JPH0812994A - Detergent composition for removing chemical conversion coating - Google Patents
Detergent composition for removing chemical conversion coatingInfo
- Publication number
- JPH0812994A JPH0812994A JP15132994A JP15132994A JPH0812994A JP H0812994 A JPH0812994 A JP H0812994A JP 15132994 A JP15132994 A JP 15132994A JP 15132994 A JP15132994 A JP 15132994A JP H0812994 A JPH0812994 A JP H0812994A
- Authority
- JP
- Japan
- Prior art keywords
- chemical conversion
- weight
- parts
- conversion film
- composition
- 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
Landscapes
- Detergent Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高強度鋼の遅れ破壊防
止に関し、特に高強度鋼材の冷間加工のために施す化成
被膜を除去する洗浄組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the prevention of delayed fracture of high strength steel, and more particularly to a cleaning composition for removing a conversion coating applied for cold working of high strength steel.
【０００２】[0002]
【従来の技術】最近、鋼素材に対して高品質化の要求が
強く、部品等の軽量化を可能にする高強度鋼材の需要が
高まっている。特に、自動車産業において、自動車の軽
量化やエンジンの高出力化が進み、締結部品としての高
強度ボルト、ねじ等が要求される。同様に、航空機部
品、橋梁用部品としてのこれらのボルトに対する関心も
高まっている。高強度ボルトの素材は、ＳＣＭ４３５
Ｈ、ＳＣＭ４４０Ｈ、ＭｎＢ１２５ＨおよびＡＳＭｎＢ
４２２Ｈ等の鋼種であるが、これらの素材はボルトに加
工した後、遅れ破壊を起こすことがしばしばある。この
遅れ破壊は、静的破壊とも呼ばれ、静的な引張応力状態
下に置かれた鋼部材が一定時間（たとえば、数分〜数
年）経過後に突然脆性的に破壊することである。2. Description of the Related Art Recently, there is a strong demand for higher quality steel materials, and there is an increasing demand for high-strength steel materials that enable weight reduction of parts and the like. In particular, in the automobile industry, the weight of automobiles and the output of engines are increasing, and high-strength bolts, screws and the like as fastening parts are required. Similarly, there is increasing interest in these bolts as aircraft parts and bridge parts. The material of high strength bolt is SCM435
H, SCM440H, MnB125H and ASMnB
Although it is a steel type such as 422H, these materials often cause delayed fracture after being processed into bolts. This delayed fracture is also called static fracture, and is a sudden brittle fracture of a steel member placed under static tensile stress after a certain period of time (for example, several minutes to several years).
【０００３】遅れ破壊の原因としては、現在までにいろ
いろ知られているが、浸りんもその要因である。浸りん
現象が、高強度ボルトの靭性を阻害するとしてＩＳＯ
（国際標準化機構）で取上げられ、ＩＳＯ８９８−１：
１９８８においては、強度区分１２．９のボルトで「引
張応力が存在する場所では、りんの濃化層があってはな
らない。」と規定されている。また、１９９０年のＪＩ
Ｓ Ｂ １０５１（鋼製のボルト、小ねじの機械的性質）
でもこの項目が追加されている。すなわち、これらの高
強度鋼部材においては、浸りんの存在が禁止されている
わけである。Various causes of delayed fracture have been known up to now, and phosphorus is also a factor. According to ISO, the phosphorus immersion phenomenon impairs the toughness of high strength bolts.
(International Organization for Standardization) ISO 898-1:
In 1988, bolts of strength class 12.9 are specified as "There should be no phosphorus enriched layer in the place where tensile stress exists". Also, JI of 1990
SB 1051 (Mechanical properties of steel bolts and machine screws)
But this item is added. That is, the presence of phosphorus is prohibited in these high strength steel members.
【０００４】この浸りんは、たとえば、ボルト製造工程
中、熱処理（焼入れ、焼戻し）前に行う冷間加工時に施
す化成被膜処理が原因と考えられている。化成被膜は、
冷間鋳造材の潤滑として用いられ、主として油脂分、金
属石鹸等の潤滑剤の下地処理の役割を果す。代表的な化
成被膜は、リン酸亜鉛被膜（ボンデライトとも呼ぶ）あ
るいはリン酸亜鉛カルシウム被膜である。It is considered that this phosphorus immersion is caused by, for example, a chemical conversion coating treatment performed during cold working performed before a heat treatment (quenching and tempering) during a bolt manufacturing process. The conversion coating is
It is used as a lubricant for cold cast materials and mainly plays a role of ground treatment for lubricants such as oil and fat and metal soap. A typical conversion coating is a zinc phosphate coating (also called bondellite) or a zinc calcium phosphate coating.
【０００５】鋼材表面にこれらの被膜が残留した状態
で、後工程の熱処理を行うと、りんは粒界より侵入し、
その後粒内に至り、鋼材中の炭素を押し退けて表面にフ
ェライト層を形成する。When a heat treatment in a later step is carried out with these films remaining on the surface of the steel material, phosphorus penetrates from the grain boundaries,
After that, it reaches the inside of the grain and pushes away carbon in the steel material to form a ferrite layer on the surface.
【０００６】浸りんを防止するために、りんを含有しな
い潤滑剤たとえば、石灰系、蓚酸塩系潤滑剤の使用が有
効であると知られている。しかし、これらの潤滑剤は、
従来のリン酸被膜より潤滑能および防錆性等が劣る。It is known that the use of a phosphorus-free lubricant, for example, a lime-based or oxalate-based lubricant, is effective for preventing phosphorus infiltration. However, these lubricants
Inferior to conventional phosphoric acid coatings in lubricity and rust resistance.
【０００７】このような状況に対して、従来より冶金的
な方法で浸りんを防止する方法が幾多検討されてきた。
たとえば、製鋼時に炉外精錬を行い、りんの含有量を
０．０１％以下に制御する方法が知られている。また、
特開平３−２４３７２１は化成被膜処理したボルトを冷
間成形し、酸化雰囲気下で特定条件の中間熱処理を行っ
た後、焼入れ焼戻し処理することにより、耐遅れ破壊性
の向上を図る方法を開示する。同様な手法で、冷間成形
したボルトを特定温度域まで急速加熱し、かつ特定時間
内に焼入れ処理を行うことにより、浸りんを防止してボ
ルトの耐遅れ破壊性を向上する方法が、特開平３−２４
３７２２に開示されている。このような冶金的な方法
（バーニングとも呼ばれる）は、一般に焼入れ温度が高
ければ浸りんを生じ、低ければ充分に化成皮膜を除去で
きない等、制御上の問題がある。[0007] In order to deal with such a situation, a number of methods for preventing phosphorus immersion by metallurgical methods have hitherto been studied.
For example, a method is known in which refining is performed outside the furnace during steelmaking to control the phosphorus content to 0.01% or less. Also,
Japanese Unexamined Patent Publication (Kokai) No. 3-243721 discloses a method for improving delayed fracture resistance by cold forming a chemical conversion coating treated bolt, performing intermediate heat treatment under specific conditions in an oxidizing atmosphere, and then performing quenching and tempering treatment. . In the same way, cold-formed bolts are rapidly heated to a specified temperature range and quenched within a specified time to prevent phosphorus infiltration and improve the delayed fracture resistance of the bolts. Kaihei 3-24
3722. Such a metallurgical method (also referred to as burning) generally has a control problem such that phosphorus is soaked if the quenching temperature is high, and the chemical conversion film cannot be sufficiently removed if the quenching temperature is low.
【０００８】一方、化学洗浄剤（ケミカルクリーナ）に
より鋼材表面の化成被膜を除去する方法も提案されてい
る。典型的には、洗浄剤は、酸あるいはアルカリ溶液か
ら成る。酸液による洗浄は、被膜が完全に除去できる反
面、水素イオンが残留し、水素が鋼材中に侵入、水素起
因の脆化を招く恐れがある。また、アルカリ液による洗
浄は、前記油脂分や金属石鹸が除去され、一見清浄な外
観となるが、化成被膜そのものは取除かれない。その他
に、重クロム酸（酸洗浄）およびエタノールアミン（ア
ルカリ洗浄）は、残留毒性の点から排水規制により使用
が望ましくない。このように、現在知られている化学洗
浄剤（方法）は、洗浄効果、使用制限等に問題があり、
あまり満足なものとは言えない。On the other hand, a method of removing the chemical conversion film on the surface of the steel material by a chemical cleaner has been proposed. Typically, the cleaning agent comprises an acid or alkaline solution. The cleaning with an acid solution may completely remove the coating film, but hydrogen ions may remain and hydrogen may penetrate into the steel material, causing embrittlement due to hydrogen. In addition, washing with an alkaline liquid removes the oil and fat and the metallic soap to give a seemingly clean appearance, but does not remove the chemical conversion coating itself. In addition, dichromic acid (acid cleaning) and ethanolamine (alkaline cleaning) are not recommended due to wastewater regulations due to residual toxicity. As described above, the currently known chemical cleaning agents (methods) have problems in cleaning effect, use limitation, etc.
It's not very satisfying.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、前記の問題
点に鑑みてなされたものであり、鋼部材表面に施工され
た化成被膜を、効率よく除去し、浸りんによる遅れ破壊
を防ぎ、しかも洗浄後洗浄対象鋼部材に残留しても、二
次的な遅れ破壊を誘起しない化成被膜除去用洗浄組成物
を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and efficiently removes a chemical conversion coating applied to the surface of a steel member to prevent delayed fracture due to phosphorus immersion. Moreover, it is an object of the present invention to provide a cleaning composition for removing a chemical conversion film, which does not induce secondary delayed fracture even if it remains on the steel member to be cleaned after cleaning.
【００１０】[0010]
【課題を解決するための手段】本発明は、キレート剤と
非イオン性界面活性剤と、残部に水とを含有して成る化
成被膜除去用洗浄組成物を要旨とする。キレート剤およ
び非イオン性界面活性剤が相乗的に働き、優れた洗浄効
果を発揮し、浸りんを防ぎ、本発明の目的を達成するこ
とができる。DISCLOSURE OF THE INVENTION The gist of the present invention is a cleaning composition for removing a chemical conversion film, which comprises a chelating agent, a nonionic surfactant, and the balance water. The chelating agent and the nonionic surfactant act synergistically to exert an excellent cleaning effect, prevent phosphorus immersion, and achieve the object of the present invention.
【００１１】本発明によれば、キレート剤を２〜２０重
量部と、非イオン性界面活性剤を５〜４０重量部と、お
よび残部に水とを含有して成る化成被膜除去用洗浄組成
物が提供される。According to the present invention, a cleaning composition for removing a chemical conversion coating, containing 2 to 20 parts by weight of a chelating agent, 5 to 40 parts by weight of a nonionic surfactant, and water as the balance. Will be provided.
【００１２】さらに本発明によれば、キレート剤を２〜
２０重量部と、非イオン性界面活性剤を５〜４０重量部
と、防食剤を０．１〜５重量部と、および残部に水とを
含有して成る化成被膜除去用洗浄組成物も提供される。Furthermore, according to the present invention, a chelating agent is added to
Also provided is a cleaning composition for removing a chemical conversion film, which comprises 20 parts by weight, 5 to 40 parts by weight of a nonionic surfactant, 0.1 to 5 parts by weight of an anticorrosive agent, and water as the balance. To be done.
【００１３】本発明の一態様によれば、前記キレート剤
はオキシカルボン酸類、アミノカルボン酸類、およびア
ミノホスホン酸類から成る群より選ばれる１種または２
種以上の化合物である化成被膜除去用洗浄組成物が提供
される。According to one embodiment of the present invention, the chelating agent is one or two selected from the group consisting of oxycarboxylic acids, aminocarboxylic acids, and aminophosphonic acids.
There is provided a conversion coating removal cleaning composition that is one or more compounds.
【００１４】本発明の別の態様によれば、前記非イオン
性界面活性剤がポリオキシエチレンアルキルエーテル
類、ポリオキシエチレンアルキルフェノールエーテル
類、ソルビタン脂肪酸エステル類、およびエチレンプロ
ピレンブロックポリマー類から成る群より選ばれる１種
または２種以上の化合物である化成被膜除去用洗浄組成
物が提供される。According to another aspect of the present invention, the nonionic surfactant is selected from the group consisting of polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, sorbitan fatty acid esters, and ethylene propylene block polymers. Provided is a cleaning composition for removing a chemical conversion film, which is one or more selected compounds.
【００１５】本発明の別の態様によれば、前記非イオン
性界面活性剤が次式 Ｒ1 −０−（ＣＨ2ＣＨ2Ｏ）n Ｈ …（１） （式中、Ｒ1 は炭素数が８〜１２の分岐していてもよい
アルキル基、そしてｎは７〜１２の整数を示す。）で表
される化合物である化成被膜除去用洗浄組成物が提供さ
れる。According to another aspect of the present invention, the in non-ionic surfactant is the formula R 1 -0- (CH 2 CH 2 O) n H ... (1) ( wherein, R 1 is the number of carbon atoms Is an optionally branched alkyl group of 8 to 12, and n is an integer of 7 to 12).
【００１６】本発明の別の態様によれば、前記非イオン
性界面活性剤が次式 Ｒ2 −Ｃ6Ｈ4 −Ｏ−（ＣＨ2ＣＨ2Ｏ）n Ｈ …（２） （式中、Ｒ2 は炭素数８〜９の直鎖状のアルキル基であ
り、そしてｎは７〜１２の整数を示す。）で表される化
合物である化成被膜除去用洗浄組成物を提供する。According to another aspect of the present invention, the nonionic surfactant is represented by the following formula R 2 —C 6 H 4 —O— (CH 2 CH 2 O) n H (2) R 2 is a linear alkyl group having 8 to 9 carbon atoms, and n is an integer of 7 to 12).
【００１７】本発明のさらに別の態様によれば、ｐＨが
５〜１０である化成被膜除去用洗浄組成物も提供され
る。According to still another aspect of the present invention, there is also provided a cleaning composition for removing a chemical conversion film having a pH of 5-10.
【００１８】[0018]
【作用】本発明者は、キレート剤の金属取り込み能力
と、非イオン性界面活性剤の洗浄能力に注目して、鋭意
研究を重ねた結果、本発明の組成物を見つけた。The present inventor has found the composition of the present invention as a result of intensive studies by paying attention to the ability of the chelating agent to take up the metal and the washing ability of the nonionic surfactant.
【００１９】以下、本発明をさらに詳しく説明する。The present invention will be described in more detail below.
【００２０】本発明で使用できるキレート剤は、代表的
には、オキシカルボン酸類、アミノカルボン酸類、およ
びアミノホスホン酸類などが挙げられる。オキシカルボ
ン酸類には、たとえば、クエン酸、グルコン酸、ヒドロ
キシ酢酸、リンゴ酸、マロン酸、酒石酸などが含まれ
る。アミノカルボン酸類には、エチレンジアミン四酢酸
（ＥＤＴＡ）、ニトリロ三酢酸（ＮＴＡ）、ジエチレン
ポリアミンペンタ酢酸、ヒドロキシエチレンジアミンポ
リ酢酸、イミノジ酢酸（ＩＤＡ）などが含まれる。アミ
ノホスホン酸類には、１−ヒドロキシエチリデン−１，
１ジホスホン酸などが含まれる。これらの群から適当な
キレート剤を１種または２種以上組合わせて使用するこ
とができる。Typical examples of the chelating agent usable in the present invention include oxycarboxylic acids, aminocarboxylic acids, and aminophosphonic acids. Oxycarboxylic acids include, for example, citric acid, gluconic acid, hydroxyacetic acid, malic acid, malonic acid, tartaric acid and the like. Aminocarboxylic acids include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenepolyaminepentaacetic acid, hydroxyethylenediaminepolyacetic acid, iminodiacetic acid (IDA), and the like. Aminophosphonic acids include 1-hydroxyethylidene-1,
1 Diphosphonic acid and the like are included. Suitable chelating agents from these groups may be used alone or in combination of two or more.
【００２１】オキシカルボン酸類では、グリコール酸が
特に好ましい。アミノカルボン酸類では、エチレンジア
ミン四酢酸が特に好ましい。アミノホスホン酸類では、
１−ヒドロキシエチリデン−１，１ジホスホン酸が特に
好ましい。Among the oxycarboxylic acids, glycolic acid is particularly preferable. Among the aminocarboxylic acids, ethylenediaminetetraacetic acid is particularly preferable. In aminophosphonic acids,
1-Hydroxyethylidene-1,1 diphosphonic acid is particularly preferred.
【００２２】本発明の組成物中、キレート剤は組成物全
量に対して２〜２０重量部存在することが好ましく、５
〜１５重量部であることが特に好ましい。キレート剤が
２重量部未満の場合は、所望のキレート効果が得られな
い。また、２０重量部以上の場合はキレート効果が向上
せず、使用量を増やすことは経済的でない。In the composition of the present invention, the chelating agent is preferably present in an amount of 2 to 20 parts by weight based on the total amount of the composition.
It is particularly preferable that the amount is ˜15 parts by weight. If the amount of the chelating agent is less than 2 parts by weight, the desired chelating effect cannot be obtained. Further, if it is 20 parts by weight or more, the chelating effect is not improved, and it is not economical to increase the amount used.
【００２３】本発明で使用できる非イオン性界面活性剤
としては、ポリオキシエチレンアルキルエーテル類、ポ
リオキシエチレンアルキルフェノールエーテル類、ソル
ビタン脂肪酸エステル類およびエチレンプロピレンブロ
ックポリマー類などが挙げられる。ポリオキシエチレン
アルキルエーテル類に属する非イオン性界面活性剤とし
ては、式（１）で表される高級アルコールのエトキシレ
ートが含まれる。式（１）では、ポリオキシエチレンオ
クチルエーテル（式中ｎ＝７）、ポリオキシエチレンラ
ウリルエーテル（式中ｎ＝９）、そしてポリオキシエチ
レンイソオクチルエーテル（式中ｎ＝７）が好ましい。
ポリオキシエチレンアルキルフェノールエーテル類に属
する非イオン性界面活性剤としては、式（２）で表され
るアルキルフェノール化合物がある。式（２）では、ポ
リオキシエチレンオクチルフェニルエーテル（式中ｎ＝
８）、ポリオキシエチレンノニルフェニルエーテル（式
中ｎ＝１０）が好ましい。非イオン性界面活性剤は、前
記のような群から選択される１種または２種以上の組合
わせを使用する。特に、好適な非イオン性界面活性剤と
しては、浸水性／親油性を示す指標であるＨＬＢ値が１
０〜１３の範囲内にあることが望ましい。Examples of the nonionic surfactant that can be used in the present invention include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, sorbitan fatty acid esters and ethylene propylene block polymers. Nonionic surfactants belonging to the polyoxyethylene alkyl ethers include ethoxylates of higher alcohols represented by formula (1). In the formula (1), polyoxyethylene octyl ether (n = 7 in the formula), polyoxyethylene lauryl ether (n = 9 in the formula), and polyoxyethylene isooctyl ether (n = 7) are preferable.
As the nonionic surfactant belonging to the polyoxyethylene alkylphenol ethers, there is an alkylphenol compound represented by the formula (2). In the formula (2), polyoxyethylene octyl phenyl ether (where n =
8) and polyoxyethylene nonylphenyl ether (n = 10 in the formula) are preferable. As the nonionic surfactant, one kind or a combination of two or more kinds selected from the above group is used. Particularly, a suitable nonionic surfactant has an HLB value of 1 which is an index showing water-immersion / lipophilicity.
It is desirable to be in the range of 0 to 13.
【００２４】本発明の組成物中、組成物全量に対して非
イオン性界面活性剤は、４〜４０重量部存在することが
好ましく、７〜３０重量部であることが特に好ましい。
５重量部未満の場合は、所望の洗浄効果を得ることが難
しく、また４０重量部以上ではキレート剤と混合したと
き分離、乳濁を生ずるため、好ましくない。In the composition of the present invention, the nonionic surfactant is preferably present in an amount of 4 to 40 parts by weight, particularly preferably 7 to 30 parts by weight, based on the total amount of the composition.
If it is less than 5 parts by weight, it is difficult to obtain a desired cleaning effect, and if it is 40 parts by weight or more, separation and emulsion will occur when mixed with a chelating agent, which is not preferable.
【００２５】本発明の特に好適な組成物は、キレート剤
としてエチレンジアミン四酢酸、グリコール酸、および
１−ヒドロキシエチリデンー１，１ジホスホン酸から成
る群より選ばれる１種または２種以上の化合物と、非イ
オン性界面活性剤としてポリオキシエチレンオクチルエ
ーテル、ポリオキシエチレンラウリルエーテル、および
ポリオキシエチレンノニルフェニルエーテルから成る群
より選ばれる１種または２種以上の化合物とそして水と
を含有して成る。化成被膜洗浄能が極めて高い具体的な
組成物は、キレート剤としてエチレンジアミン四酢酸
と、非イオン性界面活性剤としてポリオキシエチレンオ
クチルエーテルおよび水とを含有して成る。別の具体的
な組成物は、キレート剤として１ーヒドロキシエチリデ
ンー１，１ジホスホン酸および／またはエチレンジアミ
ン四酢酸と、非イオン性界面活性剤としてポリオキシエ
チレンノニルフェニルエーテルと、そして水とを含有し
て成る。A particularly preferred composition of the present invention is one or more compounds selected from the group consisting of ethylenediaminetetraacetic acid, glycolic acid, and 1-hydroxyethylidene-1,1 diphosphonic acid as a chelating agent, It comprises one or more compounds selected from the group consisting of polyoxyethylene octyl ether, polyoxyethylene lauryl ether, and polyoxyethylene nonylphenyl ether as a nonionic surfactant, and water. A specific composition having a very high conversion film cleaning ability comprises ethylenediaminetetraacetic acid as a chelating agent, polyoxyethylene octyl ether and water as a nonionic surfactant. Another specific composition contains 1-hydroxyethylidene-1,1 diphosphonic acid and / or ethylenediaminetetraacetic acid as a chelating agent, polyoxyethylene nonylphenyl ether as a nonionic surfactant, and water. It will be done.
【００２６】対象鋼部材が洗浄液によって腐食され易い
ものである場合は、前記組成物に腐食を防止する防食剤
を添加することが望ましい。防食剤を添加した化成被膜
除去用洗浄組成物も、本発明の技術範囲に含まれる。使
用できる適当な防食剤としては、ベンゾトリアゾール、
セバシン酸ソーダ、ジアルケニルコハク酸ソーダなどが
挙げられる。前記の本発明の組成物に、これらの防食剤
を１種または２種以上添加使用することができる。防食
剤の使用量は、組成物１００重量部に対して０．１〜５
重量部が好ましく、特に１〜２重量部であることが好ま
しい。添加量が０．１重量部未満では、所望の防食効果
が得られず、また添加量が５重量部以上では組成物の洗
浄能力を著しく低下させるため、好ましくない。本発明
の組成剤に、さらに必要に応じて、他の付加成分たとえ
ば補助溶剤、希釈剤、消泡剤等を添加することができ
る。これらは、当業者に公知の化合物から選ぶことがで
きる。しかしながら、添加する付加成分は、組成物の洗
浄効果、あるいは防食効果に悪影響を及ぼさないものを
選択するべきである。When the subject steel member is liable to be corroded by the cleaning liquid, it is desirable to add an anticorrosive agent for preventing corrosion to the composition. A cleaning composition for removing a chemical conversion film containing an anticorrosive agent is also included in the technical scope of the present invention. Suitable anticorrosion agents that can be used include benzotriazole,
Examples thereof include sodium sebacate and sodium dialkenyl succinate. One or more of these anticorrosive agents may be added to the composition of the present invention. The amount of the anticorrosive agent used is 0.1-5 with respect to 100 parts by weight of the composition.
It is preferably part by weight, and particularly preferably 1 to 2 parts by weight. If the added amount is less than 0.1 parts by weight, the desired anticorrosive effect cannot be obtained, and if the added amount is 5 parts by weight or more, the cleaning ability of the composition is significantly reduced, which is not preferable. If necessary, other additional components such as a cosolvent, a diluent and an antifoaming agent can be added to the composition of the present invention. These can be selected from compounds known to those skilled in the art. However, the additive component to be added should be selected so as not to adversely affect the cleaning effect or anticorrosion effect of the composition.
【００２７】本発明の組成物のｐＨは、５〜１０に調整
されることが望ましい。特に好ましいｐＨの範囲は、６
〜８の中性領域である。組成物のｐＨを前記の範囲に調
整するには、適当な中和剤を組成物に添加して行う。使
用される中和剤は、前記のキレート剤としての各種遊離
酸と反応するのみではなく、組成物を希釈して使用する
場合の緩衝剤として有用である。さらに、ｐＨを非酸性
領域に調節することは洗浄後水素イオンを鋼材中に残留
させないためにも必要である。使用できる適当な中和剤
としては、苛性ソーダ、苛性カリ、アンモニア、エタノ
ールアミン等が例示される。しかしながら、前述のよう
に排水規制の観点から、苛性ソーダまたは苛性カリを用
いることが好ましい。The pH of the composition of the present invention is preferably adjusted to 5-10. A particularly preferred pH range is 6
~ 8 neutral region. The pH of the composition is adjusted to the above range by adding an appropriate neutralizing agent to the composition. The neutralizing agent used not only reacts with the various free acids as the chelating agent, but is also useful as a buffering agent when the composition is diluted and used. Furthermore, adjusting the pH to a non-acidic region is necessary to prevent hydrogen ions from remaining in the steel product after cleaning. Examples of suitable neutralizing agents that can be used include sodium hydroxide, potassium hydroxide, ammonia, ethanolamine and the like. However, as described above, it is preferable to use caustic soda or caustic potash from the viewpoint of drainage regulation.
【００２８】本発明の組成物は、高強度鋼部材（特にボ
ルトおよびねじ）のリン酸塩被膜を洗浄除去するのに特
に有効であるが、その他の鋼部材の化成被膜の除去にも
適用できる。The composition of the present invention is particularly effective for cleaning away phosphate coatings on high strength steel components (particularly bolts and screws), but is also applicable to removing conversion coatings on other steel components. .
【００２９】以下、実施例、比較例および評価試験によ
り本発明を詳細に説明するが、これらは本発明の技術範
囲を限定するものとみなすべきではない。Hereinafter, the present invention will be described in detail with reference to Examples, Comparative Examples and evaluation tests, but these should not be regarded as limiting the technical scope of the present invention.
【００３０】[0030]
（実施例１）エチレンジアミン四酢酸（キレート剤）５
重量部、ポリオキシエチレンオクチルエーテル（非イオ
ン性界面活性剤）７重量部および水残部を混合し、１０
０重量部とした。これに苛性ソーダ若干量を添加し、混
合物のｐＨを約７．０に調整し、本発明の化成被膜除去
用洗浄組成物を得た。Example 1 Ethylenediaminetetraacetic acid (chelating agent) 5
10 parts by weight, 7 parts by weight of polyoxyethylene octyl ether (nonionic surfactant) and the balance of water are mixed to obtain 10 parts by weight.
It was 0 part by weight. A small amount of caustic soda was added to the mixture to adjust the pH of the mixture to about 7.0 to obtain the cleaning composition for removing a chemical conversion film of the present invention.
【００３１】（実施例２）エチレンジアミン四酢酸（キ
レート剤）７重量部、ポリオキシエチレンオクチルエー
テル（非イオン性界面活性剤）３０重量部、ベンゾトリ
アゾール（防食剤）２部および水残部を混合し、１００
重量部とした。これに苛性ソーダ若干量を添加し、混合
物のｐＨを約７．０に調整し、本発明の化成被膜除去用
洗浄組成物を得た。Example 2 7 parts by weight of ethylenediaminetetraacetic acid (chelating agent), 30 parts by weight of polyoxyethylene octyl ether (nonionic surfactant), 2 parts of benzotriazole (anticorrosive agent) and the balance of water were mixed. , 100
It was made into a weight part. A small amount of caustic soda was added to the mixture to adjust the pH of the mixture to about 7.0 to obtain the cleaning composition for removing a chemical conversion film of the present invention.
【００３２】（実施例３〜６）実施例１あるいは実施例
２と同様にして、所定の重量部で各成分を混合し、ｐＨ
を約７．０に調整して、下記（表１）に示す組成を有す
る本発明の化成被膜除去用洗浄組成物を得た。(Examples 3 to 6) In the same manner as in Example 1 or 2, the respective components were mixed in predetermined weight parts and pH was adjusted.
Was adjusted to about 7.0 to obtain a cleaning composition for removing a chemical conversion film of the present invention having the composition shown in (Table 1) below.
【００３３】（比較例１〜３）実施例と同様にして、所
定の重量部で各成分を混合し、ｐＨを約７．０に調整し
て、表１に示す組成を有する洗浄組成物を得た。(Comparative Examples 1 to 3) In the same manner as in Examples, the respective components were mixed in predetermined weight parts and the pH was adjusted to about 7.0 to obtain cleaning compositions having the compositions shown in Table 1. Obtained.
【００３４】[0034]
【表１】 [Table 1]
【００３５】表中、前述のとおり、実施例、比較例の各
例の組成分ともＡ．Ｂ．Ｃ．成分以外の残部は水で、合
計１００重量部である。In the table, as described above, the composition of each of the examples and comparative examples was B. C. The balance other than the components is water, which is 100 parts by weight in total.
【００３６】評価試験 化成被膜加工（リン酸亜鉛被膜）した高強度ボルト（Ｊ
ＩＳ ＳＣＭ ４３５Ｈ）を試験材料として、実施例の組
成物および比較例の組成物で洗浄を行った。洗浄効果を
被膜除去性（％）で評価した。さらに、洗浄後のボルト
の遅れ破壊性を調べ、併せて洗浄による浸りんの防止度
を評価した。 Evaluation test High strength bolts (J-phosphate coating) with chemical conversion coating (J
Using IS SCM 435H) as a test material, cleaning was performed with the composition of the example and the composition of the comparative example. The cleaning effect was evaluated by the film removing property (%). Furthermore, the delayed fracture property of the bolt after cleaning was examined, and the degree of prevention of phosphorus immersion by cleaning was also evaluated.
【００３７】（１）化成被膜除去試験 試験条件は、次のとおりである。(1) Chemical conversion film removal test The test conditions are as follows.
【００３８】先ず、アセトンで脱脂、乾燥した試験材料
の重量（Ｗ１）を測った。次に、同様に脱脂処理した材
料を６％重クロム酸水溶液中に室温で３０分間浸漬した
後、水洗、乾燥した材料の重量（Ｗ２）を測った。さら
に、脱脂処理した試験材料を６０℃に加熱した１０％洗
浄剤水溶液中に１０分間浸漬した後、水洗、乾燥した材
料の重量（Ｗ３）を測った。First, the weight (W1) of the test material degreased with acetone and dried was measured. Next, the material degreased in the same manner was immersed in a 6% dichromic acid aqueous solution at room temperature for 30 minutes, washed with water, and the weight (W2) of the dried material was measured. Further, the degreased test material was immersed in an aqueous 10% detergent solution heated to 60 ° C. for 10 minutes, washed with water, and the weight (W3) of the dried material was measured.
【００３９】被膜の除去率は、次式により求めた。The removal rate of the film was obtained by the following equation.
【００４０】[0040]
【数１】 [Equation 1]
【００４１】（２）遅れ破壊性試験 洗浄後熱処理した試験材料１０本を１組とし、５％塩酸
に３０分間浸漬後、降伏点まで締めつけ２４時間放置し
て、破壊（遅れ）された本数を数えた。(2) Delayed Fracture Test Using 10 test materials after heat treatment after washing as one set, after soaking in 5% hydrochloric acid for 30 minutes, tightening to the yield point and leaving for 24 hours, the number of fractured (delayed) samples I counted.
【００４２】評価試験の結果を表２に示す。The results of the evaluation test are shown in Table 2.
【００４３】[0043]
【表２】 [Table 2]
【００４４】表２の結果から、本発明の組成物は、空試
験、比較例の組成物に比較して、化成被膜の除去率が著
しく高く、遅れ破壊を皆無にすることが明らかになっ
た。From the results shown in Table 2, it is clear that the composition of the present invention has a significantly higher conversion conversion film removal rate than the compositions of the blank test and the comparative example, and eliminates delayed fracture. .
【００４５】[0045]
【発明の効果】本発明の化成被膜除去用組成物は、高強
度鋼部材の化成被膜を効率よく除去し、浸りんを防止す
るので、鋼材表面にフェライト層の形成が抑制され、そ
の結果遅れ破壊を皆無とするので、その利用は鋼加工業
界において極めて価値が高い。The composition for removing a chemical conversion film of the present invention efficiently removes the chemical conversion film of a high-strength steel member and prevents phosphorus infiltration, so that the formation of a ferrite layer on the surface of the steel material is suppressed, resulting in a delay. Its use is extremely valuable in the steel processing industry as it eliminates any destruction.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藪地 利夫 東京都中央区日本橋小伝馬町16番８号 朝 日化学工業株式会社東京事務所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Yabuchi 16-8 Nihonbashi Kodenmacho, Chuo-ku, Tokyo Asahi Chemical Industry Co., Ltd. Tokyo Office
Claims (7)
ン性界面活性剤を５〜４０重量部と、および残部に水と
を含有して成る化成被膜除去用洗浄組成物。1. A cleaning composition for removing a chemical conversion film, comprising 2 to 20 parts by weight of a chelating agent, 5 to 40 parts by weight of a nonionic surfactant, and the balance water.
ノカルボン酸類、およびアミノホスホン酸類から成る群
より選ばれる１種または２種以上の化合物である請求項
１記載の化成被膜除去用洗浄組成物。2. The cleaning composition for removing a chemical conversion film according to claim 1, wherein the chelating agent is one or more compounds selected from the group consisting of oxycarboxylic acids, aminocarboxylic acids, and aminophosphonic acids.
レンアルキルエーテル類、ポリオキシエチレンアルキル
フェノールエーテル類、ソルビタン脂肪酸エステル類、
およびエチレンプロピレンブロックポリマー類から成る
群より選ばれる１種または２種以上の化合物である請求
項１記載の化成被膜除去用洗浄組成物。3. The nonionic surfactant is polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, sorbitan fatty acid esters,
The cleaning composition for removing a chemical conversion film according to claim 1, which is one or more compounds selected from the group consisting of and ethylene propylene block polymers.
アルキル基、そしてｎは７〜１２の整数を示す。）で表
される化合物である請求項１記載の化成被膜除去用洗浄
組成物。Wherein in the nonionic surfactant has the formula R 1 -0- (CH 2 CH 2 O) n H ... (1) ( wherein, R 1 is be branched carbon atoms of 8 to 12 A good alkyl group, and n represents an integer of 7 to 12). The cleaning composition for removing a chemical conversion film according to claim 1.
り、そしてｎは７〜１２の整数を示す。）で表される化
合物である請求項１記載の化成被膜除去用洗浄組成物。5. The nonionic surfactant has the formula R 2 —C 6 H 4 —O— (CH 2 CH 2 O) n H (2) (wherein R 2 is a straight chain having 8 to 9 carbon atoms). The cleaning composition for removing a chemical conversion film according to claim 1, which is a compound represented by a chain-like alkyl group, and n represents an integer of 7 to 12.
ン性界面活性剤を５〜４０重量部と、防食剤を０．１〜
５重量部と、および残部に水とを含有して成る化成被膜
除去用洗浄組成物。6. A chelating agent in an amount of 2 to 20 parts by weight, a nonionic surfactant in an amount of 5 to 40 parts by weight, and an anticorrosive agent in an amount of 0.1 to 20 parts by weight.
A cleaning composition for removing a chemical conversion film, which comprises 5 parts by weight and the balance water.
〜６のいずれかに記載の化成被膜除去用洗浄組成物。7. The composition has a pH of 5 to 10.
A cleaning composition for removing a chemical conversion film according to any one of to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15132994A JP3478870B2 (en) | 1994-07-01 | 1994-07-01 | Cleaning composition for removing phosphate film from high strength steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15132994A JP3478870B2 (en) | 1994-07-01 | 1994-07-01 | Cleaning composition for removing phosphate film from high strength steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0812994A true JPH0812994A (en) | 1996-01-16 |
| JP3478870B2 JP3478870B2 (en) | 2003-12-15 |
Family
ID=15516223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15132994A Expired - Lifetime JP3478870B2 (en) | 1994-07-01 | 1994-07-01 | Cleaning composition for removing phosphate film from high strength steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3478870B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10251697A (en) * | 1997-03-12 | 1998-09-22 | Daisan Kogyo Kk | Cleaner composition for light metal |
| JP2013532751A (en) * | 2010-07-23 | 2013-08-19 | アメリカン ステリライザー カンパニー | Biodegradable concentrated neutral detergent composition |
| CN103387797A (en) * | 2012-05-11 | 2013-11-13 | 天津博克尼科技发展有限公司 | Environmentally-friendly stainless steel tableware processing polishing solution |
| CN115595595A (en) * | 2022-10-24 | 2023-01-13 | 浙江康星科技有限公司（Cn） | Neutral rust remover and preparation method and application thereof |
-
1994
- 1994-07-01 JP JP15132994A patent/JP3478870B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10251697A (en) * | 1997-03-12 | 1998-09-22 | Daisan Kogyo Kk | Cleaner composition for light metal |
| JP2013532751A (en) * | 2010-07-23 | 2013-08-19 | アメリカン ステリライザー カンパニー | Biodegradable concentrated neutral detergent composition |
| CN103387797A (en) * | 2012-05-11 | 2013-11-13 | 天津博克尼科技发展有限公司 | Environmentally-friendly stainless steel tableware processing polishing solution |
| CN115595595A (en) * | 2022-10-24 | 2023-01-13 | 浙江康星科技有限公司（Cn） | Neutral rust remover and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3478870B2 (en) | 2003-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7151080B2 (en) | Composition for stripping coatings from substrates | |
| US11332667B2 (en) | Composition for washing pickled steel plate, method for washing pickled steel plate by using same, and steel plate obtained thereby | |
| US4437898A (en) | Method and agent for passivating iron and steel surfaces | |
| JPH02240286A (en) | Improved corrosionproof composition | |
| US4631139A (en) | Corrosion inhibiting metal working fluid | |
| EP2661518B1 (en) | Method of inhibiting vapor phase corrosion and staining on stainless steel | |
| US5429764A (en) | Liquid drain opener compositions based on sulfuric acid | |
| US5614028A (en) | Method of cleaning and passivating a metal surface with acidic system and ethoxylated tertiary dodecyl mercaptan | |
| JPH06192693A (en) | Aqueous detergent composition | |
| JP3478870B2 (en) | Cleaning composition for removing phosphate film from high strength steel | |
| US20080011323A1 (en) | Method For Removing Laser Scales | |
| CN115652321A (en) | Water-soluble efficient degreasing agent and preparation method thereof | |
| JP6731236B2 (en) | Descaling promoting additive for alloy steel, acid cleaning liquid composition containing the same, and acid cleaning method | |
| JPH11158492A (en) | Detergent composition for steel sheet surface | |
| JPH08311492A (en) | Aqueous detergent composition | |
| CN114657545A (en) | Ecological descaling type rapid sedimentation passivation solution and preparation process thereof | |
| CA1123719A (en) | Method of improving surface characteristic of heat-treated metal | |
| JP7183290B2 (en) | Surface treatment agent | |
| CA1135250A (en) | Metal coating process and compositions | |
| JPH02167398A (en) | Aqueous lubricant for plastic processing of metal material and treatment therefor | |
| JPH0711467A (en) | Surface treating agent and aqueous detergent-corrosion inhibitor for metallic material and treatment of surface | |
| JP7019224B1 (en) | Water-soluble rust inhibitor composition and its usage | |
| JP3364667B2 (en) | Composition for plating pretreatment | |
| US5441572A (en) | Ambient cleaners for aluminum | |
| KR970007569B1 (en) | Neutral detergent and its method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081003 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 5 Free format text: PAYMENT UNTIL: 20081003 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 6 Free format text: PAYMENT UNTIL: 20091003 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 6 Free format text: PAYMENT UNTIL: 20091003 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101003 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 7 Free format text: PAYMENT UNTIL: 20101003 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 8 Free format text: PAYMENT UNTIL: 20111003 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 8 Free format text: PAYMENT UNTIL: 20111003 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121003 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 9 Free format text: PAYMENT UNTIL: 20121003 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 10 Free format text: PAYMENT UNTIL: 20131003 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |