JP3222176B2 - Corrosion inhibitor composition, metal pickling liquid containing the same, and method for pickling metal - Google Patents
Corrosion inhibitor composition, metal pickling liquid containing the same, and method for pickling metalInfo
- Publication number
- JP3222176B2 JP3222176B2 JP04462992A JP4462992A JP3222176B2 JP 3222176 B2 JP3222176 B2 JP 3222176B2 JP 04462992 A JP04462992 A JP 04462992A JP 4462992 A JP4462992 A JP 4462992A JP 3222176 B2 JP3222176 B2 JP 3222176B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- general formula
- following general
- corrosion inhibitor
- pickling
- 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.)
- Expired - Lifetime
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
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、金属の表面に付着して
いる錆、熱延スケールなどの酸化物皮膜を除去するため
の酸洗液に添加する腐食抑制剤に関し、特に酸洗中の金
属素地の腐食を防止し、酸洗後の金属表面を改質するた
めの添加剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a corrosion inhibitor added to a pickling solution for removing oxide films such as rust and hot-rolled scale adhered to a metal surface, and more particularly to a corrosion inhibitor used during pickling. The present invention relates to an additive for preventing corrosion of a metal substrate and modifying a metal surface after pickling.
【0002】[0002]
【従来の技術】従来、金属の表面に付着している錆、熱
延スケールなどの酸化物皮膜を除去するために、塩酸、
硫酸などの無機酸や、シュウ酸、クエン酸などの有機酸
が使用されており、特に、製鉄所における熱延スケール
を除去するために一般には塩酸が使用されている。しか
し、酸単独ではスケールの除去だけでなく金属素地の溶
解が起こるため、通常これを防止する目的で、ポリエチ
レンイミンなどの有機ポリアミンが腐食抑制剤として使
用されている。2. Description of the Related Art Conventionally, in order to remove oxide films such as rust and hot-rolled scale adhered to metal surfaces, hydrochloric acid,
Inorganic acids such as sulfuric acid, and organic acids such as oxalic acid and citric acid are used. In particular, hydrochloric acid is generally used to remove hot-rolled scale in steel works. However, since the acid alone causes the dissolution of the metal base as well as the removal of scale, an organic polyamine such as polyethyleneimine is usually used as a corrosion inhibitor for the purpose of preventing this.
【0003】しかし、酸化物皮膜の割れや粒界析出物な
ど金属母材の不均一性や、酸洗液の濃度、流速の不均一
性や酸洗液中の第2鉄イオンなどの酸化性イオンの存在
などによって金属表面に孔食が発生する場合があり、そ
の結果酸洗後の金属表面の品質が低下して、冷延、メッ
キ、伸線などの後工程に悪影響を及ぼしており、このよ
うな孔食を防止するためには、上記のような腐食抑制剤
単独では効果が充分ではない。However, non-uniformity of the metal base material, such as cracks in the oxide film and grain boundary precipitates, unevenness in the concentration and flow rate of the pickling solution, and oxidizing properties such as ferric ions in the pickling solution. Pitting corrosion may occur on the metal surface due to the presence of ions, etc., resulting in the deterioration of the quality of the metal surface after pickling, which has an adverse effect on subsequent steps such as cold rolling, plating, and wire drawing. In order to prevent such pitting corrosion, the above-mentioned corrosion inhibitor alone is not sufficiently effective.
【0004】このため、酸洗液をできるだけ均一にした
り、金属表面を覆っている酸化物皮膜に、予めベンディ
ングやスキンパスによる処理によって微細な割れを生じ
させ、酸洗時に均一に酸化物皮膜が除去されるような方
法が考えられている。[0004] For this reason, the pickling liquid is made as uniform as possible, or the oxide film covering the metal surface is finely cracked by a bending or skin pass treatment in advance, and the oxide film is uniformly removed during the pickling. There is a way to be done.
【0005】[0005]
【発明が解決しようとする課題】しかしながら、上記従
来技術、たとえば酸洗前に、金属表面の酸化物皮膜に機
械的な割れを生じさせ、均一に酸化物皮膜が除去される
ようにする方法ではベンディングやスキンパスなどの大
掛りな装置が必要となり設備コストが高く、さらに金属
素地に食い込んだ酸化物皮膜は酸洗によって均一に除去
されないため、酸洗で露出した金属素地部分とこの残留
酸化物皮膜との境界付近に孔食が発生する場合があり、
このような孔食は機械的な対応で解決することが困難で
あるという問題がある。However, in the above-mentioned prior art, for example, a method of causing a mechanical crack in an oxide film on a metal surface before pickling, so that the oxide film is uniformly removed. Large equipment such as bending and skin pass is required, and equipment cost is high.In addition, since the oxide film that has penetrated the metal substrate is not uniformly removed by pickling, the metal substrate portion exposed by pickling and the residual oxide film Pitting corrosion may occur near the boundary with
There is a problem that it is difficult to solve such pitting corrosion by mechanical measures.
【0006】また、上記に述べたような腐食抑制剤単独
では孔食の防止効果は充分ではない。Further, the corrosion inhibitor alone as described above is not sufficiently effective in preventing pitting corrosion.
【0007】本発明の目的は、金属の酸洗時に発生する
金属素地の腐食を抑制し、孔食を防止する腐食抑制剤を
提供することである。[0007] An object of the present invention is to provide a corrosion inhibitor which suppresses corrosion of a metal substrate generated during pickling of a metal and prevents pitting corrosion.
【0008】[0008]
【課題を解決するための手段】本発明は、下記(A)と
(B)との混合物から成る腐食抑制剤組成物において、 (A)分子内に1級アミン、2級アミン、3級アミンも
しくは4級アンモニウム基またはアミド基の1種または
2種以上を2個以上有する水または酸に可溶の化合物ま
たはこれらの化合物の混合物。 (B)ポリエチレングリコール、ポリプロピレングリコ
ールまたはエチレングリコールとプロピレングリコール
との共重合物。The present invention provides a corrosion inhibitor composition comprising a mixture of the following (A) and (B): (A) a primary amine, a secondary amine, and a tertiary amine in a molecule. Alternatively, a water- or acid-soluble compound having two or more quaternary ammonium groups or one or more amide groups, or a mixture of these compounds. (B) polyethylene glycol, polypropylene glycol or a copolymer of ethylene glycol and propylene glycol.
【0009】前記(A)の化合物が、下記(1)〜(1
0)に示す化合物のいずれかであり、 (1)次の一般式で表されるポリアミンThe compound of the above (A) has the following (1) to (1)
(1) a polyamine represented by the following general formula:
【化1】 (式中、nは2以上であり、R,R′R″は炭素数が1
〜3のアルキル基であり、それぞれ同一であってもよ
く、異なってもよい。)Embedded image (Wherein, n is 2 or more, and R and R′R ″ have 1 carbon atom.
To 3 alkyl groups, which may be the same or different. )
【0010】(2)次の一般式で表されるポリビニルカ
チオン樹脂(2) Polyvinyl cation resin represented by the following general formula
【化2】 Embedded image
【0011】(3)次の一般式で表されるポリアルキレ
ンポリアミン(3) Polyalkylene polyamine represented by the following general formula
【化3】 (式中、nは2以上であり、Rは炭素数1〜3のアルキ
ル基である。)Embedded image (In the formula, n is 2 or more, and R is an alkyl group having 1 to 3 carbon atoms.)
【0012】(4)次の一般式で示されるポリアミンス
ルホンおよび/またはその誘導体(4) Polyamine sulfone represented by the following general formula and / or a derivative thereof
【化4】 Embedded image
【0013】(5)次の一般式で表されるポリアミン(5) Polyamine represented by the following general formula
【化5】 Embedded image
【0014】(6)次の一般式で表される芳香族ポリア
ミン(6) Aromatic polyamine represented by the following general formula:
【化6】 (式中、nは1以上である。)Embedded image (In the formula, n is 1 or more.)
【0015】(7)次の一般式で表される芳香族ポリア
ミン(7) Aromatic polyamine represented by the following general formula:
【化7】 (式中、nは1以上である。)Embedded image (In the formula, n is 1 or more.)
【0016】(8)ポリアミド樹脂 (9)尿素樹脂 (10)分子内に2級アミンもしくは3級アミンまたは
4級アンモニウム基を少なくとも2個以上有し、一部が
架橋しており、カチオン度がpH9のときに2mg当
量、平均分子量が約10000、40%水溶液のときの
粘度、比重、pHがそれぞれ100〜400cp、1.
12〜1.13、3.0〜5.0であるところのカチオ
ン系アミン重合樹脂 かつ、前記(A)の化合物の平均分子量が100以上3
00,000以下であることを特徴とする腐食抑制剤組
成物である。(8) Polyamide resin (9) Urea resin (10) At least two or more secondary amine, tertiary amine or quaternary ammonium groups in the molecule, partially crosslinked, At pH 9, 2 mg equivalent, average molecular weight is about 10,000, and viscosity, specific gravity, and pH of a 40% aqueous solution are 100 to 400 cp, respectively.
A cationic amine polymer resin having a molecular weight of 12 to 1.13 and 3.0 to 5.0, and an average molecular weight of the compound of (A) of 100 or more and 3 or more.
It is a corrosion inhibitor composition characterized by being not more than 00,000.
【0017】[0017]
【0018】[0018]
【0019】[0019]
【0020】[0020]
【0021】[0021]
【0022】[0022]
【0023】[0023]
【0024】[0024]
【0025】[0025]
【0026】[0026]
【0027】[0027]
【0028】また本発明は、前記(B)の化合物の平均
分子量が200以上であり、エチレングリコールとプロ
ピレングリコールとの共重合物は、その重合比率がエチ
レングリコール2以上9以下、プロピレングリコールが
8以下1以上であることを特徴とする。In the present invention, the compound (B) has an average molecular weight of 200 or more, and the copolymer of ethylene glycol and propylene glycol has a polymerization ratio of ethylene glycol of 2 to 9 and propylene glycol of 8 or less. Hereinafter, the number is 1 or more.
【0029】また本発明は、無機酸および/または有機
酸の少なくとも1種の水溶液から成る金属の酸洗液1l
に、腐食抑制剤組成物の前記(A)と(B)とを添加し
たことを特徴とする金属酸洗液である。The present invention also relates to a metal pickling solution comprising at least one aqueous solution of an inorganic acid and / or an organic acid.
A metal pickling solution obtained by adding the above (A) and (B) of the corrosion inhibitor composition to the metal pickling solution.
【0030】[0030]
【0031】[0031]
【0032】また本発明は、無機酸および/または有機
酸の少なくとも1種の水溶液から成る金属の酸洗液1l
に、前記(A)と(B)とをそれぞれ10mg以上1
0,000mg以下添加したことを特徴とする。The present invention also relates to a metal pickling solution comprising at least one aqueous solution of an inorganic acid and / or an organic acid.
In addition, each of (A) and (B) is 10 mg or more and 1
It is characterized in that it is added in an amount of not more than 000 mg.
【0033】また本発明は、塩酸水溶液1lに、前記
(A)と(B)とをそれぞれ10mg以上10,000
mg以下添加したことを特徴とする。In the present invention, each of (A) and (B) is added in an amount of 10 mg or more to 10,000
mg or less.
【0034】また本発明は、塩酸水溶液1lに、腐食抑
制剤組成物の前記(A)と(B)とをそれぞれ10mg
以上10,000mg以下添加した金属酸洗液を用いる
ことを特徴とする金属の酸洗方法である。In the present invention, 10 mg of each of the corrosion inhibitor compositions (A) and (B) is added to 1 liter of an aqueous hydrochloric acid solution.
This is a method for pickling a metal, characterized by using a metal pickling solution to which 10,000 mg or less is added.
【0035】[0035]
【0036】[0036]
【0037】[0037]
【作用】本発明者は、このような問題を解決するために
鋭意研究をした結果、酸洗中の金属母材の腐食を抑制
し、孔食を防止する下記の腐食抑制剤を発明するに至っ
た。The present inventor has made intensive studies to solve such problems, and as a result, has invented the following corrosion inhibitor which suppresses corrosion of a metal base material during pickling and prevents pitting corrosion. Reached.
【0038】本発明に従えば、下記(A)と(B)との
混合物から成る腐食抑制剤を酸洗用の水溶液、特に塩酸
水溶液に添加することによって、上記の作用を行うこと
ができる。According to the present invention, the above action can be achieved by adding a corrosion inhibitor comprising a mixture of the following (A) and (B) to an aqueous solution for pickling, particularly an aqueous hydrochloric acid solution.
【0039】(A)分子内に1級アミン、2級アミン、
3級アミンもしくは4級アンモニウム基またはアミド基
の1種または2種以上を2個以上有する水または酸に可
溶の化合物であって、次の(1)〜(10)に示す平均
分子量が100以上300,000以下の化合物のいず
れか、またはこれらの2種以上の混合物。(A) a primary amine, a secondary amine,
A compound soluble in water or an acid having two or more tertiary amine or quaternary ammonium groups or two or more amide groups and having an average molecular weight of 100 shown in the following (1) to (10): Any of the compounds having a number of not less than 300,000 or less, or a mixture of two or more thereof.
【0040】(1)次の一般式で表されるポリアミン、
たとえばポリエチレンイミン(1) A polyamine represented by the following general formula:
For example, polyethylene imine
【0041】[0041]
【化1】 Embedded image
【0042】(式中、nは2以上であり、R,R′R″
は炭素数が1〜3のアルキル基であり、それぞれ同一で
あってもよく、異なってもよい。) (2)次の一般式で表されるポリビニルカチオン樹脂、
たとえばポリアクリル酸型カチオン樹脂(商品名ケミス
タット7300、三洋化成工業(株)製)、ポリビニル
ベンジル型カチオン樹脂(商品名ケミスタット6300
H、三洋化成工業(株)製)(Where n is 2 or more and R, R′R ″
Is an alkyl group having 1 to 3 carbon atoms, which may be the same or different. (2) a polyvinyl cation resin represented by the following general formula:
For example, a polyacrylic acid type cationic resin (trade name Chemistat 7300, manufactured by Sanyo Chemical Industries, Ltd.), a polyvinylbenzyl type cationic resin (trade name Chemistat 6300)
H, manufactured by Sanyo Chemical Industry Co., Ltd.)
【0043】[0043]
【化2】 Embedded image
【0044】(3)次の一般式で表されるポリアルキレ
ンポリアミン、たとえばトリエチレンテトラミン、テト
ラエチレンペンタミン、ペンタエチレンヘキサミン(3) Polyalkylene polyamine represented by the following general formula, for example, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine
【0045】[0045]
【化3】 Embedded image
【0046】(式中、nは2以上であり、Rは炭素数1
〜3のアルキル基である。) (4)次の一般式で表されるポリアミンスルホンおよび
/またはその誘導体、たとえばPAS(商品名、日東紡
績(株)製)(Wherein, n is 2 or more, and R has 1 carbon atom)
To 3 alkyl groups. (4) Polyamine sulfone represented by the following general formula and / or a derivative thereof, for example, PAS (trade name, manufactured by Nitto Boseki Co., Ltd.)
【0047】[0047]
【化4】 Embedded image
【0048】(5)次の一般式で表されるポリアミン、
たとえばポリビニルピリジン、ポリアリルアミン(5) A polyamine represented by the following general formula:
For example, polyvinyl pyridine, polyallylamine
【0049】[0049]
【化5】 Embedded image
【0050】(6)次の一般式で表される芳香族ポリア
ミン、たとえばガスカミン328(商品名、三菱瓦斯化
学(株)製)(6) An aromatic polyamine represented by the following general formula, for example, Gascamine 328 (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
【0051】[0051]
【化6】 Embedded image
【0052】(式中、nは1以上である。) (7)次の一般式で表される芳香族ポリアミン、たとえ
ばアニリックス(商品名、三井東圧化学(株)製)(In the formula, n is 1 or more.) (7) An aromatic polyamine represented by the following general formula, for example, Anilix (trade name, manufactured by Mitsui Toatsu Chemicals, Inc.)
【0053】[0053]
【化7】 Embedded image
【0054】(式中、nは1以上である。) (8)ポリアミド樹脂、たとえばスミレーズレジン63
3,636,639,650(30),675(商品
名、ともに住友化学工業(株)製)、アラフィックス1
00,125(商品名、ともに荒川化学工業(株)製) (9)尿素樹脂、たとえばスミレーズレジン614Spec
ial(商品名、住友化学工業(株)製) (10)分子内に2〜4級アミンを少なくとも2個以上
有し、一部が架橋しており、カチオン度がpH9の時に
2mg当量、平均分子量が約10000、40%水溶液
の時の粘度、比重、pHがそれぞれ100〜400c
p、1.12〜1.13、3.0〜5.0であるところ
のカチオン系アミン重合樹脂、たとえばスミレーズレジ
ンFR−2P(商品名、住友化学工業(株)製) (B)分子内にエーテル基、水酸基、エステル基または
ケトン基のうち少なくとも1種の基を有する水溶性高分
子またはこれらの2種以上の混合物。たとえばポリエチ
レングリコール、ポリプロピレングリコール、エチレン
グリコールとプロピレングリコールとの共重合物、ポリ
ビニルアルコール、ポリビニルピロリドン、ポリビニル
メチルエーテル、ヒドロキシメチルセルロース、ヒドロ
キシエチルセルロース、ヒドロキシプロポキシメチルセ
ルロース。さらに好ましくは平均分子量が200以上で
あるこれらの混合物またはエチレングリコールとプロピ
レングリコールの重合比が9:1〜2:8(エチレング
リコール2以上9以下、プロピレングリコールが8以下
1以上)のこれらの共重合物。(In the formula, n is 1 or more.) (8) Polyamide resin, for example, Sumireze resin 63
3,636,639,650 (30), 675 (trade names, both manufactured by Sumitomo Chemical Co., Ltd.), ALAPIX 1
00, 125 (trade names, both manufactured by Arakawa Chemical Industry Co., Ltd.) (9) Urea resin, for example, Sumirezu Resin 614Spec
ial (trade name, manufactured by Sumitomo Chemical Co., Ltd.) (10) At least two or more secondary quaternary amines in the molecule, partially cross-linked, 2 mg equivalent when the cation degree is pH 9, 2 mg equivalent, average The viscosity, specific gravity, and pH of a molecular weight of about 10,000 and a 40% aqueous solution are 100 to 400 c, respectively.
p, 1.12 to 1.13, 3.0 to 5.0, a cationic amine polymer resin such as Sumireze Resin FR-2P (trade name, manufactured by Sumitomo Chemical Co., Ltd.) A water-soluble polymer having at least one group selected from an ether group, a hydroxyl group, an ester group and a ketone group, or a mixture of two or more thereof. For example, polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropoxymethyl cellulose. More preferably, a mixture of these having an average molecular weight of 200 or more or a mixture of ethylene glycol and propylene glycol having a polymerization ratio of 9: 1 to 2: 8 (ethylene glycol 2 to 9 and propylene glycol 8 to 1 or more) is used. Polymer.
【0055】また本発明において腐食抑制剤の添加量
は、酸洗液1lに対し、上記(A)および(B)をそれ
ぞれ5mg以上である。特に酸洗液が塩酸水溶液の場合
は、塩酸水溶液1lに対し上記(A)および(B)をそ
れぞれ10mg以上10,000mg以下添加するのが
好ましい。In the present invention, the amount of the corrosion inhibitor added is 5 mg or more for each of the above (A) and (B) per 1 liter of the pickling solution. In particular, when the pickling solution is an aqueous hydrochloric acid solution, it is preferable to add 10 mg or more and 10,000 mg or less of each of (A) and (B) to 1 liter of the aqueous hydrochloric acid solution.
【0056】腐食抑制剤の添加量は酸洗液の種類によっ
て異なる。また塩酸水溶液を用いる場合も、酸洗液の温
度、流動状態によって異なるが、10mg/l以下の添
加量では激しい流動状態下でも効果はなく、10,00
0mg/l以上いくら加えても効果が変わらない。The amount of the corrosion inhibitor added depends on the type of the pickling solution. Also, when an aqueous hydrochloric acid solution is used, it differs depending on the temperature and the flow state of the pickling solution.
The effect remains the same even if 0 mg / l or more is added.
【0057】金属の酸洗温度は、酸洗液に塩酸水溶液を
用いる場合は、一般に10〜100℃であり、本発明の
腐食抑制剤は、この温度範囲で安定して使用することが
できる。この温度範囲は硫酸や有機酸の水溶液を酸洗液
に使用する場合または酸洗操作を加圧下で行う場合に
は、100℃以上でも使用することができる。The pickling temperature of the metal is generally 10 to 100 ° C. when an aqueous hydrochloric acid solution is used as the pickling solution, and the corrosion inhibitor of the present invention can be used stably in this temperature range. This temperature range can be used even at 100 ° C. or higher when an aqueous solution of sulfuric acid or an organic acid is used for the pickling solution or when the pickling operation is performed under pressure.
【0058】また、本発明の腐食抑制剤は使用に際して
塩酸水溶液に添加してもよく、また予め塩酸水溶液に添
加して酸洗液組成物とし、酸洗時にそのままでまたはこ
れを水で希釈して用いることもできる。Further, the corrosion inhibitor of the present invention may be added to an aqueous hydrochloric acid solution at the time of use, or may be added to an aqueous hydrochloric acid solution in advance to form a pickling solution composition. Can also be used.
【0059】本発明の腐食抑制剤は単独で塩酸水溶液に
添加してもよく、また酸化物皮膜の除去性を向上させる
ために塩酸水溶液に添加される酸洗促進剤と併用しても
何らさしつかえない。The corrosion inhibitor of the present invention may be added alone to an aqueous hydrochloric acid solution, or may be used in combination with a pickling accelerator added to an aqueous hydrochloric acid solution in order to improve the removability of an oxide film. Absent.
【0060】[0060]
【実施例】以下実施例でもって、本発明にかかる腐食抑
制剤をより具体的に説明するが、本発明はこれに限定さ
れるものではない。EXAMPLES The corrosion inhibitor according to the present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
【0061】実施例1 1l中に塩酸100gと第1鉄イオン50gと第2鉄イ
オン1gとを含む酸洗液の水溶液に、本発明の(A)と
して、平均分子量1800のポリエチレンイミン(商品
名エポミンSP−018、日本触媒化学工業(株)製)
と(B)として平均分子量1000のポリエチレングリ
コールとをそれぞれ1000mg添加した。この液を8
5℃まで加温した後、黒皮付き熱間圧延鋼板(JIS
G 3131)を1分間浸漬した。その後、孔食数、腐
食量、白色量を測定した。Example 1 In an aqueous solution of a pickling solution containing 100 g of hydrochloric acid, 50 g of ferrous ion and 1 g of ferric ion in 1 liter of polyethylene imine having an average molecular weight of 1800 (trade name) (Epomin SP-018, manufactured by Nippon Shokubai Chemical Industry Co., Ltd.)
And 1,000 mg of polyethylene glycol having an average molecular weight of 1,000 as (B). 8
After heating to 5 ° C, hot-rolled steel plate with black scale (JIS
G 3131) was soaked for 1 minute. Thereafter, the number of pits, the amount of corrosion, and the amount of white were measured.
【0062】実施例2 (A)として平均分子量80000のポリアリルアミン
(日東紡績(株)製)を用いた以外は、実施例1と同じ
である。Example 2 Example 2 is the same as Example 1 except that polyallylamine having an average molecular weight of 80000 (manufactured by Nitto Boseki Co., Ltd.) was used as (A).
【0063】実施例3 (A)としてペンタエチレンヘキサミンを用いた以外
は、実施例1と同じである。Example 3 Example 3 was the same as Example 1 except that pentaethylenehexamine was used as (A).
【0064】実施例4 (A)として平均分子量100000のポリビニルピリ
ジンを用いた以外は、実施例1と同じである。Example 4 Example 4 is the same as Example 1 except that polyvinylpyridine having an average molecular weight of 100,000 was used as (A).
【0065】実施例5 (A)として平均分子量2500のポリアミド尿素樹脂
(商品名スミレーズレジン639、住友化学工業(株)
製)を用いた以外は、実施例1と同じである。Example 5 As (A), a polyamide urea resin having an average molecular weight of 2,500 (trade name: Sumireze Resin 639, manufactured by Sumitomo Chemical Co., Ltd.)
Example 1 is the same as Example 1 except for the use of
【0066】実施例6 (A)として分子内に2〜4級アミンを少なくとも2個
以上有し、一部が架橋したカチオン度がpH9の時に2
mg当量で平均分子量が10000であり、40%水溶
液の時の25℃におけるpH、比重、粘度がそれぞれ、
3.0〜5.0、1.12〜1.13、100〜400
cpであるところのカチオン系アミン重合樹脂(商品
名、スミレーズレジンFR−2P、住友化学工業(株)
製)を用いた以外は、実施例1と同じである。Example 6 As (A), when at least two secondary or quaternary amines were present in the molecule and the degree of partially crosslinked cation was pH 9,
The average molecular weight is 10,000 in mg equivalent, and the pH, specific gravity, and viscosity at 25 ° C. of a 40% aqueous solution are respectively:
3.0-5.0, 1.12-1.13, 100-400
cp cationic amine polymer resin (trade name, Sumireze Resin FR-2P, Sumitomo Chemical Co., Ltd.)
Example 1 is the same as Example 1 except for the use of
【0067】実施例7 (A)として次の一般式で表されるところの芳香族ポリ
アミン(商品名ガスカミン328、三菱瓦斯化学(株)
製)Example 7 As (A), an aromatic polyamine represented by the following general formula (trade name: Gascamine 328, Mitsubishi Gas Chemical Co., Ltd.)
Made)
【0068】[0068]
【化6】 Embedded image
【0069】(式中、nは1以上である。)を用いた以
外は、実施例1と同じである。The same as Example 1 except that (where n is 1 or more).
【0070】実施例8 (A)として次の一般式で表されるところの芳香族ポリ
アミン(商品名アニリックス、三井東圧化学(株)製)Example 8 An aromatic polyamine represented by the following general formula (A) (trade name: Anilix, manufactured by Mitsui Toatsu Chemicals, Inc.)
【0071】[0071]
【化7】 Embedded image
【0072】(式中、nは1以上である。)を用いた以
外は、実施例1と同じである。The same as Example 1 except that (where n is 1 or more).
【0073】これらの結果を下記の比較例1〜9ととも
に表1に示す。The results are shown in Table 1 together with the following Comparative Examples 1 to 9.
【0074】比較例1〜8 実施例1〜8と同じ条件で実験を行った。ただし、ポリ
エチレングリコールは用いていない。Comparative Examples 1 to 8 Experiments were performed under the same conditions as in Examples 1 to 8. However, polyethylene glycol was not used.
【0075】比較例9 実施例1〜8と同じ条件で実験を行った。ただし、本発
明の(A)および(B)の物質は使用せず、その代わり
に市販の腐食抑制剤(イビットNo.71ON、朝日化
学工業(株)商品名)300mg/lを試験片の浸漬前
に酸洗液に添加した。Comparative Example 9 An experiment was performed under the same conditions as in Examples 1 to 8. However, the substances (A) and (B) of the present invention were not used, and instead, 300 mg / l of a commercially available corrosion inhibitor (Ibit No. 71ON, trade name of Asahi Chemical Industry Co., Ltd.) was immersed in the test piece. Previously added to the pickling solution.
【0076】[0076]
【表1】 [Table 1]
【0077】試験方法は下記のとおりである。The test method is as follows.
【0078】孔食数 1cm2の表面に派生した直径5
0μm以上の真円状の孔食の数を光学顕微鏡を使用して
100倍に拡大、目視でその数を計測した。Number of pits 1 Diameter 5 derived on the surface of 1 cm 2
The number of round pits of 0 μm or more was magnified 100 times using an optical microscope, and the number was visually measured.
【0079】腐食量は下記の式により求めた。The amount of corrosion was determined by the following equation.
【0080】[0080]
【数1】 (Equation 1)
【0081】白色度 下記の式により求めた。Whiteness was determined by the following equation.
【0082】[0082]
【数2】 (Equation 2)
【0083】ただし、Lは明度、aは赤〜緑の色相、b
は黄〜青の色相 L、a、bは、日本電色工業(株)製の測色色差計Σ−
80で測定 上記実施例1〜8および比較例1〜9の結果から、本発
明の腐食抑制剤はこれを塩酸水溶液に添加した時、腐食
量の抑制、孔食の防止および白色度の改善に顕著な効果
があることがわかる。Where L is lightness, a is red to green hue, b
Are yellow to blue hues L, a and b are colorimetric colorimeters of Nippon Denshoku Industries Co., Ltd.
From the results of Examples 1 to 8 and Comparative Examples 1 to 9, the corrosion inhibitor of the present invention, when added to an aqueous hydrochloric acid solution, suppresses the amount of corrosion, prevents pitting corrosion, and improves whiteness. It can be seen that there is a remarkable effect.
【0084】[0084]
【発明の効果】本発明によれば、腐食を抑制し、孔食を
防止し、かつ白色度も改善することができる。酸化物皮
膜に機械的に微細な割れを生じさせるベンディングロー
ルやスキンパスなどの機械的な設備が不要であるため、
設備コストが低減できることから工業的価値が大きい。According to the present invention, corrosion can be suppressed, pitting corrosion can be prevented, and whiteness can be improved. Since mechanical equipment such as bending rolls and skin passes that mechanically cause minute cracks in the oxide film is unnecessary,
The industrial value is great because the equipment cost can be reduced.
Claims (6)
腐食抑制剤組成物において、 (A)分子内に1級アミン、2級アミン、3級アミンも
しくは4級アンモニウム基またはアミド基の1種または
2種以上を2個以上有する水または酸に可溶の化合物ま
たはこれらの化合物の混合物。 (B)ポリエチレングリコール、ポリプロピレングリコ
ールまたはエチレングリコールとプロピレングリコール
との共重合物。前記(A)の化合物が、下記(1)〜
(10)に示す化合物のいずれかであり、 (1)次の一般式で表されるポリアミン 【化1】 (式中、nは2以上であり、R,R′R″は炭素数が1
〜3のアルキル基であり、それぞれ同一であってもよ
く、異なってもよい。) (2)次の一般式で表されるポリビニルカチオン樹脂 【化2】 (3)次の一般式で表されるポリアルキレンポリアミン 【化3】 (式中、nは2以上であり、Rは炭素数1〜3のアルキ
ル基である。) (4)次の一般式で示されるポリアミンスルホンおよび
/またはその誘導体 【化4】 (5)次の一般式で表されるポリアミン 【化5】 (6)次の一般式で表される芳香族ポリアミン 【化6】 (式中、nは1以上である。) (7)次の一般式で表される芳香族ポリアミン 【化7】 (式中、nは1以上である。) (8)ポリアミド樹脂 (9)尿素樹脂 (10)分子内に2級アミンもしくは3級アミンまたは
4級アンモニウム基を少なくとも2個以上有し、一部が
架橋しており、カチオン度がpH9のときに2mg当
量、平均分子量が約10000、40%水溶液のときの
粘度、比重、pHがそれぞれ100〜400cp、1.
12〜1.13、3.0〜5.0であるところのカチオ
ン系アミン重合樹脂 かつ、前記(A)の化合物の平均分子量が100以上3
00,000以下であることを特徴とする腐食抑制剤組
成物。1. A corrosion inhibitor composition comprising a mixture of the following (A) and (B): (A) a primary amine, secondary amine, tertiary amine or quaternary ammonium group or amide group in a molecule Or a water- or acid-soluble compound having two or more of one or more of the above, or a mixture of these compounds. (B) polyethylene glycol, polypropylene glycol or a copolymer of ethylene glycol and propylene glycol. The compound of the above (A) has the following (1) to
(1) a polyamine represented by the following general formula: (Wherein, n is 2 or more, and R and R′R ″ have 1 carbon atom.
To 3 alkyl groups, which may be the same or different. (2) Polyvinyl cation resin represented by the following general formula: (3) Polyalkylene polyamine represented by the following general formula: (In the formula, n is 2 or more, and R is an alkyl group having 1 to 3 carbon atoms.) (4) Polyamine sulfone represented by the following general formula and / or a derivative thereof: (5) Polyamine represented by the following general formula: (6) Aromatic polyamine represented by the following general formula: (In the formula, n is 1 or more.) (7) Aromatic polyamine represented by the following general formula: (In the formula, n is 1 or more.) (8) Polyamide resin (9) Urea resin (10) At least two or more secondary amines or tertiary amines or quaternary ammonium groups in the molecule, and a part thereof Are crosslinked, 2 mg equivalent when the cation degree is pH 9, the average molecular weight is about 10,000, and the viscosity, specific gravity, and pH when a 40% aqueous solution are 100 to 400 cp, respectively.
A cationic amine polymer resin having a molecular weight of 12 to 1.13, 3.0 to 5.0, and an average molecular weight of the compound of (A) of 100 or more and 3 or more;
A corrosion inhibitor composition having a molecular weight of not more than 00,000.
0以上であり、エチレングリコールとプロピレングリコ
ールとの共重合物は、その重合比率がエチレングリコー
ル2以上9以下、プロピレングリコールが8以下1以上
であることを特徴とする請求項1記載の腐食抑制剤組成
物。2. The compound (B) having an average molecular weight of 20
The corrosion inhibitor according to claim 1, wherein the copolymerization ratio of ethylene glycol and propylene glycol is 0 or more, and the polymerization ratio of ethylene glycol is 2 or more and 9 or less and propylene glycol is 8 or less and 1 or more. Composition.
も1種の水溶液から成る金属の酸洗液1lに、請求項1
または2の腐食抑制剤組成物の前記(A)と(B)とを
添加したことを特徴とする金属酸洗液。3. A pickling solution for a metal comprising at least one aqueous solution of an inorganic acid and / or an organic acid, 1 liter of the metal pickling solution.
Or a metal pickling solution obtained by adding the above (A) and (B) of the corrosion inhibitor composition of 2 above.
も1種の水溶液から成る金属の酸洗液1lに、前記
(A)と(B)とをそれぞれ10mg以上10,000
mg以下添加したことを特徴とする請求項3記載の金属
酸洗液。4. A metal pickling solution consisting of at least one aqueous solution of an inorganic acid and / or an organic acid, wherein each of said (A) and (B) is added in an amount of 10 mg or more to 10,000.
4. The metal pickling solution according to claim 3, wherein the amount is less than or equal to mg.
とをそれぞれ10mg以上10,000mg以下添加し
たことを特徴とする請求項4記載の金属酸洗液。5. One liter of an aqueous hydrochloric acid solution contains (A) and (B)
The metal pickling solution according to claim 4, wherein 10 mg or more and 10,000 mg or less are added, respectively.
腐食抑制剤組成物の前記(A)と(B)とをそれぞれ1
0mg以上10,000mg以下添加した金属酸洗液を
用いることを特徴とする金属の酸洗方法。6. The corrosion inhibitor composition according to claim 1, wherein (A) and (B) are each added to 1 liter of an aqueous hydrochloric acid solution.
A method for pickling a metal, comprising using a metal pickling solution to which 0 mg to 10,000 mg is added.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04462992A JP3222176B2 (en) | 1992-03-02 | 1992-03-02 | Corrosion inhibitor composition, metal pickling liquid containing the same, and method for pickling metal |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04462992A JP3222176B2 (en) | 1992-03-02 | 1992-03-02 | Corrosion inhibitor composition, metal pickling liquid containing the same, and method for pickling metal |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05239673A JPH05239673A (en) | 1993-09-17 |
JP3222176B2 true JP3222176B2 (en) | 2001-10-22 |
Family
ID=12696718
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JP04462992A Expired - Lifetime JP3222176B2 (en) | 1992-03-02 | 1992-03-02 | Corrosion inhibitor composition, metal pickling liquid containing the same, and method for pickling metal |
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KR100311853B1 (en) * | 1999-09-18 | 2001-10-18 | 명 섭 한 | Corrosion Inhibitor Composition for Acid Cleaning |
JP5683137B2 (en) * | 2010-06-03 | 2015-03-11 | 朝日化学工業株式会社 | Acid cleaning liquid for metal material and acid cleaning method for metal material |
JP6266930B2 (en) * | 2013-09-09 | 2018-01-24 | スギムラ化学工業株式会社 | Granular sludge generation inhibitor |
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