JPH06101067A - Ceramic coating liquid for preventing high temperature oxidation of stainless steel - Google Patents
Ceramic coating liquid for preventing high temperature oxidation of stainless steelInfo
- Publication number
- JPH06101067A JPH06101067A JP25448392A JP25448392A JPH06101067A JP H06101067 A JPH06101067 A JP H06101067A JP 25448392 A JP25448392 A JP 25448392A JP 25448392 A JP25448392 A JP 25448392A JP H06101067 A JPH06101067 A JP H06101067A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- coating liquid
- high temperature
- ceramic coating
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Glass Compositions (AREA)
- Chemically Coating (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高温におけるステンレ
ス鋼の耐酸化性を改善する長期安定なコーティング液に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a long-term stable coating liquid which improves the oxidation resistance of stainless steel at high temperatures.
【０００２】[0002]
【従来の技術】ステンレス鋼は耐食性、耐熱性に優れた
金属材料であり、広く利用されている。しかしながら、
大気中や酸化性雰囲気において、ステンレス鋼は高温で
酸化されるため、このような条件での使用はかなりの注
意を要する。ステンレス鋼の高温酸化を防止できれば、
用途はさらに増えるものと考えられる。従来、この対策
法として、ステンレス鋼表面に酸化アルミニウム等の微
粒子を付着させる方法やステンレス鋼表面に金属アルコ
キシドを部分加水分解した溶液を塗布、熱分解して金属
酸化物の被膜を形成する方法等が知られている。これら
の方法はステンレス鋼の表面に緻密で耐熱性の高い金属
酸化物層を形成することにより、酸素のステンレス鋼内
部への侵入を防ぎ、耐熱酸化性を改善しようとしたもの
である。2. Description of the Related Art Stainless steel is a metal material having excellent corrosion resistance and heat resistance and is widely used. However,
Since stainless steel is oxidized at a high temperature in the air or in an oxidizing atmosphere, use under such conditions requires great care. If high temperature oxidation of stainless steel can be prevented,
Applications are expected to increase further. Conventionally, as a countermeasure against this, a method of adhering fine particles such as aluminum oxide to the surface of stainless steel, a method of applying a solution of partially hydrolyzed metal alkoxide to the surface of stainless steel, and thermally decomposing it to form a film of metal oxide, etc. It has been known. These methods are intended to improve the thermal oxidation resistance by forming a dense metal oxide layer having high heat resistance on the surface of stainless steel to prevent oxygen from entering the inside of the stainless steel.
【０００３】しかし、前記の酸化アルミニウム微粒子を
付着させる方法では、被膜が多孔性になり易く、再現性
の高い耐熱酸化性が得られないという問題点があった。
また、金属アルコキシドを部分加水分解した溶液でコー
トする方法では、溶液が不安定で寿命が短く、粘度変化
が著しいため、溶液の管理が困難で、再現性がないとい
う問題点がある。However, the above-mentioned method of adhering aluminum oxide fine particles has a problem that the coating film is likely to be porous and the reproducible thermal oxidation resistance cannot be obtained.
Further, the method of coating a solution in which a metal alkoxide is partially hydrolyzed has problems that the solution is unstable, the life is short, and the viscosity changes significantly, so that the solution is difficult to manage and reproducible.
【０００４】[0004]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、ステンレス鋼の高温酸化防止用コーティン
グ液の均質性と再現性がわるく、長期安定性に欠けると
いう点である。The problem to be solved by the present invention is that the homogeneity and reproducibility of the coating solution for high-temperature oxidation prevention of stainless steel are poor, and the long-term stability is lacking.
【０００５】[0005]
【課題を解決するための手段】上記の課題を解決するた
めの手段として、本発明者が、先に発明した、Ｚｒ−Ｏ
−Ｚｒ結合を有する、透明な酸化ジルコニウム系前駆体
ポリマーゲル状物を、カルボン酸の少量の添加により、
有機溶媒に溶解して、薄膜作製用溶液とすることを主要
な特徴とする。[Means for Solving the Problems] As a means for solving the above-mentioned problems, the present inventors have previously invented Zr-O.
By adding a small amount of a carboxylic acid, a transparent zirconium oxide-based precursor polymer gel material having a -Zr bond is added.
The main feature is that it is dissolved in an organic solvent to prepare a thin film-forming solution.
【０００６】酸化ジルコニウム系前駆体ポリマーゲル固
形物は、未反応アルコキシ基がほとんどないために、大
気中の湿分に対して、長期にわたり、きわめて安定であ
る。本発明者は研究の結果、有機溶媒中に前駆体ゲル状
物を入れ、カルボン酸を少量添加することにより、前駆
体ゲル状物が完全に溶解し、透明な溶液となることを見
出した。また、この溶液をステンレス鋼表面に塗布する
ことにより、緻密な酸化物膜が形成され、ステンレス鋼
の耐高温酸化性が著しく改善されることが見出された。
さらにこの溶液は長期にわたり安定であり、粘度の変化
もなく、均質性、再現性に優れたものであった。The zirconium oxide-based precursor polymer gel solid is extremely stable against moisture in the atmosphere for a long period of time because it has almost no unreacted alkoxy groups. As a result of research, the present inventor has found that by putting the precursor gel-like material in an organic solvent and adding a small amount of carboxylic acid, the precursor gel-like material is completely dissolved to form a transparent solution. It was also found that by applying this solution to the surface of stainless steel, a dense oxide film was formed and the high temperature oxidation resistance of stainless steel was significantly improved.
Further, this solution was stable for a long period of time, had no change in viscosity, and was excellent in homogeneity and reproducibility.
【０００７】すなわち、本発明はＺｒ−Ｏ−Ｚｒ結合を
主鎖とし、側鎖の一部にＯＣＯＲ基またはＯＣＯＲ基お
よびＯ（ＣＨ2 ）2 ＮＨ2 基を有する重合体から成る、
酸化ジルコニウム前駆体ゲル状物をカルボン酸及び有機
溶媒に溶解することを特徴とするステンレス鋼の高温酸
化防止用セラミックスコーティング液である。That is, the present invention comprises a polymer having a Zr-O-Zr bond as a main chain and having an OCOR group or an OCOR group and an O (CH 2 ) 2 NH 2 group in a part of a side chain,
A ceramic coating solution for high temperature oxidation prevention of stainless steel, which comprises dissolving a zirconium oxide precursor gel in a carboxylic acid and an organic solvent.
【０００８】[0008]
【作用】本発明で適用されるステンレス鋼はフェライト
系、オーステナイト系のいずれでも構わず、ステンレス
鋼の形状においても制約はなく、板状、棒状、管状のい
ずれの形状でも良い。酸化ジルコニウム前駆体ゲル状物
を溶解する有機溶媒は特に制約はないが、コーティング
がしやすく、コーティング後の乾燥のしやすい溶剤が好
ましい。具体的にはヘキサン、ヘプタン、シクロヘキサ
ン、メチルシクロヘキサン、ベンゼン、トルエン、キシ
レン、メタノール、エタノール、イソプロピルアルコー
ル、プロピルアルコール、ブタノール、イソブチルアル
コール、メチルセロソルブ、ジオキサン等が挙げられ
る。添加するカルボン酸としては、コーティング被膜の
残留炭素量を少なくするために炭素数４以下のものが好
ましい。添加量も同様な理由から、カルボン酸／ＺｒＯ
2 ≦２（モル比）が好ましい。カルボン酸の添加は前駆
体ポリマーゲルの末端基を溶媒親和性の高いＯＣＯＲ基
に置換することで、溶解度の低い前駆体ポリマーを溶媒
に溶解可能なものにしたと考えられる。この発明によ
り、従来のジルコニウムアルコキシドの加水分解を抑制
して調製された溶液に比べて、湿分に対して非常に安定
で、粘度変化のない長期使用可能なコーティング液を調
製するという目的を実現できた。The stainless steel applied in the present invention may be either ferritic or austenitic, and the shape of the stainless steel is not limited, and may be plate-shaped, rod-shaped or tubular. The organic solvent that dissolves the zirconium oxide precursor gel is not particularly limited, but a solvent that is easy to coat and easy to dry after coating is preferable. Specific examples include hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol, isobutyl alcohol, methyl cellosolve, dioxane and the like. The carboxylic acid added preferably has 4 or less carbon atoms in order to reduce the amount of residual carbon in the coating film. For the same reason, the addition amount is carboxylic acid / ZrO.
2 ≦ 2 (molar ratio) is preferable. It is considered that the addition of the carboxylic acid made the precursor polymer having low solubility soluble in the solvent by substituting the terminal group of the precursor polymer gel with the OCOR group having high solvent affinity. This invention realizes the purpose of preparing a coating liquid that is extremely stable to moisture and has a long-term use without viscosity change, as compared with a conventional solution prepared by suppressing hydrolysis of zirconium alkoxide. did it.
【０００９】上記コーティング液を用いてのステンレス
鋼表面へのコーティングはスピンコーティング法、ロー
ルコーティング法、スプレー法、ディッピング法等のい
ずれの方法でも良い。コーティングの後、乾燥（室温〜
１５０℃）及び焼成（３００〜１０００℃）により緻密
なＺｒＯ2 膜を得ることができる。このコーティング、
乾燥、焼成の工程を１回あるいは複数回繰り返すことに
より、膜厚の異なるＺｒＯ2 膜が得られる。耐高温酸化
性を向上させるためには、数回この工程を繰り返すこと
が望ましい。The stainless steel surface may be coated with the above coating solution by any of spin coating, roll coating, spraying, dipping and the like. After coating, dry (room temperature ~
A dense ZrO 2 film can be obtained by (150 ° C.) and baking (300 to 1000 ° C.). This coating,
By repeating the steps of drying and baking once or a plurality of times, ZrO 2 films having different film thickness can be obtained. It is desirable to repeat this step several times in order to improve the high temperature oxidation resistance.
【００１０】[0010]
【実施例１】ジルコニウムｎ−プロポキシドと酢酸及び
水（ジルコニウムｎ−プロポキシド：酢酸：水＝１：
１．３３：１〔ｍｏｌ比〕）の反応により、調製した酸
化ジルコニウム前駆体ゲル状物と酢酸及びｎ−ブチルア
ルコールを混合（前駆体ゲル状物：酢酸：ｎ−ブチルア
ルコール＝１０：１：１０〔重量比〕）することによ
り、前駆体ゲル状物は完全に溶解して、透明な溶液を形
成した。この溶液をコーティング液とし、ＳＵＳ４３０
ステンレス鋼材に浸漬塗布後、乾燥し、５００℃または
７００℃で１時間焼成した試験片を作製し、８００℃の
大気中に１０時間放置した場合の酸化増量を第１表に示
す。この表からわかるように、本発明のコーティング液
によるＺｒＯ2 コーティングはステンレス鋼材の耐高温
酸化性に極めて効果があった。また、調製した、透明な
コーティング液は、大気中においても、非常に安定で、
６ヵ月放置後も、粘度変化や沈澱生成といった変化は、
まったく見られなかった。Example 1 Zirconium n-propoxide, acetic acid and water (zirconium n-propoxide: acetic acid: water = 1: 1)
1.33: 1 [molar ratio]), the zirconium oxide precursor gel-like substance prepared was mixed with acetic acid and n-butyl alcohol (precursor gel-form: acetic acid: n-butyl alcohol = 10: 1: 10 [weight ratio]), the precursor gel-like substance was completely dissolved to form a transparent solution. This solution is used as a coating liquid, and SUS430
Table 1 shows the amount of increase in oxidation when a test piece was prepared by dipping and coating on a stainless steel material, drying and firing at 500 ° C. or 700 ° C. for 1 hour, and leaving it in the air at 800 ° C. for 10 hours. As can be seen from this table, the ZrO 2 coating with the coating liquid of the present invention was extremely effective in the high temperature oxidation resistance of stainless steel materials. In addition, the prepared transparent coating liquid is very stable even in the atmosphere,
Even after being left for 6 months, changes such as viscosity change and precipitate formation
I couldn't see it at all.
【００１１】[0011]
【表１】第１表 [Table 1] Table 1
【００１２】[0012]
【実施例２】ジルコニウムｎ−プロポキシドとエタノー
ルアミン（ジルコニウムｎ−プロポキシド：エタノール
アミン＝１：１〔ｍｏｌ比〕）の反応及びその溶液と酢
酸及び水（ジルコニウムｎ−プロピキシド：酢酸：水＝
１：１：１．５〔ｍｏｌ比〕）の反応により調製した酸
化ジルコニウム前駆体ゲル状物を酢酸及びｎ−ブチルア
ルコールと混合（前駆体ゲル状物：酢酸：エチルアルコ
ール＝１０：０．４：５〔重量比〕）することにより、
前駆体ゲル状物は完全に溶解して、透明な溶液を形成し
た。この溶液をコーティング液とし、ＳＵＳ４３０ステ
ンレス鋼材に浸漬塗布後、乾燥し、５００℃または７０
０℃で１時間焼成した試験片を作製し、８００℃の大気
中に１０時間放置した場合の酸化増量を第２表に示す。
この表からわかるように、本発明のコーティング液によ
るＺｒＯ2 コーティングはステンレス鋼材の耐高温酸化
性に極めて効果があった。また、調製した、透明なコー
ティング液は、大気中においても、非常に安定で、６ヵ
月放置後も、粘度変化や沈澱生成といった変化は、まっ
たく見られなかった。Example 2 Reaction of zirconium n-propoxide with ethanolamine (zirconium n-propoxide: ethanolamine = 1: 1 [molar ratio]) and its solution with acetic acid and water (zirconium n-propoxide: acetic acid: water =)
1: 1: 1.5 [molar ratio]), the zirconium oxide precursor gel-like material prepared by the reaction was mixed with acetic acid and n-butyl alcohol (precursor gel-like material: acetic acid: ethyl alcohol = 10: 0.4). : 5 [weight ratio])
The precursor gel completely dissolved to form a clear solution. This solution is used as a coating solution, applied by dipping on SUS430 stainless steel material, and then dried to 500 ° C or 70 ° C.
Table 2 shows the amount of increased oxidation when a test piece was prepared by firing at 0 ° C for 1 hour and left in the air at 800 ° C for 10 hours.
As can be seen from this table, the ZrO 2 coating with the coating liquid of the present invention was extremely effective in the high temperature oxidation resistance of stainless steel materials. The prepared transparent coating solution was very stable even in the air, and no change such as viscosity change or precipitate formation was observed even after standing for 6 months.
【００１３】[0013]
【表２】第２表 [Table 2] Table 2
【００１４】[0014]
【発明の効果】本発明のステンレス鋼用コーティング液
は高温におけるステンレス鋼の耐酸化性を大幅に向上で
きるため、高温でのステンレス鋼の使用用途をさらに大
きく拡げることが可能となる。また、このコーティング
液は、従来のアルコキシド溶液とは異なり、大気中の湿
分の影響を受けることなく、安定に長期間の使用及び保
存ができるという利点もあり、その工業的な意義は大き
い。EFFECTS OF THE INVENTION Since the coating solution for stainless steel of the present invention can greatly improve the oxidation resistance of stainless steel at high temperature, the use of stainless steel at high temperature can be further expanded. Also, unlike the conventional alkoxide solution, this coating solution has an advantage that it can be stably used and stored for a long period of time without being affected by moisture in the atmosphere, and its industrial significance is great.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年６月１８日[Submission date] June 18, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】[0010]
【実施例１】ジルコニウムｎ−プロポキシドと酢酸及び
水（ジルコニウムｎ−プロポキシド：水：酢酸＝１：
１．３３：１〔ｍｏｌ比〕）の反応により、調製した酸
化ジルコニウム前駆体ゲル状物と酢酸及びｎ−ブチルア
ルコールを混合（前駆体ゲル状物：酢酸：ｎ−ブチルア
ルコール＝１０：１：１０〔重量比〕）することによ
り、前駆体ゲル状物は完全に溶解して、透明な溶液を形
成した。この溶液をコーティング液とし、ＳＵＳ４３０
ステンレス鋼材に浸漬塗布後、乾燥し、５００℃または
７００℃で１時間焼成した試験片を作製し、８００℃の
大気中に１０時間放置した場合の酸化増量を第１表に示
す。この表からわかるように、本発明のコーティング液
によるＺｒＯ２コーティングはステンレス鋼材の耐高温
酸化姓に極めて効果があった。また、調製した、透明な
コーティング液は、大気中においても、非常に安定で、
６ヵ月放置後も、粘度変化や沈澱生成といった変化は、
まったく見られなかった。Example 1 Zirconium n-propoxide, acetic acid and water (zirconium n-propoxide: water: acetic acid = 1:
1.33: 1 [molar ratio]), the zirconium oxide precursor gel-like substance prepared was mixed with acetic acid and n-butyl alcohol (precursor gel-form: acetic acid: n-butyl alcohol = 10: 1: 10 [weight ratio]), the precursor gel-like substance was completely dissolved to form a transparent solution. This solution is used as a coating liquid, and SUS430
Table 1 shows the amount of increase in oxidation when a test piece was prepared by dipping and coating on a stainless steel material, drying and firing at 500 ° C. or 700 ° C. for 1 hour, and leaving it in the air at 800 ° C. for 10 hours. As can be seen from this table, the ZrO 2 coating by the coating liquid of the present invention was extremely effective in high temperature oxidation resistance of stainless steel. In addition, the prepared transparent coating liquid is very stable even in the atmosphere,
Even after being left for 6 months, changes such as viscosity change and precipitate formation
I couldn't see it at all.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ２３Ｃ 18/12 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location // C23C 18/12
Claims (2)
ＯＣＯＲ基（ここで、Ｒは炭素数１〜４までの直鎖また
は分岐のあるアルキル基を示す）を有する重合体から成
る、酸化ジルコニウム前駆体ゲル状物をカルボン酸及び
有機溶媒に溶解することを特徴とするステンレス鋼の高
温酸化防止用セラミックスコーティング液。1. From a polymer having a Zr—O—Zr bond as a main chain and an OCOR group (wherein R represents a linear or branched alkyl group having 1 to 4 carbon atoms) in a side chain. And a zirconium oxide precursor gel-like material dissolved in a carboxylic acid and an organic solvent.
一部にＯＣＯＲ基およびＯ（ＣＨ2 ）2 ＮＨ2 基を有す
る重合体から成る、酸化ジルコニウム前駆体ゲル状物を
カルボン酸及び有機溶媒に溶解することを特徴とするス
テンレス鋼の高温酸化防止用セラミックスコーティング
液。2. A zirconium oxide precursor gel comprising a polymer having a Zr—O—Zr bond as a main chain and having an OCOR group and an O (CH 2 ) 2 NH 2 group in a part of its side chain is carbonized. A ceramic coating solution for high temperature oxidation prevention of stainless steel, which is dissolved in an acid and an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25448392A JPH06101067A (en) | 1992-09-24 | 1992-09-24 | Ceramic coating liquid for preventing high temperature oxidation of stainless steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25448392A JPH06101067A (en) | 1992-09-24 | 1992-09-24 | Ceramic coating liquid for preventing high temperature oxidation of stainless steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06101067A true JPH06101067A (en) | 1994-04-12 |
Family
ID=17265684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25448392A Pending JPH06101067A (en) | 1992-09-24 | 1992-09-24 | Ceramic coating liquid for preventing high temperature oxidation of stainless steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06101067A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2053144A1 (en) * | 2006-08-09 | 2009-04-29 | Nihon Parkerizing Co., Ltd. | Method for quenching of steel member, quenched steel member, and agent for protecting quenched surface |
| JP2009161840A (en) * | 2008-01-10 | 2009-07-23 | Nagoya City | Water-based zirconium corrosion prevention agent, corrosion prevention method for metal using the same, and method for producing water-based zirconium corrosion prevention agent |
| KR20200019109A (en) * | 2016-12-22 | 2020-02-21 | 엘렉트리씨트 드 프랑스 | Sol-Gel Process for Making Corrosion Resistant Coatings on Metal Substrates |
| WO2020129306A1 (en) | 2018-12-21 | 2020-06-25 | 第一稀元素化学工業株式会社 | Zirconium-containing alcohol solution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60104132A (en) * | 1983-11-12 | 1985-06-08 | Toyobo Co Ltd | Preparation of polymer |
| JPS63293178A (en) * | 1987-05-25 | 1988-11-30 | Hakusui Kagaku Kogyo Kk | Metal-containing composition for inhibiting oxidation of metallic material at high temperature and production thereof |
| JPH01149967A (en) * | 1987-12-07 | 1989-06-13 | Shoei Kagaku Kogyo Kk | Formation of thin film |
| JPH04280817A (en) * | 1991-03-08 | 1992-10-06 | Tsuchiya:Kk | Production of thin film from gelatinous material of zirconium oxide-based precursor |
-
1992
- 1992-09-24 JP JP25448392A patent/JPH06101067A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60104132A (en) * | 1983-11-12 | 1985-06-08 | Toyobo Co Ltd | Preparation of polymer |
| JPS63293178A (en) * | 1987-05-25 | 1988-11-30 | Hakusui Kagaku Kogyo Kk | Metal-containing composition for inhibiting oxidation of metallic material at high temperature and production thereof |
| JPH01149967A (en) * | 1987-12-07 | 1989-06-13 | Shoei Kagaku Kogyo Kk | Formation of thin film |
| JPH04280817A (en) * | 1991-03-08 | 1992-10-06 | Tsuchiya:Kk | Production of thin film from gelatinous material of zirconium oxide-based precursor |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2053144A1 (en) * | 2006-08-09 | 2009-04-29 | Nihon Parkerizing Co., Ltd. | Method for quenching of steel member, quenched steel member, and agent for protecting quenched surface |
| EP2053144A4 (en) * | 2006-08-09 | 2011-06-29 | Nihon Parkerizing | Method for quenching of steel member, quenched steel member, and agent for protecting quenched surface |
| JP2009161840A (en) * | 2008-01-10 | 2009-07-23 | Nagoya City | Water-based zirconium corrosion prevention agent, corrosion prevention method for metal using the same, and method for producing water-based zirconium corrosion prevention agent |
| KR20200019109A (en) * | 2016-12-22 | 2020-02-21 | 엘렉트리씨트 드 프랑스 | Sol-Gel Process for Making Corrosion Resistant Coatings on Metal Substrates |
| US11519072B2 (en) | 2016-12-22 | 2022-12-06 | Electricite De France | Sol-gel method for producing an anti-corrosion coating on a metal substrate |
| WO2020129306A1 (en) | 2018-12-21 | 2020-06-25 | 第一稀元素化学工業株式会社 | Zirconium-containing alcohol solution |
| KR20210008534A (en) | 2018-12-21 | 2021-01-22 | 다이치 키겐소 카가쿠 코교 컴퍼니 리미티드 | Alcohol solution containing zirconium |
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