JP3225473B2 - Method for producing thiourea dioxide with improved stability and flowability - Google Patents
Method for producing thiourea dioxide with improved stability and flowabilityInfo
- Publication number
- JP3225473B2 JP3225473B2 JP09036893A JP9036893A JP3225473B2 JP 3225473 B2 JP3225473 B2 JP 3225473B2 JP 09036893 A JP09036893 A JP 09036893A JP 9036893 A JP9036893 A JP 9036893A JP 3225473 B2 JP3225473 B2 JP 3225473B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- tud
- soluble polymer
- thiourea dioxide
- aqueous solution
- 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 - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は二酸化チオ尿素の安定性
及び流動性を改善する方法に関する。The present invention relates to a method for improving the stability and flowability of thiourea dioxide.
【０００２】[0002]
【従来の技術とその課題】二酸化チオ尿素（以下ＴＵＤ
と略記する）はアミノメタンスルフィン酸又はホルムア
ミジンスルフィン酸とも言われ、工業的に市販されてお
り白色粉末として入手し得る。2. Description of the Related Art Thiourea dioxide (hereinafter referred to as TUD)
Is also referred to as aminomethanesulfinic acid or formamidinesulfinic acid, and is commercially available industrially and can be obtained as a white powder.
【０００３】ＴＵＤは、その水溶液をアルカリ性にした
り、加熱することにより還元性を発揮し、その還元力は
極めて大きい。[0003] TUD exhibits reducibility by making its aqueous solution alkaline or heated, and its reductive power is extremely large.
【０００４】従ってその用途分野としては、バット染料
用還元剤、分散染料で染色した繊維の還元洗浄剤、各種
染料で染色した繊維の脱色剤、染色機械の缶体洗浄剤、
ケラチン繊維の防縮加工剤、タンパク質繊維、ポリアミ
ド繊維及びフェノール樹脂繊維の漂白剤、ポリアクリル
ニトリル繊維及びポリビニルアルコール繊維の製造工程
での脱色剤、各種染料の抜染剤、着色抜染剤、染色堅牢
度向上剤等繊維工業分野への応用、並びにパルプ漂白
剤、有機アミンの酸化防止剤、重合触媒、写真用感光助
剤、洗剤の一成分、金属イオンの還元剤、有機化合物に
属するニトロ化合物のヒドラゾン化合物又はアミンへの
還元剤、ケトンの二級アルコールへの還元剤、アルデヒ
ドの一級アルコールへの還元剤、ジサルフアイドのチオ
ールへの還元剤等多岐に亘っている。[0004] Accordingly, its fields of application include reducing agents for vat dyes, reduction cleaning agents for fibers dyed with disperse dyes, decolorizing agents for fibers dyed with various dyes, cleaning agents for dyeing machine cans,
Pre-shrinking agent for keratin fiber, bleaching agent for protein fiber, polyamide fiber and phenol resin fiber, decolorizing agent in the production process of polyacrylonitrile fiber and polyvinyl alcohol fiber, discharging agent for various dyes, coloring discharging agent, improving color fastness Pulp bleach, antioxidants for organic amines, polymerization catalysts, photosensitizers, one component of detergents, reducing agents for metal ions, hydrazone compounds of nitro compounds belonging to organic compounds Alternatively, there are a wide variety of agents such as reducing agents for amines, reducing agents for secondary alcohols of ketones, reducing agents for primary alcohols of aldehydes, and reducing agents for thiols of disulfides.
【０００５】しかしながら市販されているほとんどのＴ
ＵＤは、流動性が悪く、保存中に固結し易く、使用に当
たって軟解を要し多大な手間がかかる。またＴＵＤは常
温では安定な化合物であるが高温になると激しく分解す
る。時には軟解作業時や充填作業時に発生する摩擦熱に
よって分解することもあり、流動性の悪さが取扱い面で
しばしばトラブルの原因となっている。However, most commercially available T
UD has poor fluidity, tends to solidify during storage, requires a softening upon use, and requires a great deal of labor. TUD is a stable compound at room temperature, but decomposes violently at high temperatures. Sometimes it is decomposed by frictional heat generated at the time of softening work or filling work, and poor fluidity often causes troubles in handling.
【０００６】更にＴＵＤは保存中に徐々に酸を生成しな
がら黄変化することも知られている。黄変化したＴＵＤ
は還元力の低下を招き、酸やアルカリにも不溶のイオウ
を生じるため、流動性の良好な固結しない安定なＴＵＤ
の要求が増々高まってきている。[0006] It is also known that TUD changes its yellow color while producing acid gradually during storage. TUD that changed yellow
Causes a reduction in reducing power and generates sulfur insoluble in acids and alkalis.
Demands are increasing.
【０００７】ＴＵＤの製造方法としては、チオ尿素と過
酸化水素を溶媒中で反応させて得る方法が数多く報告が
されており、これらの方法は使用されている溶媒の種類
により非水系溶媒と水溶媒に大別されるが、いずれも収
率向上や純度向上に関するものであり、安定性や流動性
の向上についての提案はほとんどみられない。一般に粒
径が大きくなれば流動性は向上するがＴＵＤの場合、Ｔ
ＵＤの溶解度は室温で約３ｗｔ％と小さく、粒径の増大
に伴い溶解速度が著しく低下するという欠点を有してい
る。As a method for producing TUD, there have been reported many methods for obtaining thiourea and hydrogen peroxide by reacting them in a solvent. These methods depend on the type of solvent used, and include a nonaqueous solvent and water. Although they are roughly classified into solvents, they are all related to improvement in yield and purity, and there are few proposals for improvement in stability and fluidity. Generally, as the particle size increases, the fluidity improves, but in the case of TUD, T
The solubility of UD is as low as about 3 wt% at room temperature, and has a disadvantage that the dissolution rate is significantly reduced as the particle size increases.
【０００８】本発明者らは、流動性を向上させても溶解
速度が低下せず、固結しない安定なＴＵＤを製造する方
法について鋭意研究を重ねた結果、効果の顕著な本発明
に到達した。The present inventors have conducted intensive studies on a method for producing a stable TUD which does not decrease the dissolution rate even if the fluidity is improved and does not solidify, and as a result, the present invention has achieved a remarkable effect. .
【０００９】[0009]
【課題を解決するための手段】本発明はＴＵＤの結晶を
水溶性重合体の水溶液で処理することを特徴とする安定
性及び流動性の向上したＴＵＤの製造法である。SUMMARY OF THE INVENTION The present invention is a process for producing a TUD having improved stability and fluidity, which comprises treating a TUD crystal with an aqueous solution of a water-soluble polymer.
【００１０】本発明に供するＴＵＤは特に限定されない
が、通常ＴＵＤの製造工程を経て得られたＴＵＤスラリ
ーを脱液して得られた湿潤状のＴＵＤ結晶又はそれを乾
燥したＴＵＤ結晶が用いられる。The TUD used in the present invention is not particularly limited, but a wet TUD crystal obtained by dewatering a TUD slurry obtained through a TUD manufacturing process or a TUD crystal obtained by drying the same is used.
【００１１】本発明はかかるＴＵＤ結晶を水溶性重合体
の水溶液で処理するものである。本発明で使用される水
溶性重合体は非アルカリ性のものが好ましく、具体例と
しては、ポリビニルアルコール、ポリエチレングリコー
ル、ポリビニルピロリドン、ポリエチレンオキサイド等
の合成品、ヒドロキシプロピルセルロース、メチルセル
ロース、ヒドロキシエチルセルロース、エチルセルロー
ス等の半合成品、デキストリン、サイクロデキストリ
ン、グルコース、マルトース、マルトトリオース、マル
トテトラオース、マルトペンタオース、マルトヘキサオ
ース、オリゴ糖、でんぷん等の天然品がある。The present invention is to treat such TUD crystals with an aqueous solution of a water-soluble polymer. The water-soluble polymer used in the present invention is preferably a non-alkaline polymer. Specific examples thereof include polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone, synthetic products such as polyethylene oxide, hydroxypropylcellulose, and methylcell.
There are semi-synthetic products such as loose , hydroxyethylcellulose and ethylcellulose, and natural products such as dextrin, cyclodextrin, glucose, maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose, oligosaccharides and starch.
【００１２】水溶性重合体の使用量はＴＵＤに対し通常
０．０５〜５重量％、好ましくは０．５〜２重量％であ
る。少なすぎると効果がなく、また多すぎると経済的で
ない。The amount of the water-soluble polymer used is usually 0.05 to 5% by weight, preferably 0.5 to 2% by weight, based on TUD. Too little is ineffective and too much is not economical.
【００１３】水溶性重合体は処理時に水溶液であること
を要する。通常予め水溶液にして供されるが、処理時に
水分を共存させることによって水溶液化してもよい。The water-soluble polymer must be an aqueous solution at the time of processing. Usually, an aqueous solution is provided beforehand, but the aqueous solution may be formed by coexisting water during the treatment.
【００１４】処理手段としては水溶性重合体の水溶液を
ＴＵＤ結晶と混合するかスプレー等で噴霧した後、この
ＴＵＤ結晶を流動層乾燥や振動流動乾燥機等を用いて流
動下に乾燥させたり、押し出し、転動、圧縮、攪拌、又
は転動流動等の造粒技術で一般的に用いられている造粒
機に供給した後乾燥させる方法が好ましい。また遠心分
離機中にスプレー噴霧したり、乾燥機内にスプレー噴霧
する等の方法も好ましい。As a treatment means, an aqueous solution of a water-soluble polymer is mixed with a TUD crystal or sprayed or the like, and then the TUD crystal is dried under a fluidized state using a fluidized bed dryer or a vibrating fluidized dryer, or the like. A method of drying after supplying to a granulator generally used in a granulation technique such as extrusion, tumbling, compression, stirring or tumbling flow is preferable. Further, a method of spraying into a centrifuge or spraying into a dryer is also preferable.
【００１５】このような処理によりＴＵＤ結晶中に存在
した１００μ以下の微結晶の割合が減少すると共に、溶
解速度の低下を伴うことなく流動性が向上し、さらに保
存中の黄変化や酸分の上昇の防止性といった安定性も向
上するのである。By such a treatment, the proportion of microcrystals of 100 μm or less present in the TUD crystal is reduced, the flowability is improved without lowering the dissolution rate, and yellowing and acid content during storage are further improved. It also improves stability, such as the ability to prevent the rise.
【００１６】以下に本発明の実施例を挙げるが、これは
例示を目的とするものであって、これにより本発明を限
定するものではない。Examples of the present invention will be described below, but these are for the purpose of illustration, and do not limit the present invention.
【００１７】[0017]
【実施例】ＴＵＤスラリーより脱液して得られたＴＵＤ
湿結晶２．５ｋｇに対して、水溶性重合体の水溶液を混
合した後、流動層乾燥機にて乾燥した。得られたＴＵＤ
について平均粒径、流動性、固結度及び水溶安定度を測
定した結果を表１に示した。[Example] TUD obtained by dewatering from TUD slurry
After mixing the aqueous solution of the water-soluble polymer with 2.5 kg of the wet crystals, the mixture was dried with a fluid bed dryer. Obtained TUD
Table 1 shows the results of measuring the average particle size, fluidity, degree of consolidation, and stability of water solubility of the samples.
【００１８】（ａ）ｂ値；日本電色工業株式会社製 測
色色差計モデル１００１ＤＰを用いて測定した。 （ＣＯＬＯＲ ＡＮＤ ＣＯＬＯＲ ＤＩＦＦＥＲＥＮ
ＣＥ ＭＥＴＥＲ）ｂ値が正値を示すと黄色を帯び負値
を示すと青味を帯びていることを示す。(A) b value: Measured using a colorimetric colorimeter model 1001DP manufactured by Nippon Denshoku Industries Co., Ltd. (COLOR AND COLOR DIFFEREN
If the CE METER) b value shows a positive value, it indicates yellowish, and if it indicates a negative value, it indicates blueish.
【００１９】（ｂ）酸分はサンプル５ｇを取り５０ｍｌ
の純水とメチルレッドを指示薬としＮ／１０ ＮａＯＨ
で滴定した。(B) For the acid content, take 5 g of a sample and take 50 ml.
N / 10 NaOH using pure water and methyl red as indicators
Was titrated.
【００２０】（ｃ）ＴＵＤは高温になる程安定性が悪い
為、加速試験として５０℃保存とした。(C) Since the stability of TUD becomes worse as the temperature increases, it was stored at 50 ° C. as an acceleration test.
【００２１】（ｄ）安息角は筒井理化学器械株式会社製
Ａ．Ｂ．Ｄ粉体特性測定器（Ａ．Ｂ．Ｄ−７２形）を
用いて測定した。(D) The angle of repose is calculated by A. Tsutsui Chemical Instruments Co., Ltd. B. It measured using the D powder characteristic measuring device (ABD-72 type).
【００２２】（ｅ）固結度は８５ｍｍ×１２０ｍｍ厚さ
０．２ｍｍの高密度ポリエチレン製の袋にサンプル２０
０ｇを充填し上部より４ｔ／ｍ２の圧力をかけ３週間放
置その後固結したサンプルを２ｃｍ角に切り取り破壊す
るまでの硬度を測定した（筒井理化学器械 簡易粒体硬
度計）。(E) The consolidation degree was 85 mm × 120 mm, and the sample 20 was placed in a high-density polyethylene bag having a thickness of 0.2 mm.
After filling with 0 g, applying a pressure of 4 t / m 2 from the upper part, and leaving it for 3 weeks, the solidified sample was cut into 2 cm squares, and the hardness up to breaking was measured (Tsutsui Rikakiki Simplified Particle Hardness Tester).
【００２３】（ｆ）マルトテトラオースはマルトテトラ
オース ５０％、マルトトリオース８％、マルトース
７％、グルコース ２％、マルトペンタオース ２％、
オリゴ糖テキストリン ３０％から成る。Ｒｕｎ ７〜
１２のマルトオリゴ糖はグルコース ４．４％、マルト
ース １３．４％、マルトトリオース ７．９％、マル
トテトラオース ７．６％、マルトペンタオース ７．
６％、マルトヘキサオース＋マルトヘプタオース ４
０．０％、その他の糖 １９．１％から成るものであ
る。(F) Maltotetraose is maltotetraose 50%, maltotriose 8%, maltose
7%, glucose 2%, maltopentaose 2%,
Oligosaccharide textulin consists of 30%. Run 7 ~
Twelve maltooligosaccharides are glucose 4.4%, maltose 13.4%, maltotriose 7.9%, maltotetraose 7.6%, maltopentaose 7.
6%, maltohexaose + maltoheptaose 4
0.01%, other sugars 19.1%.
【００２４】（ｇ）ＲＵＮ １３のＰＥＧは重合度２
０，０００、Ｎｏ．１４のＰＥＧは重合度５，０００。
Ｒｕｎ １５のＰＶＡはケン化度９８．５±０．５ｍｏ
ｌ％、Ｒｕｎ １６はケン化度８８．０±１．５ｍｏｌ
％、重合度は共に５００。(G) PEG of RUN 13 has a degree of polymerization of 2
000, No. PEG of 14 has a degree of polymerization of 5,000.
Run 15 PVA has a saponification degree of 98.5 ± 0.5 mo
1%, Run 16 has a saponification degree of 88.0 ± 1.5 mol
% And the degree of polymerization are both 500.
【００２５】（ｈ）Ｒｕｎ １７重合度２７００〜７５
００、Ｒｕｎ １８は１５，０００〜２０，０００。(H) Run 17 polymerization degree 2700-75
00, Run 18 is 15,000 to 20,000.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
フロントページの続き (56)参考文献 特開 平４−145064（ＪＰ，Ａ) 特開 昭48−46577（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 381/14 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuation of the front page (56) References JP-A-4-145064 (JP, A) JP-A-48-46577 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 381 / 14 CA (STN) REGISTRY (STN)
Claims (4)
水溶液で処理することを特徴とする安定性及び流動性の
向上した二酸化チオ尿素の製造法。1. A method for producing thiourea dioxide having improved stability and fluidity, comprising treating crystals of thiourea dioxide with an aqueous solution of a water-soluble polymer.
に対し０．０５〜５重量％である請求項１記載の方法。2. The method according to claim 1, wherein the amount of the water-soluble polymer used is 0.05 to 5% by weight based on thiourea dioxide.
溶液を該結晶に混合又はスプレーし且つ該結晶を流動状
態で乾燥させるか又は造粒機を用いる造粒処理の後乾燥
させることによって行なう請求項１又は２記載の方法。3. The treatment with an aqueous solution of a water-soluble polymer is carried out by mixing or spraying the aqueous solution with the crystals and drying the crystals in a fluid state or by drying after a granulation treatment using a granulator. The method according to claim 1.
ポリエチレングリコール、ポリビニルピロリドン、ポリ
エチレンオキサイド、ヒドロキシプロピルセルロース、
メチルセルロース、ヒドロキシエチルセルロース、エチ
ルセルロース、デキストリン、サイクロデキストリン、
グルコース、マルトース、マルトトリオース、マルトテ
トラオース、マルトペンタオース、マルトヘキサオー
ス、オリゴ糖及びでんぷんからなる群から選ばれたもし
くは２種以上である請求項１〜３のいづれか１項記載の
方法。4. The water-soluble polymer is polyvinyl alcohol,
Polyethylene glycol, polyvinylpyrrolidone, polyethylene oxide, hydroxypropylcellulose,
Methylcellulose , hydroxyethylcellulose, ethylcellulose, dextrin, cyclodextrin,
The method according to any one of claims 1 to 3, wherein the method is selected from the group consisting of glucose, maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose, oligosaccharide and starch, or two or more thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09036893A JP3225473B2 (en) | 1993-03-12 | 1993-03-12 | Method for producing thiourea dioxide with improved stability and flowability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09036893A JP3225473B2 (en) | 1993-03-12 | 1993-03-12 | Method for producing thiourea dioxide with improved stability and flowability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06263721A JPH06263721A (en) | 1994-09-20 |
| JP3225473B2 true JP3225473B2 (en) | 2001-11-05 |
Family
ID=13996615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09036893A Expired - Fee Related JP3225473B2 (en) | 1993-03-12 | 1993-03-12 | Method for producing thiourea dioxide with improved stability and flowability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3225473B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5208621A (en) * | 1989-03-06 | 1993-05-04 | Minolta Camera Kabushiki Kaisha | Photographic sysetm capable of recording therein photographing data and reading out the same and film structure for use in the photographic system |
| AT401274B (en) * | 1993-11-23 | 1996-07-25 | Degussa Austria Gmbh | METHOD FOR BLEACHING TEXTILE ARTICLES |
| NZ335804A (en) * | 1998-05-20 | 2000-12-22 | Degussa | Bleaching formulation comprising formamidinesulfinic acid, an anti-coating agent and silica |
| DE10303023A1 (en) * | 2003-01-27 | 2004-08-05 | Degussa Ag | Compositions containing formamidine sulfinic acid, process for their preparation and their use |
| CN109574896A (en) * | 2018-12-12 | 2019-04-05 | 濮阳宏业环保新材料股份有限公司 | A kind of high stability thiourea dioxide and its production technology |
-
1993
- 1993-03-12 JP JP09036893A patent/JP3225473B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06263721A (en) | 1994-09-20 |
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