WO2020217519A1 - Smut removal composition - Google Patents

Smut removal composition Download PDF

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Publication number
WO2020217519A1
WO2020217519A1 PCT/JP2019/018126 JP2019018126W WO2020217519A1 WO 2020217519 A1 WO2020217519 A1 WO 2020217519A1 JP 2019018126 W JP2019018126 W JP 2019018126W WO 2020217519 A1 WO2020217519 A1 WO 2020217519A1
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acid
smut
salt
weight
hydrogen peroxide
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PCT/JP2019/018126
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French (fr)
Japanese (ja)
Inventor
敏史 上恐
勇介 藤井
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朝日化学工業株式会社
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Priority to JP2019556297A priority Critical patent/JP6670424B1/en
Priority to PCT/JP2019/018126 priority patent/WO2020217519A1/en
Publication of WO2020217519A1 publication Critical patent/WO2020217519A1/en

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    • 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

Definitions

  • the present invention relates to a smut removing composition capable of removing smut that may occur on the surface after pickling a steel material.
  • the descale treatment of the hot-rolled steel strip is performed by immersing the steel strip in an acid solution such as hydrochloric acid or sulfuric acid.
  • an acid solution such as hydrochloric acid or sulfuric acid.
  • the scale itself dissolves in the acid solution, or the acid solution reaches the steel surface through cracks in the scale, causing metal dissolution and hydrogen generation, and the scale desorbs from the steel surface.
  • the acid solution is rinsed with warm water and dried. At this time, a black insoluble residue called smut may adhere to the surface of the steel material.
  • This smut is a general term for black and brown substances that firmly adhere to the surface of steel when the scale and steel strip base are melted by pickling, and the carbon contained in the steel is a fine powder. It is considered that the steel sheet is formed in the form of iron ions or iron ions during pickling are reprecipitated on the surface of the steel sheet as iron oxide or iron hydroxide during washing and drying. Adhesion of smut darkens the color tone of the steel sheet and causes color unevenness.
  • this smut remains on the surface, it adversely affects the lubrication treatment and various surface treatments in the subsequent process, and the value of the steel material is significantly reduced, so it is necessary to remove it.
  • Patent Documents 1 to 3 shown below As a method for removing this smut, methods such as Patent Documents 1 to 3 shown below have been proposed.
  • Patent Document 1 is a method in which a steel material is pickled with sulfuric acid and then immersed in a nitric acid aqueous solution containing HNO 3 of 400 g / L or more at 25 to 80 ° C. to remove smut.
  • nitric acid is not preferable because it has a problem of environmental pollution due to the generation of NO X caused by nitrogen and also dissolves not only the smut but also the surface of the steel material.
  • Patent Document 2 The method of Patent Document 2 is characterized in that a steel material is treated with permanganate under an alkaline aqueous solution, the treated solution is regenerated by electrolytic oxidation, and recycled.
  • manganese is a heavy metal, and it takes a lot of time and effort to treat the treatment liquid such as reusing and reusing and washing water after smut treatment, which requires a lot of cost.
  • Patent Document 3 is a method of smut treatment with a 0.5 to 10% phosphonate aqueous solution having a pH value of 4 to 9. This method has a relatively small environmental load as compared with the methods of Patent Documents 1 and 2, but has a problem that a sufficient smut removing ability cannot be obtained.
  • an object of the present invention is mainly to use the phosphonate method of Patent Document 3 having a relatively small environmental load, and to further improve the effect by adding the third component in order to obtain a more effective smut removing ability.
  • the purpose is.
  • the present invention is a smut removing composition containing one or more of phosphonic acid and / or a salt thereof, hydrogen peroxide, and water.
  • the present invention is also characterized in that the phosphonic acid and / or a salt thereof has 1 to 4 phosphonic acid groups in one molecule.
  • the present invention is also characterized in that the concentration of the phosphonic acid and / or a salt thereof is 0.5% by weight or more, and the concentration of hydrogen peroxide is 0.5% by weight or more.
  • the present invention is characterized in that the pH is 1 to 8.
  • the phosphonic acid is a phosphonic acid selected from 1-hydroxyethylidene-1,1 diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid, and the salt of the phosphonic acid. Is an alkali metal salt, ammonium salt or organic amine salt.
  • the phosphonic acid-based smut removing composition of the present invention By using the phosphonic acid-based smut removing composition of the present invention, a stable smut removing effect can be obtained, and the industrial benefit thereof is great.
  • the present invention is a smut-removing composition containing one or more of phosphonic acid and / or a salt thereof and hydrogen peroxide, and the phosphonic acid or a salt thereof contains at least one or more organic substances in the molecule.
  • the compound may be any compound containing a phosphonic acid group, and is not particularly limited.
  • phosphonic acid examples include methyldiphosphonic acid, etylidene diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropyridene-1,1-diphosphonic acid, and 1-hydroxybuty.
  • Reden-1,1-diphosphonic acid ethylaminobismethylenephosphonic acid, dodecylaminobismethylenephosphonic acid, ethylenediaminebismethylenephosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, 1,2-propylenediaminetetramethylenephosphonic acid Acid, hexamethylenediamine tetramethylenephosphonic acid, cyclohexanediaminetetramethylenephosphonic acid, glycol etherdiaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, triethylenetetraminehexamethylenephosphonic acid, tri2-aminoethylaminehexamethylenephosphonic acid, tetra Examples thereof include ethylenepentamine heptamethylenephosphonic acid, pentaethylenehexamine octamethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and aminotrimethylenephosphonic acid.
  • 1-hydroxyethylidene-1,1 diphosphonic acid aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid are preferable.
  • Examples of the phosphonate include alkali metal salts such as sodium salt, potassium salt, magnesium salt and calcium salt of the phosphonic acid, alkaline earth metal salts, ammonium salts and salts with organic amines. Of these, alkali metal salts, ammonium salts and organic amine salts are preferable.
  • the above-mentioned phosphonic acid or a salt thereof is not limited to one kind, and two or more kinds may be used in combination, or free phosphonic acid and a salt thereof may be used in combination.
  • hydrogen peroxide can be suitably used even if it is a hydrogen peroxide solution.
  • the concentration of phosphonic acid and / or a salt thereof is preferably 0.5 to 10% by weight, and the concentration of hydrogen peroxide is preferably 0.5 to 10% by weight, more preferably.
  • the smut-removing composition of the present invention can be produced by mixing phosphonic acid or a salt thereof and hydrogen peroxide in water, and phosphonic acid or a salt thereof and either hydrogen peroxide in water. The other that dissolves and remains may be added to the solution.
  • the solution thus obtained may be used as it is as a smut removing composition, or may be used by adjusting the pH to a predetermined range, if desired.
  • the pH range is 1-8, preferably 3-8, more preferably 3-7.
  • the pH can be adjusted by adding a pH adjusting agent to the solution, and as the pH adjusting agent, an inorganic acid, an alkaline agent, or the like can be appropriately used.
  • the smut removing composition of the present invention can further contain a chelating agent, a surfactant, a water-soluble organic solvent and the like.
  • a chelating agent aminocarboxylic acid, oxycarboxylic acid, nitrilotriacetic acid and the like can be used.
  • a nonionic surfactant As the surfactant, a nonionic surfactant, an anionic surfactant, or the like can be used.
  • water-soluble organic solvent a glycol-based solvent, an alcohol-based solvent, or the like can be used.
  • the smut removing composition of the present invention can be used in pickling of metals such as carbon steel and alloy steel, and the pickled metal is put into the removing composition of the present invention or a diluted solution thereof at room temperature or under heating. It can be used by a method such as dipping.
  • the carbon steel to which the smut was attached prepared in the above step was immersed in 150 mL of each composition shown in Table 1 in a 200 mL beaker.
  • the immersion temperature was 70 ° C. and the immersion time was 10 minutes.
  • the L value and b value before removing the smut were L value 40 and b value 8.
  • the L value and the b value were evaluated according to the following criteria, and the lower evaluation was adopted as the evaluation result.
  • Example 1 2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to bring the pH to 3. Then, 2% by weight of hydrogen peroxide was added to make the balance water.
  • Example 2 1% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 3. Then, 0.5% by weight of hydrogen peroxide was added to make the balance water.
  • Example 3 0.5% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 3. Then, 10% by weight of hydrogen peroxide was added to make the balance water.
  • Example 4 10% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to bring the pH to 3. Then, 2% by weight of hydrogen peroxide was added to make the balance water.
  • Example 5 2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to bring the pH to 5. Then, 3% by weight of hydrogen peroxide was added to make the balance water.
  • Example 6 2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to bring the pH to 7. Then, 3% by weight of hydrogen peroxide was added to make the balance water.
  • Example 7 2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 8. Then, 3% by weight of hydrogen peroxide was added to make the balance water.
  • Example 8 2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous sodium hydroxide solution to bring the pH to 3. Then, 3% by weight of hydrogen peroxide was added to make the balance water.
  • Example 9 2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous ammonium solution to adjust the pH to 3. Then, 3% by weight of hydrogen peroxide was added to make the balance water.
  • Example 10 2% by weight of aminotrimethylene phosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 3. Then, 2% by weight of hydrogen peroxide was added to make the balance water.
  • Example 11 2% by weight of ethylenediaminetetramethylenephosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 3. Then, 2% by weight of hydrogen peroxide was added to make the balance water.
  • Example 12 2% by weight of diethylenetriamine pentamethylenephosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 3. Then, 2% by weight of hydrogen peroxide was added to make the balance water.
  • Comparative Example 1 2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 5, and the balance was water.
  • Comparative Example 2 3% by weight of hydrogen peroxide was added to make the balance water.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
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Abstract

The purpose of the present invention is to provide a smut removal composition which is stable and has a further improved effect by improving a smut removal method using a phosphonate having a relatively small environmental load. The smut removal composition comprises one or two or more phosphonic acids and/or salts thereof, hydrogen peroxide and water.

Description

スマット除去組成物Smut removal composition
　本発明は、鋼材の酸洗後、表面に生ずることのあるスマットを除去できるスマット除去組成物に関する。 The present invention relates to a smut removing composition capable of removing smut that may occur on the surface after pickling a steel material.
　熱延鋼帯の脱スケール処理、いわゆる「酸洗」は、塩酸、硫酸などの酸液に鋼帯を浸漬して行う。酸洗時には、スケール自体が酸液へ溶解し、あるいはスケール中の亀裂を通って酸液が鋼材表面に到達し金属の溶解と水素発生が起こり、スケールが鋼材表面から脱離する。 The descale treatment of the hot-rolled steel strip, so-called "pickling", is performed by immersing the steel strip in an acid solution such as hydrochloric acid or sulfuric acid. During pickling, the scale itself dissolves in the acid solution, or the acid solution reaches the steel surface through cracks in the scale, causing metal dissolution and hydrogen generation, and the scale desorbs from the steel surface.
　酸洗後は、酸液を温水で洗い流し乾燥させるが、このとき鋼材表面にスマットといわれる黒色の不溶解性残渣が付着することがある。 After pickling, the acid solution is rinsed with warm water and dried. At this time, a black insoluble residue called smut may adhere to the surface of the steel material.
　このスマットというのは、酸洗によりスケール、鋼帯素地が溶解した際に、鋼の表面に強固に付着する黒色や茶褐色の物質を総称したものであり、鉄鋼に含まれていた炭素が微粉末状になったものや、酸洗中の鉄イオンが水洗乾燥時に酸化鉄や水酸化鉄として鋼板表面に再析出したものからなると考えられている。スマットの付着は鋼板の色調を暗くするとともに、色むらを生じさせる。 This smut is a general term for black and brown substances that firmly adhere to the surface of steel when the scale and steel strip base are melted by pickling, and the carbon contained in the steel is a fine powder. It is considered that the steel sheet is formed in the form of iron ions or iron ions during pickling are reprecipitated on the surface of the steel sheet as iron oxide or iron hydroxide during washing and drying. Adhesion of smut darkens the color tone of the steel sheet and causes color unevenness.
　さらにこれに加えて、このスマットが表面に残留していると、後工程の潤滑処理や各種表面処理に悪影響を与え、鋼材価値を著しく下げるため、除去する必要が生ずる。 Furthermore, in addition to this, if this smut remains on the surface, it adversely affects the lubrication treatment and various surface treatments in the subsequent process, and the value of the steel material is significantly reduced, so it is necessary to remove it.
　このスマットを除去する方法としては、下記に示す特許文献１～特許文献３などの方法が提案されている。 As a method for removing this smut, methods such as Patent Documents 1 to 3 shown below have been proposed.
　特許文献１の方法は、鋼材を硫酸酸洗後、４００ｇ／Ｌ以上のＨＮＯ３を含有する２５～８０℃の硝酸水溶液中に浸漬してスマット除去を行う方法である。しかし硝酸は窒素に起因するＮＯＸの発生による環境汚染の問題があり、また、スマットだけではなく鋼材表面も溶解するため、好ましくない。 The method of Patent Document 1 is a method in which a steel material is pickled with sulfuric acid and then immersed in a nitric acid aqueous solution containing HNO 3 of 400 g / L or more at 25 to 80 ° C. to remove smut. However, nitric acid is not preferable because it has a problem of environmental pollution due to the generation of NO X caused by nitrogen and also dissolves not only the smut but also the surface of the steel material.
　特許文献２の方法は、鋼材をアルカリ水溶液下の過マンガン酸で処理し、処理後の溶液を電解酸化で再生して、循環再使用することを特徴としている。しかしマンガンは重金属であり、再生再使用など処理液やスマット処理後の水洗水の処理、手間を要し多大な経費を要する。しかも、将来的にはこのような重金属の使用が禁止されるおそれが多分にある。 The method of Patent Document 2 is characterized in that a steel material is treated with permanganate under an alkaline aqueous solution, the treated solution is regenerated by electrolytic oxidation, and recycled. However, manganese is a heavy metal, and it takes a lot of time and effort to treat the treatment liquid such as reusing and reusing and washing water after smut treatment, which requires a lot of cost. Moreover, there is a high possibility that the use of such heavy metals will be prohibited in the future.
　特許文献３の方法は、ＰＨ値を４～９に調製した、０．５～１０％のホスホン酸塩水溶液でスマット処理をする方法である。この方法は、前記特許文献１、２の方法に比べて環境負荷は比較的小さいが、十分なスマット除去能力が得られないという問題がある。 The method of Patent Document 3 is a method of smut treatment with a 0.5 to 10% phosphonate aqueous solution having a pH value of 4 to 9. This method has a relatively small environmental load as compared with the methods of Patent Documents 1 and 2, but has a problem that a sufficient smut removing ability cannot be obtained.
特開昭６１－６９９８９号公報Japanese Unexamined Patent Publication No. 61-69089 特開平６－３３０３５９号公報Japanese Unexamined Patent Publication No. 6-330359 特許第３２０７６３６号公報Japanese Patent No. 3207636
　本発明者らは、スマット除去効果を向上させるため、ホスホン酸および／またはホスホン酸塩に種々の添加物の添加を試みた結果、過酸化水素の添加が最も効果のあることを発見し本発明を完成した。 As a result of trying to add various additives to phosphonic acid and / or phosphonate in order to improve the smut removing effect, the present inventors have found that the addition of hydrogen peroxide is the most effective. Was completed.
　すなわち、本発明の目的は、環境負荷が比較的小さい特許文献３のホスホン酸塩による方法を主体にして、より効果的なスマット除去能力を得るため、第三成分添加による効果のさらなる向上を計ることを目的とする。 That is, an object of the present invention is mainly to use the phosphonate method of Patent Document 3 having a relatively small environmental load, and to further improve the effect by adding the third component in order to obtain a more effective smut removing ability. The purpose is.
　本発明は、ホスホン酸および／またはその塩の１種あるいは２種以上と、過酸化水素と、水と、を含むスマット除去組成物である。
　また本発明は、前記ホスホン酸および／またはその塩が１分子内にホスホン酸基を１～４有することを特徴とする。 The present invention is a smut removing composition containing one or more of phosphonic acid and / or a salt thereof, hydrogen peroxide, and water.
The present invention is also characterized in that the phosphonic acid and / or a salt thereof has 1 to 4 phosphonic acid groups in one molecule.
　また、本発明は、前記ホスホン酸および／またはその塩の濃度が０．５重量％以上であり、過酸化水素の濃度が０．５重量％以上であることを特徴とする。 The present invention is also characterized in that the concentration of the phosphonic acid and / or a salt thereof is 0.5% by weight or more, and the concentration of hydrogen peroxide is 0.5% by weight or more.
　さらに、本発明は、ｐＨが１～８であることを特徴とする。 Further, the present invention is characterized in that the pH is 1 to 8.
　また本発明は、前記ホスホン酸が１－ヒドロキシエチリデン－１，１ジホスホン酸、アミノトリメチレンホスホン酸、エチレンジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸より選ばれるホスホン酸であり、前記ホスホン酸の塩がアルカリ金属塩、アンモニウム塩または有機アミン塩であることを特徴とする。 Further, in the present invention, the phosphonic acid is a phosphonic acid selected from 1-hydroxyethylidene-1,1 diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid, and the salt of the phosphonic acid. Is an alkali metal salt, ammonium salt or organic amine salt.
　本発明のホスホン酸系スマット除去組成物を用いることにより、安定したスマット除去効果を得ることができ、その産業的利益は多大なものがある。 By using the phosphonic acid-based smut removing composition of the present invention, a stable smut removing effect can be obtained, and the industrial benefit thereof is great.
　本発明は、ホスホン酸および／またはその塩の１種あるいは２種以上と、過酸化水素とを含むスマット除去組成物であり、ホスホン酸またはその塩としては、分子内に少なくとも１つ以上の有機ホスホン酸基を含む化合物であればよく、特に限定されない。 The present invention is a smut-removing composition containing one or more of phosphonic acid and / or a salt thereof and hydrogen peroxide, and the phosphonic acid or a salt thereof contains at least one or more organic substances in the molecule. The compound may be any compound containing a phosphonic acid group, and is not particularly limited.
　かかるホスホン酸としては、具体的には、メチルジホスホン酸、エチリデンジホスホン酸、１－ヒドロキシエチリデン－１，１－ジホスホン酸、１－ヒドロキシプロピリデン－１，１－ジホスホン酸、１－ヒドロキシブチリデン－１，１－ジホスホン酸、エチルアミノビスメチレンホスホン酸、ドデシルアミノビスメチレンホスホン酸、エチレンジアミンビスメチレンホスホン酸、アミノトリメチレンホスホン酸、エチレンジアミンテトラメチレンホスホン酸、１，２－プロピレンジアミンテトラメチレンホスホン酸、ヘキサメチレンジアミンテトラメチレンホスホン酸、シクロヘキサンジアミンテトラメチレンホスホン酸、グリコールエーテルジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸、トリエチレンテトラミンヘキサメチレンホスホン酸、トリ２－アミノエチルアミンヘキサメチレンホスホン酸、テトラエチレンペンタミンヘプタメチレンホスホン酸、ペンタエチレンヘキサミンオクタメチレンホスホン酸、２－ホスホノブタン－１，２，４－トリカルボン酸、アミノトリメチレンホスホン酸などがあげられる。 Specific examples of such phosphonic acid include methyldiphosphonic acid, etylidene diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropyridene-1,1-diphosphonic acid, and 1-hydroxybuty. Reden-1,1-diphosphonic acid, ethylaminobismethylenephosphonic acid, dodecylaminobismethylenephosphonic acid, ethylenediaminebismethylenephosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, 1,2-propylenediaminetetramethylenephosphonic acid Acid, hexamethylenediamine tetramethylenephosphonic acid, cyclohexanediaminetetramethylenephosphonic acid, glycol etherdiaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, triethylenetetraminehexamethylenephosphonic acid, tri2-aminoethylaminehexamethylenephosphonic acid, tetra Examples thereof include ethylenepentamine heptamethylenephosphonic acid, pentaethylenehexamine octamethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and aminotrimethylenephosphonic acid.
　このうち、本発明においては、１－ヒドロキシエチリデン－１，１ジホスホン酸、アミノトリメチレンホスホン酸、エチレンジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸が好ましい。 Of these, in the present invention, 1-hydroxyethylidene-1,1 diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid are preferable.
　また、ホスホン酸塩としては、前記ホスホン酸のナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩などのアルカリ金属塩、アルカリ土類金属塩のほか、アンモニウム塩、有機アミンとの塩があげられる。このうち、アルカリ金属塩、アンモニウム塩、有機アミン塩が好ましい。 Examples of the phosphonate include alkali metal salts such as sodium salt, potassium salt, magnesium salt and calcium salt of the phosphonic acid, alkaline earth metal salts, ammonium salts and salts with organic amines. Of these, alkali metal salts, ammonium salts and organic amine salts are preferable.
　上記のホスホン酸またはその塩は、１種のみに限らず、２種以上を併用してもよく、遊離のホスホン酸とその塩とを併用してもよい。 The above-mentioned phosphonic acid or a salt thereof is not limited to one kind, and two or more kinds may be used in combination, or free phosphonic acid and a salt thereof may be used in combination.
　本発明においては、過酸化水素は、過酸化水素水であっても好適に使用することができる。 In the present invention, hydrogen peroxide can be suitably used even if it is a hydrogen peroxide solution.
　本発明のスマット除去組成物において、ホスホン酸および／またはその塩の濃度が０．５～１０重量％であり、過酸化水素の濃度が０．５～１０重量％であることが好ましく、より好ましくは、ホスホン酸および／またはその塩の濃度が０．５～１０重量％であり、過酸化水素濃度が０．５～６重量％である。 In the smut removing composition of the present invention, the concentration of phosphonic acid and / or a salt thereof is preferably 0.5 to 10% by weight, and the concentration of hydrogen peroxide is preferably 0.5 to 10% by weight, more preferably. Has a phosphonic acid and / or salt concentration thereof of 0.5 to 10% by weight and a hydrogen peroxide concentration of 0.5 to 6% by weight.
　本発明のスマット除去組成物は、ホスホン酸またはその塩と、過酸化水素とを水に混合することにより製造することができ、ホスホン酸またはその塩と、過酸化水素のいずれか一方を水に溶解し、残る他方を前記溶液に加えてもよい。 The smut-removing composition of the present invention can be produced by mixing phosphonic acid or a salt thereof and hydrogen peroxide in water, and phosphonic acid or a salt thereof and either hydrogen peroxide in water. The other that dissolves and remains may be added to the solution.
　かくして得られた溶液は、そのままスマット除去組成物として使用してもよく、所望により、ｐＨを所定の範囲に調整して使用してもよい。ｐＨの範囲は、1～８、好ましくは３～８、より好ましくは３～７である。ｐＨの調整は、ｐＨ調整剤を前記溶液に加えることにより行うことができ、ｐＨ調整剤としては、無機酸、アルカリ剤などを適宜使用することができる。 The solution thus obtained may be used as it is as a smut removing composition, or may be used by adjusting the pH to a predetermined range, if desired. The pH range is 1-8, preferably 3-8, more preferably 3-7. The pH can be adjusted by adding a pH adjusting agent to the solution, and as the pH adjusting agent, an inorganic acid, an alkaline agent, or the like can be appropriately used.
　本発明のスマット除去組成物は、さらにキレート剤、界面活性剤、水溶性有機溶剤などを含有させることができる。キレート剤としては、アミノカルボン酸、オキシカルボン酸、ニトリロトリ酢酸等を用いることができる。 The smut removing composition of the present invention can further contain a chelating agent, a surfactant, a water-soluble organic solvent and the like. As the chelating agent, aminocarboxylic acid, oxycarboxylic acid, nitrilotriacetic acid and the like can be used.
　界面活性剤としては、非イオン性界面活性剤、アニオン活性剤等を用いることができる。 As the surfactant, a nonionic surfactant, an anionic surfactant, or the like can be used.
　水溶性有機溶剤としては、グリコール系溶剤、アルコール系溶剤等を用いることができる。 As the water-soluble organic solvent, a glycol-based solvent, an alcohol-based solvent, or the like can be used.
　本発明のスマット除去組成物は、炭素鋼、合金鋼等の金属の酸洗浄において用いることができ、酸洗された前記金属を本発明の除去組成物もしくはその希釈液に、常温ないし加温下に、浸漬するなどの方法で使用することができる。 The smut removing composition of the present invention can be used in pickling of metals such as carbon steel and alloy steel, and the pickled metal is put into the removing composition of the present invention or a diluted solution thereof at room temperature or under heating. It can be used by a method such as dipping.
　以下、実施例により、本発明をさらに詳細に説明するが、本発明は、その精神または主要な特徴から逸脱することなく、他のいろいろな形態で実施できる。したがって、前述の実施形態はあらゆる点で単なる例示に過ぎず、本発明の範囲は特許請求の範囲に示すものであって、明細書本文には何ら拘束されない。さらに、特許請求の範囲に属する変形や変更は全て本発明の範囲内のものである。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention can be carried out in various other forms without departing from its spirit or main features. Therefore, the above-described embodiment is merely an example in all respects, and the scope of the present invention is shown in the claims and is not bound by the text of the specification. Furthermore, all modifications and modifications that fall within the scope of the claims are within the scope of the present invention.
＜評価方法＞
　評価方法としては、スケールの付着した炭素鋼（３０ｍｍ各２ｍｍ厚）を７０℃の１０％硫酸に３０分間浸漬してスケールを除去してスマットを発生させた。その後、水道水にて炭素鋼に付着した酸を水洗した。水洗後、ドライヤーにより炭素鋼表面を乾燥させて、スマットの付着した炭素鋼を準備した。 <Evaluation method>
As an evaluation method, carbon steel with scale attached (30 mm, 2 mm thick each) was immersed in 10% sulfuric acid at 70 ° C. for 30 minutes to remove the scale and generate a smut. Then, the acid adhering to the carbon steel was washed with tap water. After washing with water, the surface of the carbon steel was dried with a dryer to prepare carbon steel to which smut was attached.
　上記工程にて準備したスマットの付着した炭素鋼を２００ｍＬのビーカーに表１に示す各組成物１５０ｍＬに浸漬した。浸漬温度は７０℃、浸漬時間は１０分とした。その後、炭素鋼を取り出し、水道水にて水洗して、ドライヤーにて乾燥後の炭素鋼表面を分光測色計（コニカミノルタ株式会社製、ＣＭ－５１２ｍ３Ａ）の照射角４５°におけるＬ値、ｂ値にて評価した。なお、スマット除去前のＬ値、ｂ値はＬ値４０、ｂ値８であった。 The carbon steel to which the smut was attached prepared in the above step was immersed in 150 mL of each composition shown in Table 1 in a 200 mL beaker. The immersion temperature was 70 ° C. and the immersion time was 10 minutes. Then removed carbon steel, and washed with water with tap water, colorimeter spectral carbon steel surface after drying at drier (Konica Minolta Co., Ltd., CM-512m3A) L value at the irradiation angle of 45 °, b Evaluated by value. The L value and b value before removing the smut were L value 40 and b value 8.
　評価方法は、下記の基準において、Ｌ値およびｂ値をそれぞれ評価し、低い方の評価を、評価結果として採用した。 As the evaluation method, the L value and the b value were evaluated according to the following criteria, and the lower evaluation was adopted as the evaluation result.
Ｌ値
　７０以上＝◎、５５～７０未満＝〇、５１～５５未満＝△、５１未満＝× L value 70 or more = ◎, 55 to less than 70 = 〇, 51 to less than 55 = △, less than 51 = ×
ｂ値
２．０未満＝◎、２．０～４．０未満＝〇、４．０～５．０未満＝△、５．０以上＝× b value less than 2.0 = ◎, 2.0 to less than 4.0 = 〇, 4.0 to less than 5.0 = △, 5.0 or more = ×
実施例１
　１－ヒドロキシエチリデン－１，１ジホスホン酸２重量％を水酸化カリウム水溶液で中和して、ｐＨ３にした。その後、過酸化水素を２重量％添加して、残部を水とした。 Example 1
2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to bring the pH to 3. Then, 2% by weight of hydrogen peroxide was added to make the balance water.
実施例２
　１－ヒドロキシエチリデン－１，１ジホスホン酸１重量％を水酸化カリウム水溶液で中和して、ｐＨ３にした。その後、過酸化水素を０．５重量％添加して、残部を水とした。 Example 2
1% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 3. Then, 0.5% by weight of hydrogen peroxide was added to make the balance water.
実施例３
　１－ヒドロキシエチリデン－１，１ジホスホン酸０．５重量％を水酸化カリウム水溶液で中和して、ｐＨ３にした。その後、過酸化水素を１０重量％添加して、残部を水とした。 Example 3
0.5% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 3. Then, 10% by weight of hydrogen peroxide was added to make the balance water.
実施例４
　１－ヒドロキシエチリデン－１，１ジホスホン酸１０重量％を水酸化カリウム水溶液で中和して、ｐＨ３にした。その後、過酸化水素を２重量％添加して、残部を水とした。 Example 4
10% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to bring the pH to 3. Then, 2% by weight of hydrogen peroxide was added to make the balance water.
実施例５
　１－ヒドロキシエチリデン－１，１ジホスホン酸２重量％を水酸化カリウム水溶液で中和して、ｐＨ５にした。その後、過酸化水素を３重量％添加して、残部を水とした。 Example 5
2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to bring the pH to 5. Then, 3% by weight of hydrogen peroxide was added to make the balance water.
実施例６
　１－ヒドロキシエチリデン－１，１ジホスホン酸２重量％を水酸化カリウム水溶液で中和して、ｐＨ７にした。その後、過酸化水素を３重量％添加して、残部を水とした。 Example 6
2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to bring the pH to 7. Then, 3% by weight of hydrogen peroxide was added to make the balance water.
実施例７
　１－ヒドロキシエチリデン－１，１ジホスホン酸２重量％を水酸化カリウム水溶液で中和して、ｐＨ８にした。その後、過酸化水素を３重量％添加して、残部を水とした。 Example 7
2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 8. Then, 3% by weight of hydrogen peroxide was added to make the balance water.
実施例８
　１－ヒドロキシエチリデン－１，１ジホスホン酸２重量％を水酸化ナトリウム水溶液で中和して、ｐＨ３にした。その後、過酸化水素を３重量％添加して、残部を水とした。 Example 8
2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous sodium hydroxide solution to bring the pH to 3. Then, 3% by weight of hydrogen peroxide was added to make the balance water.
実施例９
　１－ヒドロキシエチリデン－１，１ジホスホン酸２重量％をアンモニウム水溶液で中和して、ｐＨ３にした。その後、過酸化水素を３重量％添加して、残部を水とした。 Example 9
2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous ammonium solution to adjust the pH to 3. Then, 3% by weight of hydrogen peroxide was added to make the balance water.
実施例１０
　アミノトリメチレンホスホン酸２重量％を水酸化カリウム水溶液で中和して、ｐＨ３にした。その後、過酸化水素を２重量％添加して、残部を水とした。 Example 10
2% by weight of aminotrimethylene phosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 3. Then, 2% by weight of hydrogen peroxide was added to make the balance water.
実施例１１
　エチレンジアミンテトラメチレンホスホン酸２重量％を水酸化カリウム水溶液で中和して、ｐＨ３にした。その後、過酸化水素を２重量％添加して、残部を水とした。 Example 11
2% by weight of ethylenediaminetetramethylenephosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 3. Then, 2% by weight of hydrogen peroxide was added to make the balance water.
実施例１２
　ジエチレントリアミンペンタメチレンホスホン酸２重量％を水酸化カリウム水溶液で中和して、ｐＨ３にした。その後、過酸化水素を２重量％添加して、残部を水とした。 Example 12
2% by weight of diethylenetriamine pentamethylenephosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 3. Then, 2% by weight of hydrogen peroxide was added to make the balance water.
比較例１
　１－ヒドロキシエチリデン－１，１ジホスホン酸２重量％を水酸化カリウム水溶液で中和して、ｐＨ５にして残部を水とした。 Comparative Example 1
2% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid was neutralized with an aqueous potassium hydroxide solution to adjust the pH to 5, and the balance was water.
比較例２
　過酸化水素を３重量％添加して、残部を水とした。 Comparative Example 2
3% by weight of hydrogen peroxide was added to make the balance water.
　結果は、表１に示すとおりである。 The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Claims (5)

  1. 　ホスホン酸および／またはその塩の１種あるいは２種以上と、過酸化水素と、水と、を含むことを特徴とするスマット除去組成物。 A smut removing composition comprising one or more of phosphonic acid and / or a salt thereof, hydrogen peroxide, and water.
  2. 　前記ホスホン酸および／またはその塩が１分子内にホスホン酸基を１～４有することを特徴とする請求項１に記載のスマット除去組成物。 The smut removing composition according to claim 1, wherein the phosphonic acid and / or a salt thereof has 1 to 4 phosphonic acid groups in one molecule.
  3. 　前記ホスホン酸および／またはその塩の濃度が０．５重量％以上であり、かつ過酸化水素の濃度が０．５重量％以上であることを特徴とする請求項１または２に記載のスマット除去組成物。 The smut removal according to claim 1 or 2, wherein the concentration of the phosphonic acid and / or a salt thereof is 0.5% by weight or more, and the concentration of hydrogen peroxide is 0.5% by weight or more. Composition.
  4. 　ｐＨが１～８であることを特徴とする請求項１～３のいずれか１に記載のスマット除去組成物。 The smut removing composition according to any one of claims 1 to 3, wherein the pH is 1 to 8.
  5. 　前記ホスホン酸が、１－ヒドロキシエチリデン－１，１ジホスホン酸、アミノトリメチレンホスホン酸、エチレンジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸より選ばれるホスホン酸であり、前記ホスホン酸の塩がアルカリ金属塩、アンモニウム塩または有機アミン塩のいずれかであることを特徴とする請求項１～４のいずれか１に記載のスマット除去組成物。 The phosphonic acid is a phosphonic acid selected from 1-hydroxyethylidene-1,1 diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid, and the salt of the phosphonic acid is an alkali metal salt. The smut removing composition according to any one of claims 1 to 4, which is either an ammonium salt or an organic amine salt.
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JPH0273983A (en) * 1988-09-07 1990-03-13 Nippon Parkerizing Co Ltd Acidic washing solution for aluminum
JPH07113190A (en) * 1993-10-18 1995-05-02 Mitsubishi Heavy Ind Ltd Smut removing liquid
JP2000144463A (en) * 1998-11-17 2000-05-26 Nippon Peroxide Co Ltd Smut removing agent for aluminum metal
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JP2004068068A (en) * 2002-08-05 2004-03-04 Nippon Parkerizing Co Ltd Combined material and method for producing the same
JP2011127140A (en) * 2009-12-15 2011-06-30 Mitsubishi Gas Chemical Co Inc Surface treatment method for chromium-molybdenum steel
CN107254682A (en) * 2017-06-23 2017-10-17 深圳市威通科技有限公司 Scale remover

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0273983A (en) * 1988-09-07 1990-03-13 Nippon Parkerizing Co Ltd Acidic washing solution for aluminum
JPH07113190A (en) * 1993-10-18 1995-05-02 Mitsubishi Heavy Ind Ltd Smut removing liquid
JP2000144463A (en) * 1998-11-17 2000-05-26 Nippon Peroxide Co Ltd Smut removing agent for aluminum metal
JP2003519290A (en) * 1999-12-30 2003-06-17 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン Luster / passivation of metal surfaces without risk of nitrogen oxide release
JP2004068068A (en) * 2002-08-05 2004-03-04 Nippon Parkerizing Co Ltd Combined material and method for producing the same
JP2011127140A (en) * 2009-12-15 2011-06-30 Mitsubishi Gas Chemical Co Inc Surface treatment method for chromium-molybdenum steel
CN107254682A (en) * 2017-06-23 2017-10-17 深圳市威通科技有限公司 Scale remover

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