JP3305112B2 - Stabilized sodium percarbonate particles and method for producing the same - Google Patents
Stabilized sodium percarbonate particles and method for producing the sameInfo
- Publication number
- JP3305112B2 JP3305112B2 JP09170394A JP9170394A JP3305112B2 JP 3305112 B2 JP3305112 B2 JP 3305112B2 JP 09170394 A JP09170394 A JP 09170394A JP 9170394 A JP9170394 A JP 9170394A JP 3305112 B2 JP3305112 B2 JP 3305112B2
- Authority
- JP
- Japan
- Prior art keywords
- sodium percarbonate
- particles
- coating
- aqueous solution
- sodium
- 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】本発明は保存安定性の高い過炭酸
ナトリウムの粒子およびその製造方法に関する。本発明
の過炭酸ナトリウム粒子は漂白剤組成物または漂白成分
を含む家庭用洗剤等に好適に利用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to sodium percarbonate particles having high storage stability and a method for producing the same. The sodium percarbonate particles of the present invention are suitably used for a bleaching composition or a household detergent containing a bleaching component.
【０００２】[0002]
【従来の技術】過炭酸ナトリウム、過ホウ酸ナトリウム
のような過酸化水素化付加化合物が粉末状の洗浄剤組成
物（家庭用合成洗剤）に漂白成分として配合されること
が知られている。過炭酸ナトリウム、過ホウ酸ナトリウ
ム等は洗濯に際して溶解し、分解して漂白作用を発揮す
る。この場合過ホウ酸ナトリウムは低温での溶解速度が
遅く、特に水あるいはぬるま湯等を主として使用する我
が国の事情においては洗剤に配合する漂白成分としては
漂白効果の点で余り好ましくない。一方、過炭酸ナトリ
ウムは低温における溶解速度がはやく漂白効果を充分に
発揮出来ることから近年急激に需要が増大しつつある。2. Description of the Related Art It is known that hydrogen peroxide adducts such as sodium percarbonate and sodium perborate are blended as a bleaching component in a powdery detergent composition (a household synthetic detergent). Sodium percarbonate, sodium perborate, and the like dissolve during washing and decompose to exert a bleaching action. In this case, the dissolution rate of sodium perborate at a low temperature is low. Particularly in Japan in which water or lukewarm water is mainly used, it is not very preferable as a bleaching component as a bleaching component to be added to a detergent. On the other hand, the demand for sodium percarbonate is rapidly increasing in recent years because the dissolution rate at a low temperature is fast and the bleaching effect can be sufficiently exhibited.
【０００３】しかしながら、過炭酸ナトリウムは過ホウ
酸ナトリウムに比べ水分に対して鋭敏であり、洗浄剤組
成物中の水分、あるいは空気中の湿気、水分によっても
常温で比較的分解され易い。又洗浄剤組成物中にはゼオ
ライト、酵素等の過炭酸ナトリウムの分解を促進する物
質も含まれており、これらと接触して分解されやすい傾
向がある。そこで従来より過炭酸ナトリウムの分解を防
止、抑制し、安定化した過炭酸ナトリウムを得る方法が
種々提案されている。即ち、過炭酸ナトリウム製造の際
の晶出時に安定剤（メタケイ酸ソーダ、マグネシウム化
合物、キレート剤等）を添加して安定化を図る、過炭酸
ナトリウムの湿潤造粒時にバインダーもしくは添加剤
（りん酸塩等）を添加して安定化を図る、乾燥された過
炭酸ナトリウム粒子の表面を被覆して安定化を図るなど
である。その中でも過炭酸ナトリウムの粒子を種々の被
覆剤で被覆する第３の方法が最も有力である。被覆剤と
してはアルカリ土類金属塩、あるいは炭酸ナトリウムと
硫酸ナトリウムとの混合塩等、種々提案されている。[0003] However, sodium percarbonate is more sensitive to moisture than sodium perborate, and is relatively easily decomposed at room temperature by moisture in the detergent composition or moisture in the air. The detergent composition also contains substances that promote the decomposition of sodium percarbonate such as zeolites and enzymes, and tends to be easily decomposed by contact with these substances. Therefore, various methods for obtaining stabilized sodium percarbonate by preventing and suppressing the decomposition of sodium percarbonate have conventionally been proposed. That is, a stabilizer (sodium metasilicate, magnesium compound, chelating agent, etc.) is added during crystallization during the production of sodium percarbonate to stabilize it. A binder or additive (phosphoric acid) is added during wet granulation of sodium percarbonate. Salt, etc.) for stabilization, or to coat the surface of the dried sodium percarbonate particles for stabilization. Among them, the third method of coating sodium percarbonate particles with various coating agents is most effective. Various coating agents have been proposed, such as alkaline earth metal salts or mixed salts of sodium carbonate and sodium sulfate.
【０００４】例えばアルカリ土類金属塩で被覆する方法
としては特公昭５７−７０８１号の方法が知られてい
る。この方法は過炭酸ナトリウム粒子の表面をアルカリ
土類金属塩水溶液と接触反応させ、過炭酸ナトリウム表
面上に炭酸アルカリ土類金属塩から成る膜を形成させる
方法であり、この方法はたしかに過炭酸ナトリウムの安
定性を幾分高める事が出来るが次のような２つの欠点を
有している。１つは過炭酸ナトリウム中の炭酸ナトリウ
ムとアルカリ土類金属塩とが反応し、遊離した過酸化水
素が乾燥時に分解するので過炭酸ナトリウムとしての有
効成分が減少する。もう１つは不溶性の炭酸アルカリ土
類金属塩が生成する事により溶解速度が著しく遅くな
り、実用的でない。一方炭酸ナトリウムと硫酸ナトリウ
ムとの混合塩で被覆する（特公昭５８−２４３６１）方
法の場合は溶解性は比較的良いが、洗剤との配合安定性
は未被覆の過炭酸ナトリウムに比較してわずかに向上し
ているものの実用レベルには達していない。[0004] For example, as a method of coating with an alkaline earth metal salt, the method of Japanese Patent Publication No. 57-7081 is known. In this method, the surface of sodium percarbonate particles is contacted and reacted with an aqueous solution of an alkaline earth metal salt to form a film made of an alkaline earth metal salt on the surface of the sodium percarbonate. Can be somewhat improved, but has the following two disadvantages. One is that sodium carbonate in sodium percarbonate reacts with an alkaline earth metal salt, and the liberated hydrogen peroxide is decomposed during drying, so that the active ingredient as sodium percarbonate is reduced. The other is that the dissolution rate becomes extremely slow due to the formation of an insoluble alkaline earth metal carbonate, which is not practical. On the other hand, in the case of coating with a mixed salt of sodium carbonate and sodium sulfate (Japanese Patent Publication No. 58-24361), the solubility is relatively good, but the blending stability with detergent is slightly lower than that of uncoated sodium percarbonate. However, it has not reached the practical level.
【０００５】[0005]
【発明が解決しようとする課題】過炭酸ナトリウム成分
の安定性と過炭酸ナトリウム粒子の溶解性という相反す
る要素を同時に満足させることは困難である。特に、洗
剤成分と配合すると、過炭酸ナトリウム成分の安定性が
低下する傾向がある。本発明の目的は、特に洗剤との配
合安定性に優れた安定性を有し、溶解速度の大きい過炭
酸ナトリウム粒子を提供することである。It is difficult to simultaneously satisfy the conflicting factors of the stability of the sodium percarbonate component and the solubility of sodium percarbonate particles. In particular, when blended with a detergent component, the stability of the sodium percarbonate component tends to decrease. An object of the present invention is to provide sodium percarbonate particles having high stability especially in blending stability with a detergent and having a high dissolution rate.
【０００６】[0006]
【課題を解決するための手段】本発明者らはかかる問題
点を解決するため鋭意検討した結果、過炭酸ナトリウム
の粒子に、アルカリ金属の炭酸塩の水溶液、けい酸塩と
の水溶液および硫酸マグネシウム水溶液を噴霧し、乾燥
して被覆層を形成させて得られた過炭酸ナトリウムの粒
子は溶解速度も良く、かつ洗剤との配合安定性も非常に
良好である事を見い出し、本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, an aqueous solution of an alkali metal carbonate, an aqueous solution of a silicate, and magnesium sulfate were added to sodium percarbonate particles. The sodium percarbonate particles obtained by spraying an aqueous solution and drying to form a coating layer were found to have a good dissolution rate and very good blending stability with a detergent, and completed the present invention. .
【０００７】過炭酸ナトリウムの被覆は、具体的には次
のように実施される。すなわち、過炭酸ナトリウムの粒
子に、アルカリ金属の炭酸塩とけい酸塩との混合物の水
溶液を噴霧しながら乾燥して被覆第一層を形成後、さら
に硫酸マグネシウム水溶液を噴霧しながら乾燥して被覆
第二層を形成せしめる。また、過炭酸ナトリウムの粒子
に、アルカリ金属の炭酸塩とけい酸塩との混合物の水溶
液及び硫酸マグネシウム水溶液の２種の水溶液をそれぞ
れ別々のノズルで同時に噴霧しながら乾燥して被覆層を
形成せしめてもよい。この時噴霧する順序を逆にして、
先に硫酸マグネシウムを噴霧し、ついでアルカリ金属の
炭酸塩とけい酸塩との混合水溶液を噴霧した場合は、有
効酸素が低下し、また溶解速度が遅くなる。さらに、過
炭酸ナトリウムの粒子に、アルカリ金属の炭酸塩の水溶
液、けい酸塩の水溶液及び硫酸マグネシウム水溶液の３
種の水溶液をそれぞれ別々のノズルで同時にまたは逐次
噴霧しながら乾燥して被覆層を形成せしめてもよい。[0007] The coating of sodium percarbonate is specifically carried out as follows. That is, the particles of sodium percarbonate are dried while spraying an aqueous solution of a mixture of an alkali metal carbonate and a silicate to form a coating first layer, and then dried while spraying an aqueous magnesium sulfate solution to form a coating. Form two layers. Further, two kinds of aqueous solutions of an aqueous solution of a mixture of an alkali metal carbonate and a silicate and two aqueous solutions of a magnesium sulfate aqueous solution are simultaneously sprayed onto separate particles of sodium percarbonate with separate nozzles to form a coating layer. Is also good. At this time, reverse the order of spraying,
When magnesium sulfate is sprayed first and then a mixed aqueous solution of an alkali metal carbonate and silicate is sprayed, the available oxygen decreases and the dissolution rate decreases. Further, an aqueous solution of an alkali metal carbonate, an aqueous solution of a silicate and an aqueous solution of magnesium sulfate are added to the sodium percarbonate particles.
The aqueous solutions of the seeds may be dried simultaneously or sequentially with separate nozzles to form a coating layer.
【０００８】本発明で使用される過炭酸ナトリウムは公
知の方法で反応、晶出、脱水して製造された湿粉状の過
炭酸ナトリウム（含水率６〜１５％）をバインダーとと
もに捏和式の造粒機で凝集造粒し、次いで押出機で整粒
し、乾燥させて得られる。また、湿粉状の過炭酸ナトリ
ウムと造粒工程および／または被覆工程などから回収さ
れた、けい酸塩成分、硫酸マグネシウム成分またはアル
カリ金属の炭酸塩成分などの被覆剤成分を一部含む回収
過炭酸ナトリウムとを混合して造粒した過炭酸ナトリウ
ムもまた好適に使用される。湿粉状の過炭酸ナトリウム
と回収過炭酸ナトリウムの重量配合比は、５０：５０〜
９９：１の範囲が好ましい。特に回収過炭酸ナトリウム
が径が３００μｍ以下、好ましくは５〜１００μｍの微
粉状である場合には、過炭酸ナトリウムの安定性がより
向上する。The sodium percarbonate used in the present invention is prepared by kneading a wet powdered sodium percarbonate (water content: 6 to 15%) produced by reaction, crystallization and dehydration by a known method together with a binder. It is obtained by coagulation and granulation by a granulator, then sizing by an extruder, and drying. In addition, the recovered powder partially containing wet powdered sodium percarbonate and a coating component such as a silicate component, a magnesium sulfate component or an alkali metal carbonate component recovered from the granulation step and / or the coating step. Sodium percarbonate granulated by mixing with sodium carbonate is also preferably used. The weight ratio of the wet powdered sodium percarbonate to the recovered sodium percarbonate is 50: 50-
A range of 99: 1 is preferred. In particular, when the recovered sodium percarbonate is in the form of fine powder having a diameter of 300 μm or less, preferably 5 to 100 μm, the stability of sodium percarbonate is further improved.
【０００９】本発明で使用される造粒工程後、被覆工程
前の過炭酸ナトリウムの粒子は、径が通常３００〜２０
００μｍ、好ましくは５００〜１０００μｍのものが使
用される。被覆剤としてのアルカリ金属の炭酸塩として
は炭酸ナトリウム、炭酸カリウム、炭酸リチウムなどが
使用し得る。またこれらを併用しても良い。中でも経済
上の利便さから炭酸ナトリウムが最も好ましい。The particles of sodium percarbonate used in the present invention after the granulation step and before the coating step usually have a diameter of 300 to 20.
Those having a size of 00 μm, preferably 500 to 1000 μm are used. As a carbonate of an alkali metal as a coating agent, sodium carbonate, potassium carbonate, lithium carbonate and the like can be used. These may be used in combination. Among them, sodium carbonate is most preferred from the economical convenience.
【００１０】アルカリ金属の炭酸塩の被覆量は過炭酸ナ
トリウム(Na2CO3・3/2H2O2)１モルに対して０．０７５
モル〜０．１８モルが好ましい。すなわち、過炭酸ナト
リウム（分子量１５７）１００部（重量、以下同様）に
対してアルカリ金属の炭酸塩が炭酸ナトリウム（分子量
１０６）の場合には５部〜１２部である。被覆量が０．
０７５モル以下の場合には洗剤との配合安定性が不足す
る。逆に０．１８モル以上の場合には溶解速度が遅くな
るだけでなく経済性の点でも好ましくない。The coating amount of the alkali metal carbonate is 0.075 per mol of sodium percarbonate (Na 2 CO 3 .3 / 2H 2 O 2 ).
Mol to 0.18 mol is preferred. That is, when the alkali metal carbonate is sodium carbonate (molecular weight 106), the amount is 5 to 12 parts with respect to 100 parts (weight, the same applies hereinafter) of sodium percarbonate (molecular weight 157). The coating amount is 0.
When the amount is 075 mol or less, the blending stability with the detergent is insufficient. On the other hand, when it is 0.18 mol or more, not only the dissolution rate becomes slow but also it is not preferable from the viewpoint of economic efficiency.
【００１１】被覆剤としてのけい酸塩としては、オルト
ケイ酸ナトリウム、メタケイ酸ナトリウム、水ガラス１
号、２号、３号等のナトリウム塩が使用し得る。中でも
水ガラス類は液状であって使用上の利便の点で好まし
い。けい酸塩の被覆量は、未被覆の過炭酸ナトリウム１
モルに対してＳｉＯ2 として０．０１モル〜０．０６モ
ルが好ましい。すなわち過炭酸ナトリウム１００部に対
してけい酸塩中のＳｉＯ2 （分子量６０．３）は０．４
部〜２．２部である。少なすぎると被覆の延展性が低下
し、洗剤との配合安定性が不十分となる。逆に多すぎる
と溶解速度が遅くなる。As the silicate as a coating agent, sodium orthosilicate, sodium metasilicate, water glass 1
Nos. 2, 2 and 3 may be used. Among them, water glasses are liquid and are preferable in terms of convenience in use. The coating amount of silicate is 1% of uncoated sodium percarbonate.
0.01 mol to 0.06 mol is preferable as SiO 2 with respect to the mol. That is, SiO 2 (molecular weight 60.3) in silicate is 0.4 with respect to 100 parts of sodium percarbonate.
Parts to 2.2 parts. If the amount is too small, the spreadability of the coating is reduced, and the mixing stability with the detergent becomes insufficient. Conversely, if it is too large, the dissolution rate will be slow.
【００１２】被覆剤としての硫酸マグネシウムの被覆量
は、未被覆の過炭酸ナトリウム１モルに対して０．００
６モル〜０．０６モルが好ましい。すなわち過炭酸ナト
リウム１００部に対して硫酸マグネシウム（分子量１２
０．３）０．４５部〜４．５部である。なお被覆量が
０．００６モル以下だと洗剤との配合安定性が不十分と
なる。逆に被覆量が０．０６モル以上だと溶解速度が遅
くなる。なお上記の被覆剤の他に従来知られているキレ
ート剤（たとえば、ニトリロトリ酢酸、エチレンジアミ
ン四酢酸またはその塩）等を被覆剤と併用して過炭酸ナ
トリウムを安定化させても良い。各被覆剤の比率は、特
許請求範囲内の被覆量であれば特に制限はないが、通常
アルカリ金属の炭酸塩に対するけい酸塩および硫酸マグ
ネシウムがモル比で１：０．０５：０．０３〜１：０．
８：０．８、好ましくは１：０．１：０．１〜１：０．
４：０．４から選ばれる。[0012] The coating amount of magnesium sulfate as a coating agent is 0.001 mol per mol of uncoated sodium percarbonate.
6 mol to 0.06 mol is preferred. That is, magnesium sulfate (molecular weight 12
0.3) 0.45 to 4.5 parts. If the coating amount is 0.006 mol or less, the mixing stability with the detergent becomes insufficient. Conversely, if the coating amount is 0.06 mol or more, the dissolution rate becomes slow. In addition to the above-mentioned coating agent, a conventionally known chelating agent (for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid or a salt thereof) or the like may be used in combination with the coating agent to stabilize sodium percarbonate. The ratio of each coating agent is not particularly limited as long as the coating amount is within the scope of the claims. Usually, the molar ratio of the silicate and the magnesium sulfate to the alkali metal carbonate is 1: 0.05: 0.03 to 1: 0.
8: 0.8, preferably 1: 0.1: 0.1 to 1: 0.
4: 0.4.
【００１３】過炭酸ナトリウムを被覆する場合、これら
の被覆剤を溶かす溶媒としてはこれらを溶かす溶媒の中
から選ばれるが、溶解度が高く、安全かつ安価である水
が最も好ましい。次に被覆剤の噴霧時の濃度は、使用温
度に於ける飽和溶解濃度以下であれば良いが、余り低い
濃度では乾燥に時間を要するだけでなく蒸発させる水の
熱量が大となり経済性の点で好ましくない。一方余りに
高い濃度では配管やノズルにおいて結晶が析出し、閉塞
しやすく好ましくない。従ってアルカリ金属の炭酸塩の
液濃度は５〜２０重量％が好ましく、７〜１５重量％が
さらに好ましい。けい酸塩の液濃度（ＳｉＯ2 として）
は０．５〜９重量％が好ましく、１〜６重量％がさらに
好ましい。一方硫酸マグネシウムの液濃度は３〜２５重
量％が好ましく、５〜２０重量％がさらに好ましい。In the case of coating with sodium percarbonate, the solvent for dissolving these coating agents is selected from the solvents for dissolving them, but water having high solubility, safe and inexpensive is most preferable. Next, the concentration of the coating agent at the time of spraying may be lower than the saturation dissolution concentration at the operating temperature. However, if the concentration is too low, not only the time is required for drying but also the amount of heat of the water to be evaporated becomes large, and the economical efficiency is reduced. Is not preferred. On the other hand, if the concentration is too high, crystals will precipitate in the pipes and nozzles, and are undesirably easily clogged. Therefore, the liquid concentration of the alkali metal carbonate is preferably 5 to 20% by weight, more preferably 7 to 15% by weight. Liquid concentration of silicate (as SiO 2 )
Is preferably 0.5 to 9% by weight, more preferably 1 to 6% by weight. On the other hand, the liquid concentration of magnesium sulfate is preferably 3 to 25% by weight, and more preferably 5 to 20% by weight.
【００１４】噴霧乾燥時の過炭酸ナトリウムの温度は４
０〜９５℃、好ましくは５０〜９０℃である。過炭酸ナ
トリウムの温度が低すぎる場合は過炭酸ナトリウム粒子
が凝集するので好ましくない。一方過炭酸ナトリウムの
温度が高すぎる場合は過炭酸ナトリウムが分解する傾向
があり、また被覆剤の結晶が成長するなどして延展性が
悪くなり均一な被覆が出来にくくなる。The temperature of sodium percarbonate during spray drying is 4
The temperature is 0 to 95 ° C, preferably 50 to 90 ° C. If the temperature of the sodium percarbonate is too low, the sodium percarbonate particles are undesirably aggregated. On the other hand, if the temperature of sodium percarbonate is too high, sodium percarbonate tends to decompose, and the crystal of the coating material grows, and the spreadability becomes poor, so that uniform coating becomes difficult.
【００１５】[0015]
【実施例】次に本発明の方法を実施例、比較例により更
に具体的に説明する。なお本発明はこれら実施例に制限
されることなく実施することが出来る。実施例中の％は
特に記載がない限り重量％を意味する。Next, the method of the present invention will be described more specifically with reference to examples and comparative examples. The present invention can be implemented without being limited to these examples. In the examples,% means% by weight unless otherwise specified.
【００１６】実施例１ 平均粒径５００μｍの過炭酸ナトリウム（有効酸素量１
４．４％）３００ｇを流動乾燥式被覆装置（ヤマト科学
（株）製“パルビスコーティング”）の多孔板上に置
き、ついで０．２５Ｍ3 ／ｍｉｎの空気を送り込んで流
動化させた。その後入口空気を加温することにより、流
動中の過炭酸ナトリウムの温度を７５℃まで昇温させ
た。７５℃で温度が安定した後流動させたままで、多孔
板より１０ｃｍ上の位置にある噴霧ノズルより炭酸ナト
リウム及び１号水ガラスの混合液〔Ｎａ2 ＣＯ3 濃度
５．５重量％、１号水ガラス濃度（ＳｉＯ2 として）１
重量％〕６００ｇを８ｇ／ｍｉｎの流量で７５分間かけ
て噴霧し続けた。噴霧終了後５分乾燥を行ない被覆第一
層を形成せしめた。ついでノズルを交換後５重量％の硫
酸マグネシウム水溶液９０ｇを５ｇ／ｍｉｎの流量で１
８分間かけて噴霧を行なった。先程と同様に噴霧終了後
５分乾燥し、被覆第二層を形成せしめた。なお被覆中の
過炭酸ナトリウムの温度は７３〜７７℃でコントロール
した。固形分としての各成分の被覆量は下記の通りであ
る。 被覆第一層中の炭酸ナトリウム：３３．０ｇ（原料過炭
酸ナトリウムの11.0％） 被覆第一層中の１号水ガラス（SiO2として）：６．０ｇ
（原料過炭酸ナトリウムの2.0 ％） 被覆第二層中の硫酸マグネシウム：４．５ｇ（原料過炭
酸ナトリウムの1.5 ％） 冷却後被覆された過炭酸ナトリウムを取り出したが凝集
物は全く観察されなかった。EXAMPLE 1 Sodium percarbonate having an average particle size of 500 μm (effective oxygen amount 1
4.4%) 300 g was placed in a fluidized drying type coating apparatus perforated plate on the (Yamato Scientific Co., Ltd. "Pal bis coating"), was then fluidized by feeding air 0.25M 3 / min. Thereafter, by heating the inlet air, the temperature of the flowing sodium percarbonate was raised to 75 ° C. After the temperature was stabilized at 75 ° C., while the fluid was kept flowing, a mixed solution of sodium carbonate and No. 1 water glass [Na 2 CO 3 concentration of 5.5% by weight and No. 1 water] was sprayed from a spray nozzle located 10 cm above the perforated plate. Glass concentration (as SiO 2 ) 1
% By weight] was sprayed at a flow rate of 8 g / min for 75 minutes. After the spraying, the coating was dried for 5 minutes to form a first coating layer. After replacing the nozzle, 90 g of a 5% by weight aqueous magnesium sulfate solution was added at a flow rate of 5 g / min.
Spraying was performed over 8 minutes. After the spraying was completed, the coating was dried for 5 minutes to form a second coating layer. The temperature of sodium percarbonate in the coating was controlled at 73 to 77 ° C. The coating amount of each component as a solid content is as follows. Sodium carbonate in first coating layer: 33.0 g (11.0% of raw material sodium percarbonate) No. 1 water glass (as SiO 2 ) in first coating layer: 6.0 g
(2.0% of raw material sodium percarbonate) Magnesium sulfate in the coated second layer: 4.5 g (1.5% of raw material sodium percarbonate) After cooling, the coated sodium percarbonate was taken out, but no aggregate was observed. .
【００１７】得られた過炭酸ナトリウムの有効酸素量を
チオ硫酸ナトリウム滴定で求めたところ、１２．６％で
あった。これは被覆時に有効酸素が分解することなく、
被覆剤がほぼ理論値どおり被覆された事を示している。 （理論値：14.4％×(1/(1+0.145))=12.6％） 得られた被覆された過炭酸ナトリウム粒子の溶解性、洗
剤と混合しての保存安定性試験を以下のように実施し
た。この結果を有効酸素量、及び溶解速度の結果ととも
に表１に示した。得られた過炭酸ナトリウム粒子は溶解
性が良い上に、配合安定性は非常に良好であり、後述す
る未被覆過炭酸ナトリウムに比較して大幅な安定度の向
上が認められた。The effective oxygen content of the obtained sodium percarbonate was determined by sodium thiosulfate titration to be 12.6%. This means that available oxygen does not decompose during coating,
This indicates that the coating agent was coated almost as expected. (Theoretical value: 14.4% × (1 / (1 + 0.145)) = 12.6%) The solubility of the obtained coated sodium percarbonate particles and the storage stability test after mixing with a detergent were carried out as follows. did. The results are shown in Table 1 together with the results of the available oxygen amount and the dissolution rate. The obtained sodium percarbonate particles had good solubility and very good blending stability, and a significant improvement in stability was observed as compared with uncoated sodium percarbonate described below.
【００１８】溶解性試験 ５ｇの過炭酸ナトリウム粒子を水１リットルに入れて２
０℃、２００ｒｐｍで撹拌下、電気伝導度法で調べるこ
とにより、粒子が完全に溶解するのに要する時間を測定
した。Solubility test 5 g of sodium percarbonate particles are placed in 1 liter of water and 2
The time required for the particles to completely dissolve was measured by conducting an electrical conductivity method at 0 ° C. and stirring at 200 rpm.
【００１９】保存安定性試験 ３０℃、８０％相対湿度下で１日充分吸湿させた合成ゼ
オライト４Ａ粉末１ｇと被覆された過炭酸ナトリウム粒
子１ｇとをポリエチ袋（（株）生産日本社製、商品名ユ
ニパックＡ−４、水透過性有り）に入れてよくふり混ぜ
る。これを３０℃、８０％相対湿度下、４日間放置し保
存前後の有効酸素量を分析し、ゼオライトとの加速配合
安定性を調べた。結果は、４日間保存後の有効酸素量残
存率で評価した。なお、有効酸素量はチオ硫酸ナトリウ
ム滴定で求め、有効酸素量残存率は下式で算出した。Storage stability test 1 g of synthetic zeolite 4A powder and 1 g of coated sodium percarbonate particles, which had been sufficiently absorbed for one day at 30 ° C. and 80% relative humidity, were placed in a polyethylene bag (manufactured by Nippon Shokuhin Co., Ltd.) (Uni-Pack A-4, with water permeability) and mix well. This was allowed to stand at 30 ° C. and 80% relative humidity for 4 days, and the amount of available oxygen before and after storage was analyzed, and the accelerated blending stability with zeolite was examined. The results were evaluated based on the residual ratio of available oxygen after storage for 4 days. The available oxygen amount was determined by sodium thiosulfate titration, and the available oxygen remaining rate was calculated by the following equation.
【数１】 有効酸素量残存率（％）＝（保存後の有効酸
素量）÷（保存前の有効酸素量）×１００## EQU1 ## Effective oxygen remaining rate (%) = (available oxygen after storage) / (available oxygen before storage) × 100
【００２０】保存安定性試験 市販のコンパクト洗剤（ゼオライト、酵素等を含む）１
３００ｇに被覆された過炭酸ナトリウム粒子または未被
覆の過炭酸ナトリウム粒子２００ｇ（洗剤に対して１
３．３％）を均一に混合し、カートン紙箱に入れてビニ
ールテープで密封した。これを３０℃、８０％相対湿度
に維持された恒温槽中に２１日間保存した。結果は、保
存安定性試験と同様に２１日間保存後の有効酸素量残
存率で評価した。Storage stability test Commercially available compact detergent (including zeolite, enzyme, etc.) 1
200 g of sodium percarbonate particles coated on 300 g or uncoated sodium percarbonate particles (1
(3.3%) was uniformly mixed, placed in a carton box and sealed with vinyl tape. This was stored for 21 days in a thermostat maintained at 30 ° C. and 80% relative humidity. The results were evaluated by the residual ratio of available oxygen after storage for 21 days as in the storage stability test.
【００２１】実施例２ 被覆剤量をそれぞれ下記のように変化させた以外はすべ
て実施例１と同様にして被覆過炭酸ナトリウムを得た。 炭酸ナトリウム：２４．８ｇ（原料過炭酸ナトリウムの
８．３％） １号水ガラス（SiO2として）：４．５ｇ（原料過炭酸ナ
トリウムの１．５％） 硫酸マグネシウム：１０．５ｇ（原料過炭酸ナトリウム
の３．５％） 得られた過炭酸ナトリウムの有効酸素量を分析した所１
２．７％であった。これは被覆時に過炭酸ナトリウムが
分解することなく、被覆剤がほぼ理論どおり被覆された
事を示している。また実施例１と同じ方法で溶解性を調
べた所２．５分で溶解した。実施例１と同様に配合安定
性を調べたが良好であり、この結果を表１に示した。Example 2 A coated sodium percarbonate was obtained in the same manner as in Example 1 except that the amount of the coating agent was changed as follows. Sodium carbonate: 24.8 g (8.3% of raw material sodium percarbonate) No. 1 water glass (as SiO 2 ): 4.5 g (1.5% of raw material sodium percarbonate) Magnesium sulfate: 10.5 g (raw material (3.5% of sodium carbonate) The amount of available oxygen in the obtained sodium percarbonate was analyzed.
2.7%. This indicates that the coating agent was coated almost as theoretically without decomposition of sodium percarbonate during coating. When solubility was examined in the same manner as in Example 1, it was dissolved in 2.5 minutes. The blending stability was examined in the same manner as in Example 1, but it was good. The results are shown in Table 1.
【００２２】実施例３ 被覆剤種として炭酸ナトリウムのかわりに炭酸カリウ
ム、１号水ガラスのかわりに３号水ガラスをいずれも同
濃度で使用した以外はすべて実施例１と同様にして被覆
過炭酸ナトリウムを得た。 炭酸カリウム：３３．０ｇ（原料過炭酸ナトリウムの１
１．０％） ３号水ガラス（SiO2として）：６．０ｇ（原料過炭酸ナ
トリウムの２．０％） 硫酸マグネシウム：４．５ｇ（原料過炭酸ナトリウムの
１．５％） 得られた過炭酸ナトリウムの溶解性、配合安定性を求
め、この結果を同様に表１に示した。Example 3 Coated percarbonate was prepared in the same manner as in Example 1 except that potassium carbonate was used in place of sodium carbonate as the coating agent species and water glass No. 3 was used in place of water glass No. 1 at the same concentration. Sodium was obtained. Potassium carbonate: 33.0 g (1 of raw material sodium percarbonate)
1.0%) No. 3 water glass (as SiO 2 ): 6.0 g (2.0% of raw material sodium percarbonate) Magnesium sulfate: 4.5 g (1.5% of raw material sodium percarbonate) The solubility and blending stability of sodium carbonate were determined, and the results are also shown in Table 1.
【００２３】実施例４ 平均粒径５００μｍの過炭酸ナトリウム（有効酸素量１
４．４％）１２ｋｇを流動乾燥装置（フジパウダル製
“ミゼットドライヤー”）の多孔板上に置き、ついで
３．２Ｍ3 ／ｍｉｎの空気を送り込んで流動化させた。
その後入口空気を１２０〜１５０℃に加温させ流動中の
過炭酸ナトリウムの温度を７５℃まで昇温させた。７５
℃で過炭酸ナトリウムの温度が安定した後流動させたま
まで、多孔板より４０ｃｍ上の位置にある２本の噴霧ノ
ズルより、炭酸ナトリウム及び１号水ガラスの混合液
〔（炭酸ナトリウム濃度１６．５重量％、１号水ガラス
濃度（ＳｉＯ2 として）３重量％）〕と硫酸マグネシウ
ム水溶液（１０重量％）とをそれぞれ別々のノズルで同
時に噴霧し始めた。炭酸ナトリウム及び１号水ガラスの
混合液８ｋｇは１０５ｇ／分の速度で約７６分かかっ
た。一方硫酸マグネシウム水溶液１．８ｋｇは２３．７
ｇ／分の速度で約７６分かかりほぼ同時に被覆が終了し
た。なお被覆中の温度は７３〜７７℃でコントロールし
た。被覆終了後も５分間加熱空気を流し続け、乾燥を行
った。ついでエアーヒーターの加熱を停止し冷風を流し
て冷却した。冷却後被覆された過炭酸ナトリウムを取り
出したが凝集物は全く観察されなかった。なお固形分と
しての各成分の被覆量は下記の通りである。 炭酸ナトリウム：１．３２ｋｇ（原料過炭酸ナトリウム
の１１．０％） １号水ガラス（SiO2として）：０．２４ｋｇ（原料過炭
酸ナトリウムの２．０％） 硫酸マグネシウム：０．１８ｋｇ（原料過炭酸ナトリウ
ムの１．５％） 得られた過炭酸ナトリウムの溶解性、配合安定性を求
め、この結果を表１に示した。実施例１、２、３の多層
噴霧と比較して同時噴霧の場合、溶解性がやや遅くなる
ぐらいでほとんど品質的には変わらない過炭酸ナトリウ
ムが得られる事がわかった。Example 4 Sodium percarbonate having an average particle size of 500 μm (effective oxygen amount 1
4.4%) 12 kg was placed on the perforated plate of the fluidized drying apparatus (Fujipaudaru Ltd. "Midget Dryer"), was then fluidized by feeding air 3.2M 3 / min.
Thereafter, the inlet air was heated to 120 to 150 ° C., and the temperature of the flowing sodium percarbonate was raised to 75 ° C. 75
After the temperature of sodium percarbonate was stabilized at 0 ° C., while the fluid was kept flowing, a mixture of sodium carbonate and No. 1 water glass [(sodium carbonate concentration 16.5) was passed through two spray nozzles 40 cm above the perforated plate. %, The first water glass concentration (as SiO 2 , 3% by weight)] and an aqueous solution of magnesium sulfate (10% by weight) were simultaneously sprayed from separate nozzles. 8 kg of the mixture of sodium carbonate and No. 1 water glass took about 76 minutes at a rate of 105 g / min. On the other hand, 1.8 kg of aqueous magnesium sulfate solution is 23.7.
It took about 76 minutes at a rate of g / min to complete the coating at about the same time. The temperature during coating was controlled at 73 to 77 ° C. After the coating was completed, the heated air was kept flowing for 5 minutes to perform drying. Then, heating of the air heater was stopped, and cooling was performed by flowing cool air. After cooling, the coated sodium percarbonate was removed, but no aggregates were observed. The coating amount of each component as a solid content is as follows. Sodium carbonate: 1.32 kg (11.0% of raw material sodium percarbonate) No. 1 water glass (as SiO 2 ): 0.24 kg (2.0% of raw material sodium percarbonate) Magnesium sulfate: 0.18 kg (raw material The solubility and blending stability of the obtained sodium percarbonate were determined, and the results are shown in Table 1. In the case of the simultaneous spraying as compared with the multilayer sprays of Examples 1, 2, and 3, it was found that sodium percarbonate with almost no change in quality was obtained as the solubility was slightly delayed.
【００２４】実施例５ 実施例４における炭酸ナトリウムと１号水ガラスの混合
液の替わりに炭酸カリウムと３号水ガラスの混合液を同
濃度で使用した以外はすべて実施例４と同様にして被覆
された過炭酸ナトリウムを得た。 炭酸カリウム：１．３２ｋｇ（原料過炭酸ナトリウムの
１１．０％） ３号水ガラス（SiO2として）：０．２４ｋｇ（原料過炭
酸ナトリウムの２．０％） 硫酸マグネシウム：０．１８ｋｇ（原料過炭酸ナトリウ
ムの１．５％） 得られた過炭酸ナトリウムの溶解性、配合安定性を求
め、この結果を表１に示した。Example 5 Coating was carried out in the same manner as in Example 4 except that a mixture of potassium carbonate and No. 3 water glass was used in the same concentration in place of the mixture of sodium carbonate and No. 1 water glass in Example 4. The obtained sodium percarbonate was obtained. Potassium carbonate: 1.32 kg (11.0% of raw material sodium percarbonate) No. 3 water glass (as SiO 2 ): 0.24 kg (2.0% of raw material sodium percarbonate) Magnesium sulfate: 0.18 kg (raw material The solubility and blending stability of the obtained sodium percarbonate were determined, and the results are shown in Table 1.
【００２５】表１からわかるように本発明の製造された
過炭酸ナトリウム粒子は、完全に溶解するのに要する時
間が２〜２．５分と短く、かつ、洗剤と配合した時、２
１日保存後でも約１０％しか分解しない。すなわち、本
発明の過炭酸ナトリウム粒子は、いずれも溶解性および
洗剤との配合安定性において共に良い特性を示し、漂白
剤組成物または漂白成分を含む家庭用洗剤等に使用する
ために特性バランスの良好なものである。As can be seen from Table 1, the sodium percarbonate particles produced according to the present invention require only 2 to 2.5 minutes to completely dissolve, and when formulated with a detergent,
Decomposes only about 10% after one day storage. That is, the sodium percarbonate particles of the present invention both exhibit good properties in terms of solubility and blending stability with a detergent, and have a property balance for use in a bleaching composition or a household detergent containing a bleaching component. It is good.
【００２６】比較例１ 本発明の原料に使用した被覆されていない過炭酸ナトリ
ウムの溶解性、配合安定性を求め、この結果を比較の為
に同様に表２に示した。Comparative Example 1 The solubility and blending stability of uncoated sodium percarbonate used as a raw material of the present invention were determined, and the results are similarly shown in Table 2 for comparison.
【００２７】比較例２ 実施例１における２層目の噴霧を行わなかった以外はす
べて実施例１と同様にして被覆された過炭酸ナトリウム
を得た。 炭酸ナトリウム：３３．０ｇ（原料過炭酸ナトリウムの
１１．０％） １号水ガラス（SiO2として）：６．０ｇ（原料過炭酸ナ
トリウムの２．０％） 得られた過炭酸ナトリウムの溶解性、配合安定性を求
め、この結果を同様に表２に示した。配合安定性は実施
例１のようには大幅な改善はみられなかった。Comparative Example 2 A coated sodium percarbonate was obtained in the same manner as in Example 1 except that the spraying of the second layer in Example 1 was not performed. Sodium carbonate: 33.0 g (11.0% of raw material sodium percarbonate) No. 1 water glass (as SiO 2 ): 6.0 g (2.0% of raw material sodium percarbonate) Solubility of obtained sodium percarbonate The composition stability was determined, and the results are also shown in Table 2. The blending stability was not significantly improved as in Example 1.
【００２８】比較例３実施例１における１層目の噴霧を
行わなかった以外はすべて実施例１と同様にして被覆さ
れた過炭酸ナトリウムを得た。 硫酸マグネシウム：４．５ｇ（原料過炭酸ナトリウムの
１．５％） 得られた過炭酸ナトリウムの溶解性、配合安定性を求
め、この結果を同様に表２に示した。配合安定性は実施
例１のようには大幅な改善はみられなかった。また被覆
剤による希釈分以上の有効酸素量の低下がみられた。 理論有効酸素量：１４．４％×（１／（１＋０．０１５））＝１４．２％ 実測有効酸素量： １３．９％Comparative Example 3 A coated sodium percarbonate was obtained in the same manner as in Example 1 except that the first layer was not sprayed. Magnesium sulfate: 4.5 g (1.5% of raw material sodium percarbonate) The solubility and blending stability of the obtained sodium percarbonate were determined, and the results are shown in Table 2. The blending stability was not significantly improved as in Example 1. In addition, a decrease in the amount of available oxygen more than the amount diluted by the coating agent was observed. Theoretical effective oxygen amount: 14.4% × (1 / (1 + 0.015)) = 14.2% Actually measured effective oxygen amount: 13.9%
【００２９】比較例４ 平均粒径５００μｍの過炭酸ナトリウム（有効酸素量１
４．４％）３００ｇを流動乾燥式被覆装置（ヤマト科学
（株）製“パルビスコーティング”）の多孔板上に置
き、ついで０．２５Ｍ3 ／ｍｉｎの空気を送り込んで流
動化させた。その後入口空気を加温させ流動中の過炭酸
ナトリウムの温度を７５℃まで昇温させた。７５℃で温
度が安定した後流動させたままで、多孔板より１０ｃｍ
上の位置にある噴霧ノズルより、塩化マグネシウム水溶
液（１０％塩化マグネシウム濃度）１８０ｇを５ｇ／ｍ
ｉｎの流量で３６分かけて噴霧した。噴霧終了後被覆装
置より内容物を取り出し、真空乾燥機に移した。そして
５０℃で３mmHgにして４時間乾燥した。 塩化マグネシウム：１８．０ｇ（原料過炭酸ナトリウム
粒子の６％） 得られた過炭酸ナトリウムの溶解性、配合安定性を求
め、この結果を同様に表２に示した。配合安定性は実施
例１のようには大幅な改善はみられなかった。特にゼオ
ライトとの配合安定性は比較例１の未被覆に近い低い安
定性であった。また被覆剤による希釈分以上の有効酸素
量の大幅な濃度低下がみられた。 理論有効酸素量：１４．４％×（１／（１＋０．０６））＝１３．６％ 実測有効酸素量： １２．９％ さらに溶解に５分もかかっており、低温で洗濯する日本
の環境には適用し難い結果であった。Comparative Example 4 Sodium percarbonate having an average particle size of 500 μm (effective oxygen amount 1
4.4%) 300 g was placed in a fluidized drying type coating apparatus perforated plate on the (Yamato Scientific Co., Ltd. "Pal bis coating"), was then fluidized by feeding air 0.25M 3 / min. Thereafter, the inlet air was heated to raise the temperature of the flowing sodium percarbonate to 75 ° C. After the temperature is stabilized at 75 ° C., it is kept flowing and 10 cm from the perforated plate.
180 g of magnesium chloride aqueous solution (10% magnesium chloride concentration) was sprayed at 5 g / m from the spray nozzle at the upper position.
Spraying was performed over 36 minutes at a flow rate of in. After the spraying was completed, the contents were taken out of the coating apparatus and transferred to a vacuum dryer. And it dried at 50 degreeC and 3 mmHg for 4 hours. Magnesium chloride: 18.0 g (6% of the raw material sodium percarbonate particles) The solubility and blending stability of the obtained sodium percarbonate were determined. The results are shown in Table 2. The blending stability was not significantly improved as in Example 1. In particular, the blending stability with zeolite was as low as that of Comparative Example 1 which was not coated. In addition, a significant decrease in the effective oxygen concentration over the dilution by the coating agent was observed. Theoretical effective oxygen content: 14.4% x (1 / (1 + 0.06)) = 13.6% Actual available oxygen content: 12.9% In addition, it takes 5 minutes to dissolve, and the environment in Japan where washing is performed at low temperature Was difficult to apply.
【００３０】比較例５ 平均粒径５００μｍの過炭酸ナトリウム（有効酸素量１
４．４％）３００ｇを流動乾燥式被覆装置（ヤマト科学
（株）製“パルビスコーティング”）の多孔板上に置
き、ついで０．２５Ｍ3 ／ｍｉｎの空気を送り込んで流
動化させた。その後入口空気を加温させ流動中の過炭酸
ナトリウムの温度を５０℃まで昇温させた。５０℃で温
度が安定した後流動させたままで、多孔板より１０ｃｍ
上の位置にある噴霧ノズルより、炭酸ナトリウムと硫酸
ナトリウムとの混合塩水溶液（炭酸ナトリウム濃度８．
８％、硫酸ナトリウム濃度１１．２％）１５０ｇを５ｇ
／ｍｉｎの流量で３０分かけて噴霧した。噴霧終了後１
０分間その温度でガスだけ流し続けて乾燥を完全にし
た。その後冷風にして３０℃まで冷却した後被覆された
過炭酸ナトリウムを取り出した所、わずかに凝集物が観
察された。 炭酸ナトリウム：１３．２ｇ（原料過炭酸ナトリウム粒
子の４．４％） 硫酸ナトリウム：１６．８ｇ（原料過炭酸ナトリウム粒
子の５．６％） 得られた過炭酸ナトリウムの溶解性、配合安定性を求
め、この結果を同様に表２に示した。溶解性は好ましい
が、配合安定性は実施例１のようには大幅な改善はみら
れなかった。Comparative Example 5 Sodium percarbonate having an average particle size of 500 μm (effective oxygen amount 1
4.4%) 300 g was placed in a fluidized drying type coating apparatus perforated plate on the (Yamato Scientific Co., Ltd. "Pal bis coating"), was then fluidized by feeding air 0.25M 3 / min. Thereafter, the inlet air was heated to raise the temperature of the flowing sodium percarbonate to 50 ° C. After the temperature is stabilized at 50 ° C., it is kept flowing and 10 cm from the perforated plate.
From the spray nozzle at the upper position, a mixed salt aqueous solution of sodium carbonate and sodium sulfate (sodium carbonate concentration of 8.
8%, sodium sulfate concentration 11.2%)
/ Min at a flow rate of 30 minutes. After spraying 1
Drying was complete by continuing to flow only gas at that temperature for 0 minutes. After cooling to 30 ° C. with cold air, the coated sodium percarbonate was taken out, and a slight aggregate was observed. Sodium carbonate: 13.2 g (4.4% of raw material sodium percarbonate particles) Sodium sulfate: 16.8 g (5.6% of raw material sodium percarbonate particles) The results were similarly shown in Table 2. Although the solubility is favorable, the blending stability was not significantly improved as in Example 1.
【００３１】比較例６ 炭酸ナトリウムを使用せず、１号水ガラスのみの水溶液
を使用して被覆第１層を形成した以外はすべて実施例１
と同様にして被覆された過炭酸ナトリウム粒子を得た。 １号水ガラス（SiO2として）：３９ｇ（原料過炭酸ナト
リウム粒子の１３％） 硫酸マグネシウム：４．５ｇ（原料過炭酸ナトリウム粒
子の１．５％） 得られた過炭酸ナトリウム粒子の有効酸素量量、溶解
性、配合安定性を求め、この結果を表２に示した。安定
性は幾分改善されているものの、溶解性は著しく低下し
た。Comparative Example 6 Example 1 was repeated except that the first coating layer was formed using an aqueous solution of No. 1 water glass without using sodium carbonate.
In the same manner as above to obtain coated sodium percarbonate particles. No. 1 water glass (as SiO 2 ): 39 g (13% of raw material sodium percarbonate particles) Magnesium sulfate: 4.5 g (1.5% of raw material sodium percarbonate particles) Effective oxygen content of obtained sodium percarbonate particles The amount, solubility and formulation stability were determined and the results are shown in Table 2. Although the stability was somewhat improved, the solubility was significantly reduced.
【００３２】被覆された過炭酸ナトリウム粒子の諸特性Properties of coated sodium percarbonate particles
【表１】 実施例 １ ２ ３ ４ ５ 溶解性（分） ２．５ ２．５ ２．５ ２．０ ２．５ 保存安定性 ９０ ９０ ８９ ９１ ９０ 保存安定性 ９１ ９０ ８７ ９０ ９０ Table 1 Example 1 2 3 4 5 Solubility (min) 2.5 2.5 2.5 2.0 2.0 2.5 Storage stability 90 90 89 91 90 Storage stability 91 90 87 90 90
【００３３】被覆された過炭酸ナトリウム粒子の諸特性Properties of coated sodium percarbonate particles
【表２】 比較例 １ ２ ３ ４ ５ ６ 溶解性（分） １．５ ３．０ ３．５ ５．０ １．５ １０．０ 保存安定性 ３０ ６７ ３５ ４３ ４８ ８４ 保存安定性 ５０ ６２ ５５ ７５ ５５ ６７ Table 2 Comparative Example 1 2 3 4 5 6 Solubility (min) 1.5 3.0 3.5 5.0 1.5 10.0 10.0 Storage stability 30 67 35 43 48 84 Storage stability 50 62 55 75 55 67
【００３４】[0034]
【発明の効果】本発明の過炭酸ナトリウム粒子は溶解速
度も良く、かつ洗剤との配合安定性も非常に良好であ
る。本発明の過炭酸ナトリウム粒子は表面がけい酸塩、
硫酸マグネシウム、アルカリ金属の炭酸塩および／また
はこれら相互の反応生成物によってむらなく被覆され、
水分その他の分解促進物と、過炭酸ナトリウムとを遮断
して、特に優れた安定化効果が得られる。本発明の過炭
酸ナトリウム粒子は、分解促進性のあるゼオライトや合
成洗剤との配合安定性が極めてすぐれている。さらに、
本発明の過炭酸ナトリウム粒子は溶解速度も大きいの
で、低温での洗濯が日常的な日本の環境下でも充分利用
出来る。The sodium percarbonate particles of the present invention have a good dissolution rate and a very good blending stability with a detergent. The sodium percarbonate particles of the present invention have a surface silicate,
Uniformly coated with magnesium sulfate, alkali metal carbonate and / or their mutual reaction products,
By blocking moisture and other decomposition promoting substances and sodium percarbonate, a particularly excellent stabilizing effect can be obtained. The sodium percarbonate particles of the present invention have extremely excellent blending stability with zeolites having a decomposition promoting property and synthetic detergents. further,
Since the sodium percarbonate particles of the present invention have a high dissolution rate, washing at a low temperature can be sufficiently used even in a daily Japanese environment.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡辺 進 三重県四日市市日永東２丁目４番16号 三菱瓦斯化学株式会社 四日市工場内 (56)参考文献 特開 平６−40709（ＪＰ，Ａ) 特開 平４−31308（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 15/10 C11D 3/395 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Susumu Watanabe 2-4-1-16 Hinagahigashi, Yokkaichi-shi, Mie Mitsubishi Gas Chemical Co., Ltd. Yokkaichi Plant (56) References JP-A-6-40709 (JP, A JP-A-4-31308 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C01B 15/10 C11D 3/395
Claims (6)
硫酸マグネシウムおよびアルカリ金属の炭酸塩の水溶液
を噴霧、乾燥して被覆層を形成せしめることを特徴とす
る安定化された過炭酸ナトリウムの粒子の製造方法。Claims: 1. Particles of sodium percarbonate, silicate,
A method for producing stabilized sodium percarbonate particles, comprising spraying and drying an aqueous solution of magnesium sulfate and an alkali metal carbonate to form a coating layer.
４０〜９５℃であることを特徴とする請求項１記載の安
定化された過炭酸ナトリウムの粒子の製造方法。2. The method for producing stabilized sodium percarbonate particles according to claim 1, wherein the temperature of the sodium percarbonate during spray drying is 40 to 95 ° C.
て、湿粉状の過炭酸ナトリウムと、造粒工程または被覆
工程から回収された、けい酸塩成分、硫酸マグネシウム
成分またはアルカリ金属の炭酸塩成分などの被覆剤成分
を一部含む回収過炭酸ナトリウムとの混合物からなる過
炭酸ナトリウム粒子を使用することを特徴とする請求項
１記載の過炭酸ナトリウム粒子の製造方法。3. The sodium percarbonate particles to be coated are wet powder sodium percarbonate and a silicate component, a magnesium sulfate component or a carbonate component of an alkali metal recovered from a granulation step or a coating step. 2. The method for producing sodium percarbonate particles according to claim 1, wherein sodium percarbonate particles comprising a mixture with recovered sodium percarbonate partially containing a coating agent component such as the above are used.
属の炭酸塩とけい酸塩との混合物の水溶液を噴霧、乾燥
して被覆第一層を形成後、さらに硫酸マグネシウム水溶
液を噴霧、乾燥して被覆第二層を形成せしめることを特
徴とする請求項１記載の安定化された過炭酸ナトリウム
の粒子の製造方法。4. An aqueous solution of a mixture of an alkali metal carbonate and a silicate is sprayed onto particles of sodium percarbonate and dried to form a first coating layer, and then a magnesium sulfate aqueous solution is sprayed and dried to coat the particles. The method for producing stabilized sodium percarbonate particles according to claim 1, wherein a second layer is formed.
属の炭酸塩とけい酸塩との混合物の水溶液及び硫酸マグ
ネシウム水溶液とをそれぞれ別々のノズルで同時に噴
霧、乾燥して被覆層を形成せしめることを特徴とする請
求項１記載の安定化された過炭酸ナトリウムの粒子の製
造方法。5. A coating layer is formed by simultaneously spraying and drying an aqueous solution of a mixture of an alkali metal carbonate and a silicate and an aqueous solution of magnesium sulfate on sodium percarbonate particles using separate nozzles. The method for producing stabilized sodium percarbonate particles according to claim 1, wherein
属の炭酸塩の水溶液、けい酸塩の水溶液及び硫酸マグネ
シウム水溶液とをそれぞれ別々のノズルで同時に噴霧、
乾燥して被覆層を形成せしめることを特徴とする請求項
１記載の安定化された過炭酸ナトリウムの粒子の製造方
法。6. An aqueous solution of an alkali metal carbonate, an aqueous solution of a silicate, and an aqueous solution of magnesium sulfate are simultaneously sprayed onto particles of sodium percarbonate using separate nozzles.
The method for producing stabilized sodium percarbonate particles according to claim 1, wherein the coating layer is formed by drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09170394A JP3305112B2 (en) | 1993-05-06 | 1994-04-28 | Stabilized sodium percarbonate particles and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-105552 | 1993-05-06 | ||
| JP10555293 | 1993-05-06 | ||
| JP09170394A JP3305112B2 (en) | 1993-05-06 | 1994-04-28 | Stabilized sodium percarbonate particles and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0717703A JPH0717703A (en) | 1995-01-20 |
| JP3305112B2 true JP3305112B2 (en) | 2002-07-22 |
Family
ID=26433148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09170394A Expired - Fee Related JP3305112B2 (en) | 1993-05-06 | 1994-04-28 | Stabilized sodium percarbonate particles and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3305112B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036599A (en) * | 2004-07-28 | 2006-02-09 | Mitsubishi Gas Chem Co Inc | Sodium percarbonate particle having excellent safety and stability |
-
1994
- 1994-04-28 JP JP09170394A patent/JP3305112B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0717703A (en) | 1995-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5462804A (en) | Stabilized particle of sodium percarbonate | |
| JP3599737B2 (en) | Coated sodium peroxycarbonate particles, process for producing the same, and detergent, detergent and bleach compositions containing the compound | |
| US5478488A (en) | Detergent composition containing alkali metal peroxysalt stabilized with alkali metal sulfate and chloride | |
| CA2310348C (en) | Granular coated sodium percarbonate for detergent and its manufacturing process | |
| JP2002517371A (en) | Coated sodium percarbonate particles, their preparation, their use in detergent compositions and detergent compositions containing them | |
| JPH06340403A (en) | Sodium percarbonate particle coated with coating material and preparation thereof | |
| KR100357943B1 (en) | Stabilization method of alkali metal and carbonate fine particles | |
| JPH02137710A (en) | Manufacture of sodium peroxycarbonate carrier | |
| KR930006689B1 (en) | Process for producing stabilized sodium percarbonate | |
| KR20050089975A (en) | Sodium percarbonate particles with improved storage stability | |
| JPH07502770A (en) | Granular percarbonate laundry bleach containing layered silicate stabilizers | |
| JPH04187508A (en) | Stable sodium percarbonate granule and production thereof | |
| US4120812A (en) | Polyethylene glycol-stabilized peroxygens | |
| JP3305112B2 (en) | Stabilized sodium percarbonate particles and method for producing the same | |
| JP3305111B2 (en) | Stabilized sodium percarbonate particles and method for producing the same | |
| JP3314526B2 (en) | Method for producing stabilized sodium percarbonate particles | |
| JPH0437119B2 (en) | ||
| JPH0559960B2 (en) | ||
| JP2869310B2 (en) | Stable sodium percarbonate, method for producing the same, and bleaching detergent composition containing stable sodium percarbonate | |
| JPH0139962B2 (en) | ||
| KR100321534B1 (en) | Method for preparing abrasion resistant sodium percarbonate with fast dissolution rate and sodium percarbonate prepared therefrom | |
| JPS621563B2 (en) | ||
| JP3838276B2 (en) | Stabilized and highly soluble sodium percarbonate particles | |
| JPH09227108A (en) | Stable sodium percarbonate excellent in solubility | |
| US5744055A (en) | Stable monopersulfate triple salt and its method of preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080510 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090510 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090510 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100510 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100510 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110510 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |