｗｔ％、残部を水とした溶液をよく攪拌して液
温を２５±５Ｃとし、これを急冷用の冷却槽に満す。Experimental Example 10 The acid composition A shown in Experimental Example 1 was mixed with 1 Qwt% of nickel oxalate. O,,25wt%, zinc oxalate 0
．． A solution containing 025 wt% and the remainder water is stirred well to bring the liquid temperature to 25±5 C, and the solution is filled into a cooling tank for rapid cooling.
この一方、前記実験例１の被処理材（銅ろうセットせず
）を無酸化雰囲気において、平偏加熱を行なった後に加
熱炉本体に移行せしめて９００Ｃで５分間加熱する。On the other hand, the material to be treated of Experimental Example 1 (without copper soldering) was subjected to planar heating in a non-oxidizing atmosphere, and then transferred to the heating furnace body and heated at 900C for 5 minutes.
次いで被処理材を７００ｔＺ’まで炉冷した後、上記急
冷用の冷却槽に約３０秒間浸漬し、その後冷却槽から取
シ出し、エアブロ−によって水切りを行なう。Next, the material to be treated is furnace-cooled to 700 tZ', then immersed in the cooling tank for quenching for about 30 seconds, then taken out from the cooling tank, and drained by air blowing.
このように処理した被処理材の表面には酸化スケールも
なく、外観は良好であった。There was no oxidized scale on the surface of the treated material treated in this way, and the appearance was good.
そして、この後被処理材に前記実験例１と同様の化成皮
膜処理及び塗装処理を施す。After this, the treated material is subjected to the same chemical conversion coating treatment and painting treatment as in Experimental Example 1.
以上によって得られた被処理材の表面に形成された塗膜
の外観性、密着性及び耐蝕性等の塗膜物性は極めて良好
であった。The physical properties of the coating film formed on the surface of the treated material thus obtained, such as appearance, adhesion, and corrosion resistance, were extremely good.
また酸組成物の溶液に添加する二種以上のシュウ酸塩を
夫々異ならせ、他の条件及び処理は実験例１０と同一と
した実験例１１乃至実験例１３を行なったが、急冷処理
後の被処理材表面には酸化スケールはなく、且つ外観も
良好で、更に化成皮膜性にも優れ、該化成皮膜表面に形
成した塗膜の外観性、密着性、耐蝕性等も、一種類のシ
ュウ酸塩を単独で添加した場合よりも更に向上していた
。In addition, Experimental Examples 11 to 13 were conducted in which the two or more types of oxalates added to the solution of the acid composition were different, and the other conditions and treatments were the same as Experimental Example 10. There is no oxidation scale on the surface of the treated material, the appearance is good, and it also has excellent chemical conversion coating properties, and the appearance, adhesion, corrosion resistance, etc. This was even more improved than when the acid salt was added alone.
以上の実験例１０乃至実験例１３をまとめて下記の表４
に示す。The above Experimental Examples 10 to 13 are summarized in Table 4 below.
Shown below.
以上の説明で明らかな如く、本発明によれば、無酸化雰
囲気において炉中ろう付等の高熱処理された鋼材に塗装
を施す際の前処理剤を、リン酸讐水溶性溶剤及びキレー
ト剤を含み且つ該リン酸の濃度を０．０５〜５，０ｗｔ
％とじた酸組成物の溶液に、３〜１０００ ｍｇ／４の
シュウ酸塩を添加することによって構成し、更に上記前
処理剤を急冷用の冷却槽等に満たすことで塗装前の鋼材
を急冷処理するようにしたので、急冷時に生じる鋼材表
面の酸化スケールを瞬時にして除去でき、且つ一時防錆
効果も発揮する。したがって塗装下地としての化成皮膜
性を大巾に向上し、更にこの化成皮膜表面に形成される
塗膜物性をも高めることができる。As is clear from the above description, according to the present invention, a phosphoric acid, a water-soluble solvent, and a chelating agent are used as a pretreatment agent when coating steel materials that have been subjected to high heat treatment such as furnace brazing in a non-oxidizing atmosphere. and the concentration of the phosphoric acid is 0.05 to 5.0 wt.
It is composed by adding 3 to 1000 mg/4 oxalate to a solution of a diluted acid composition, and then quenching the steel material before painting by filling a cooling tank etc. for quenching with the above pretreatment agent. This treatment instantly removes the oxidized scale on the surface of the steel material that occurs during rapid cooling, and also provides a temporary rust prevention effect. Therefore, the properties of the chemical conversion film as a base for painting can be greatly improved, and the physical properties of the coating film formed on the surface of this chemical conversion film can also be improved.
また本発明によれば、独立した酸洗工程及びこれに連続
する中和工程等を不要とするので、工程数及び斯る工程
に必要とされる設備の削減が可能となり、もって処理時
間の短縮と工場内における塗装前処理用の設備が占有す
る面積を可及的に減少せしめることができる。Further, according to the present invention, since an independent pickling process and a subsequent neutralization process are not required, it is possible to reduce the number of processes and the equipment required for such processes, thereby shortening the processing time. The area occupied by equipment for pre-painting treatment in the factory can be reduced as much as possible.
更に本発明に係る塗装前処理剤はその調整が容易であり
、′高品質の塗膜を安価に形成することができる。そし
て上記の如き各効果によってリヤフォーク等の製品のコ
ストダウンにもつながる等多大の利点を有する。Furthermore, the pre-painting treatment agent according to the present invention can be easily adjusted, and a high-quality coating film can be formed at low cost. The above-mentioned effects have many advantages such as reducing the cost of products such as rear forks.
図面は本発明の好適な実施例を示すものであり、第１図
は本発明に係る塗装の前処理剤及び前処理方法を適用し
た炉中ろう付装置の概略を示す側面図、第２図は酸組成
物溶液中のリン酸濃度と化成皮膜性との関係を示す線図
、第３図は酸組成物溶液に添加するシュウ酸塩の濃度と
化成皮膜性との関係を示す線図である。
尚、図面中７は予備加熱室、８は加熱炉、９は炉冷室、
１０は冷却室、１４は冷却槽、１９は処理液である。
特許出願人 本田技研工業株式会社
代理人 弁理士下田容一部
同 弁理士 大 橋 邦 彦The drawings show preferred embodiments of the present invention, and FIG. 1 is a side view schematically showing a furnace brazing apparatus to which the coating pretreatment agent and pretreatment method of the present invention are applied, and FIG. Figure 3 is a diagram showing the relationship between the phosphoric acid concentration in the acid composition solution and the chemical conversion coating property, and Figure 3 is a diagram showing the relationship between the concentration of oxalate added to the acid composition solution and the chemical conversion coating property. be. In addition, in the drawing, 7 is a preheating chamber, 8 is a heating furnace, 9 is a furnace cooling chamber,
10 is a cooling chamber, 14 is a cooling tank, and 19 is a processing liquid. Patent applicant: Honda Motor Co., Ltd. Agent: Patent attorney Yo Shimoda Patent attorney: Kunihiko Ohashi
Claims (2)
リン酸濃度を００５〜５．Ｑｗｔ％とじた酸組成物溶液
にシュウ酸塩を３〜１０００ ｍｍ４添加してなる無酸
化雰囲気において高熱処理された鋼材の塗装前処理剤。(1) Contains phosphoric acid, a water-soluble solvent, and a chemical agent, and has a phosphoric acid concentration of 005 to 5. A pre-painting agent for steel materials subjected to high heat treatment in a non-oxidizing atmosphere, which is prepared by adding 3 to 1000 mm4 of oxalate to a Qwt% acid composition solution.
鋼材を炉冷室において炉冷し、次いで１ノン酸、水溶性
溶剤及びキｖ−）剤を含み、リン酸濃度を０．０５〜５
．Ｑｗｔ％とした酸組成物溶液にシュウ酸塩を添加した
処理液によって上記鋼材を急冷し、この後塗装下地とし
ての化成皮膜を鋼材表面に形成するようにした鋼材の塗
装前処理方法。(2) Steel materials that have been subjected to high heat treatment in a heating furnace in a non-oxidizing atmosphere are cooled in a furnace cold room, and then treated with a phosphoric acid concentration of 0.05 to 5, containing a non-oxidizing acid, a water-soluble solvent and a chemical agent.
．． A method for pre-painting a steel material, which comprises rapidly cooling the steel material with a treatment solution prepared by adding oxalate to an acid composition solution adjusted to Qwt%, and then forming a chemical conversion film on the surface of the steel material as a base for painting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14596681A JPS6036474B2 (en) | 1981-09-14 | 1981-09-14 | Pre-painting treatment agent and method for steel materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14596681A JPS6036474B2 (en) | 1981-09-14 | 1981-09-14 | Pre-painting treatment agent and method for steel materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5848678A true JPS5848678A (en) | 1983-03-22 |
| JPS6036474B2 JPS6036474B2 (en) | 1985-08-20 |
Family
ID=15397118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14596681A Expired JPS6036474B2 (en) | 1981-09-14 | 1981-09-14 | Pre-painting treatment agent and method for steel materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6036474B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016198934A (en) * | 2015-04-09 | 2016-12-01 | 新日鐵住金株式会社 | Polyolefin coated steel material subjected to base chemical conversion treatment |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03122186U (en) * | 1990-03-23 | 1991-12-13 |
-
1981
- 1981-09-14 JP JP14596681A patent/JPS6036474B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016198934A (en) * | 2015-04-09 | 2016-12-01 | 新日鐵住金株式会社 | Polyolefin coated steel material subjected to base chemical conversion treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6036474B2 (en) | 1985-08-20 |
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