JP2006131455A - Sodium percarbonate particle excellent in foaming and solubility - Google Patents
Sodium percarbonate particle excellent in foaming and solubility Download PDFInfo
- Publication number
- JP2006131455A JP2006131455A JP2004322310A JP2004322310A JP2006131455A JP 2006131455 A JP2006131455 A JP 2006131455A JP 2004322310 A JP2004322310 A JP 2004322310A JP 2004322310 A JP2004322310 A JP 2004322310A JP 2006131455 A JP2006131455 A JP 2006131455A
- Authority
- JP
- Japan
- Prior art keywords
- sodium percarbonate
- water
- solubility
- little
- foaming
- 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.)
- Granted
Links
Landscapes
- Detergent Compositions (AREA)
Abstract
Description
本発明は、水に対する発泡溶解性に優れ、取り扱い中に破砕、摩耗の少ない過炭酸ナトリウム粒子の製造方法に関する。本発明の過炭酸ナトリウム粒子は、漂白剤組成物として好適に利用される。 The present invention relates to a method for producing sodium percarbonate particles having excellent foam solubility in water and being less crushed and worn during handling. The sodium percarbonate particles of the present invention are suitably used as a bleaching composition.
過炭酸ナトリウムは、分解生成物が主に水と酸素であることから、環境に対する影響が少なく、酸素系漂白剤として幅広く利用されている。過炭酸ナトリウムは、温水に対する溶解性は良いものの低温の水には比較的溶けにくい。また色柄の衣服等に付着して部分的に漂白剤成分濃度が高くなることから、脱色や繊維強度の低下等を起こさないために、溶解性の向上と溶け残りがないことが求められている。また過炭酸ナトリウムは粉末状で取り扱われるため、使用の際の粉立ちの少ないことも求められている。 Sodium percarbonate has little influence on the environment because its decomposition products are mainly water and oxygen, and is widely used as an oxygen bleach. Although sodium percarbonate has good solubility in hot water, it is relatively insoluble in low-temperature water. In addition, since the concentration of the bleach component is partially increased by adhering to colored clothes, etc., in order not to cause decolorization or decrease in fiber strength, there is a need for improved solubility and no undissolved residue. Yes. In addition, since sodium percarbonate is handled in a powder form, it is also required to have less dusting when used.
過炭酸ナトリウムの低温での溶解性を向上させる方法の一つとして、加熱処理を行い過炭酸ナトリウムに発泡性を持たせる方法が挙げられる（特許文献１参照）。しかし、加熱による発泡性の付与だけで所望の溶解性を得るためには高温で長時間の加熱処理が必要となり、その間に有効酸素の分解が進み有効な手段ではない。また加熱処理により過炭酸ナトリウムの粒子強度が弱くなり、取り扱い中に破砕、磨耗による微粉が多量に発生し、粉立ちが多くなることも問題となる。 One method for improving the solubility of sodium percarbonate at low temperatures is to heat-treat sodium percarbonate to give foaming properties (see Patent Document 1). However, in order to obtain a desired solubility only by imparting foamability by heating, heat treatment for a long time at high temperature is required, and during this time, decomposition of effective oxygen advances and is not an effective means. Moreover, the particle strength of sodium percarbonate is weakened by the heat treatment, and a large amount of fine powder is generated due to crushing and wear during handling, resulting in a problem of increased dusting.
高級アルコールのエチレンオキサイド付加物等の非イオン界面活性剤を添加して浮上性をもたせ、これを加熱処理して溶解性を良くする方法も提案されているが、粒子強度が弱くなり破砕、磨耗による微粉発生で粉立ちが多くなる問題は解決されない（特許文献２参照）。また、過炭酸ナトリウム粒子を金属塩で被覆し、処理温度を９５℃〜１０５℃とすることで水に溶解した際に発泡して溶解させる方法が開示されているが、溶解性は不十分で更なる改良が求められている（特許文献３参照）。
本発明の目的は、従来技術における上記のような問題を解決し、水に溶解する際の発泡溶解性に優れ、取り扱い中に破砕、摩耗の少ない過炭酸ナトリウム粒子を提供することにある。 An object of the present invention is to solve the above-described problems in the prior art, and to provide sodium percarbonate particles that are excellent in foam solubility when dissolved in water and are less crushed and worn during handling.
本発明者らはかかる問題を解決するため鋭意検討を行い、本発明を完成させた。すなわち本発明は、過炭酸ナトリウム粒子に水溶性高分子を０．１〜１５重量％被覆し、５０℃〜１２０℃で加熱処理を行うことを特徴とする、発泡浮上しながら溶解するとともに、取り扱い中に破砕、摩耗の少ない過炭酸ナトリウム粒子の製造方法に関するものである。 The present inventors have intensively studied to solve such problems, and completed the present invention. That is, the present invention is characterized in that sodium percarbonate particles are coated with 0.1 to 15% by weight of a water-soluble polymer and heat-treated at 50 ° C. to 120 ° C. The present invention relates to a method for producing sodium percarbonate particles with less crushing and wear.
本発明の過炭酸ナトリウム粒子は、水に溶解する際に発泡するとともに水中で浮上しながらすばやく溶ける。また底に沈降しての溶け残り分が極めて少なく、特に攪拌がない、あるいは攪拌をほとんど行わない状態での溶解性に優れている。しかも本発明品は粒子強度が強く、破砕、磨耗による微粉発生が少なく取り扱いに際しての粉立ちが少ない。 The sodium percarbonate particles of the present invention foam when dissolved in water and quickly dissolve while floating in water. In addition, the amount of undissolved residue after sinking to the bottom is extremely small, and the solubility in a state where there is no stirring or almost no stirring is excellent. In addition, the product of the present invention has a high particle strength, less generation of fine powder due to crushing and abrasion, and less dusting during handling.
本発明をさらに詳しく説明する。過炭酸ナトリウムは、水中で炭酸ナトリウムと過酸化水素を反応させ、析出した結晶を遠心分離機等で分離し、得られた過炭酸ナトリウム結晶を用いて造粒を行う。造粒は捏和式造粒機による凝集造粒、スクリーンを有する押し出し造粒機による押し出し造粒など挙げられるが限定されない。造粒時に過炭酸ナトリウムの助燃性を低減するための希釈剤として、無機塩を添加することができる。具体例としては炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、硫酸ナトリウムなど挙げられる。また造粒の際に各種バインダーが使用でき、無機系バインダーとして珪酸塩、マグネシウム塩などが、有機系バインダーとしてポリビニルアルコール、カルボキシメチルセルロースなどが挙げられるが限定はしない。 The present invention will be described in more detail. Sodium percarbonate reacts with sodium carbonate and hydrogen peroxide in water, separates the precipitated crystals with a centrifugal separator or the like, and granulates using the obtained sodium percarbonate crystals. Examples of the granulation include, but are not limited to, agglomeration granulation using a kneading granulator and extrusion granulation using an extrusion granulator having a screen. An inorganic salt can be added as a diluent for reducing the supporting property of sodium percarbonate during granulation. Specific examples include sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfate and the like. Various types of binders can be used during granulation. Examples of inorganic binders include silicates and magnesium salts. Examples of organic binders include polyvinyl alcohol and carboxymethyl cellulose, but are not limited thereto.
造粒した過炭酸ナトリウム粒子は乾燥した後、水溶性高分子で被覆する。この場合の水溶性高分子としては、ポリエチレングリコール、ポリビニルアルコール、ポリアクリル酸、ポリアクリル酸ナトリウムがあげられるが、なかでもポリエチレングリコールが好ましい。ポリエチレングリコールは、分子量が１０００〜２００００、好ましくは２０００〜２００００の範囲のものが適している。また、水溶性高分子は２種類以上を混合して使用してもよい。 The granulated sodium percarbonate particles are dried and then coated with a water-soluble polymer. Examples of the water-soluble polymer in this case include polyethylene glycol, polyvinyl alcohol, polyacrylic acid, and sodium polyacrylate. Among them, polyethylene glycol is preferable. Polyethylene glycol having a molecular weight of 1000 to 20000, preferably 2000 to 20000 is suitable. Two or more water-soluble polymers may be mixed and used.
被覆は、過炭酸ナトリウム粒子を加熱空気で流動させ、水溶性高分子を水溶液で噴霧する方法が一般的であるが限定はしない。また、無機塩を被覆した過炭酸ナトリウム粒子に水溶性高分子を重ねて被覆することも可能である。この場合の無機塩としては、例えば炭酸塩、重炭酸塩、硫酸塩、珪酸塩、ホウ酸塩が挙げられる。また、水溶性高分子と無機塩を混合して被覆することも可能である。水溶性高分子の量は、過炭酸ナトリウムに対して０．１重量％〜１５重量％であり、好ましくは０．５重量％〜１０重量％である。被覆量が０．１重量％以下であると所望の浮上性が得られず、被覆量が１５重量％を超えると粒子強度に改善は見られず、更なる増量は経済的でない。 For coating, a method of flowing sodium percarbonate particles with heated air and spraying a water-soluble polymer with an aqueous solution is common but not limited. It is also possible to coat the sodium percarbonate particles coated with an inorganic salt with a water-soluble polymer. Examples of inorganic salts in this case include carbonates, bicarbonates, sulfates, silicates, and borates. It is also possible to coat by mixing a water-soluble polymer and an inorganic salt. The amount of the water-soluble polymer is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on sodium percarbonate. If the coating amount is 0.1% by weight or less, the desired floating property cannot be obtained, and if the coating amount exceeds 15% by weight, no improvement is seen in the particle strength, and further increase in the amount is not economical.
過炭酸ナトリウム粒子の被覆後、加熱処理を行う。加熱温度は、５０℃〜１２０℃であり、好ましくは９５℃〜１２０℃、さらに好ましくは１００〜１０５℃である。加熱後は、有効酸素の分解を抑制するために直ちに冷却する。冷却方法は空気をそのまま、あるいは除湿して用いる方法、窒素を使用する方法等が挙げられるが限定はしない。冷却後の温度は４０℃以下にするのが好ましい。 After coating with sodium percarbonate particles, heat treatment is performed. The heating temperature is 50 ° C to 120 ° C, preferably 95 ° C to 120 ° C, more preferably 100 ° C to 105 ° C. Immediately after heating, in order to suppress decomposition of available oxygen. Examples of the cooling method include, but are not limited to, a method using air as it is or dehumidifying, a method using nitrogen, and the like. The temperature after cooling is preferably 40 ° C. or lower.
加熱処理した過炭酸ナトリウム粒子は、篩分けにより２，０００μ以上の大粒子を１重量％以下に、１８０μ以下の微粒子を３重量％以下にするのが好ましい。２，０００μを越える大粒子が多いと崩壊し易く浮上性が著しく低下する。一方１８０μｍより小さい微粉が多いと粉立ちが多くなる。 The heat-treated sodium percarbonate particles are preferably screened to make 2,000 μm or more large particles 1% by weight or less and 180 μm or less fine particles 3% by weight or less. If there are many large particles exceeding 2,000 μm, the particles are easily disintegrated and the flying property is remarkably lowered. On the other hand, when there are many fine powders smaller than 180 micrometers, powdering will increase.
また、本発明の方法で得られた過炭酸ナトリウム粒子は、界面活性剤、活性化剤、安定化剤、香料等の成分を加えて衣料用の漂白剤組成物とすることができる。また、この他にも台所用漂白剤、風呂釜洗浄剤、排水管クリーナー、洗濯槽クリーナー等の種々の用途に利用できる。 Moreover, the sodium percarbonate particle | grains obtained by the method of this invention can add components, such as surfactant, an activator, a stabilizer, and a fragrance | flavor, and can be used as the bleaching composition for clothes. In addition, it can be used for various applications such as kitchen bleach, bath tub cleaner, drain pipe cleaner, and washing tub cleaner.
次いで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限定されるものではない。 Next, the method of the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited to these examples.
実施例１
炭酸ナトリウムと過酸化水素を水溶液中で反応し、生成した過炭酸ナトリウムの結晶を遠心分離機によって分離、脱水して１０重量％の水分を含む湿潤状態の過炭酸ナトリウムを得た。湿潤状態の過炭酸ナトリウムに東ソー製重炭酸ナトリウムを過炭酸ナトリウムに対して乾燥状態基準で２０重量％とバインダーとして硫酸マグネシウムを０．２重量％および珪酸ナトリウム０．２５重量％を加え、さらに水を加えて含水率を１１％に調整した。次に捏和式乾燥機、整粒機の順に造粒を行った後に７０℃で２時間乾燥して、平均粒径５００μｍの過炭酸ナトリウム粒子を得た。
Example 1
Sodium carbonate and hydrogen peroxide were reacted in an aqueous solution, and the produced sodium percarbonate crystals were separated by a centrifuge and dehydrated to obtain wet sodium percarbonate containing 10% by weight of water. Toso sodium carbonate in a wet state is added 20% by weight of sodium bicarbonate made by Tosoh on a basis of sodium percarbonate, 0.2% by weight of magnesium sulfate and 0.25% by weight of sodium silicate as a binder, and water. Was added to adjust the water content to 11%. Next, granulation was performed in the order of a kneading dryer and a granulator, followed by drying at 70 ° C. for 2 hours to obtain sodium percarbonate particles having an average particle diameter of 500 μm.
得られた過炭酸ナトリウム粒子３００ｇを流動乾燥機（ヤマト科学（株）製パルビスミニベット）を用い、加熱空気で過炭酸ナトリウムを流動させながら平均分子量６０００のポリエチレングリコールを１０重量％含む水溶液１５０ｇを噴霧して被覆した。被覆後加 熱空気の温度を１００℃に保ち流動させながら９０分間の加熱を行った。加熱品を冷却後上網目開き１４００μｍ、下網目開き２５０μｍを設置した振動篩を用いて大粒子と小粒子を取り除いた。得られた過炭酸ナトリウム粒子について、水に投入した際の浮上性及び式（１）で定義される崩壊性を導出した。測定結果を表１に示す。 Using 300 g of the obtained sodium percarbonate particles, 150 g of an aqueous solution containing 10% by weight of polyethylene glycol having an average molecular weight of 6000 while flowing sodium percarbonate with heated air using a fluid dryer (Yamato Kagaku Co., Ltd. Parvis mini bed). Were spray coated. After coating, the heated air was kept at a temperature of 100 ° C. and heated for 90 minutes while flowing. After cooling the heated product, large particles and small particles were removed using a vibrating sieve provided with an upper mesh opening of 1400 μm and a lower mesh opening of 250 μm. About the obtained sodium percarbonate particle | grains, the floating property at the time of throwing into water and the disintegration property defined by Formula (1) were derived. The measurement results are shown in Table 1.
＜崩壊性測定方法＞
篩で１８０μｍ以下の粒径をカットした試料１００ｇを５００ｍｌポリエチレン製広口瓶に入れ、振とう機により１０分間振とう後、篩で１８０μｍ以下の微粉を１８０μｍの篩で篩分け、１８０μｍ以下の微粉発生量を測定した。
<Method of measuring disintegration>
Put 100 g of sample with a particle size of 180 μm or less with a sieve into a 500 ml polyethylene jar and shake for 10 minutes with a shaker. The amount was measured.
＜浮上性測定方法＞
１０００ｍｌのビーカーに１０℃の水１０００ｇを入れ、ビーカーの中央部に試料１ｇを投入して浮上してくる過炭酸ナトリウム粒子の量を目視にて判定し、A〜Eにランク付けする。
<Floatability measurement method>
Place 1000 g of water at 10 ° C. into a 1000 ml beaker, put 1 g of sample in the center of the beaker, visually determine the amount of sodium percarbonate particles that rise, and rank A to E.
実施例２
被覆する１０重量％ポリエチレングリコール水溶液の量を６０ｇとした以外は実施例１と同様の操作を実施した。測定結果を表１に示す。
Example 2
The same operation as in Example 1 was performed except that the amount of the 10 wt% polyethylene glycol aqueous solution to be coated was changed to 60 g. The measurement results are shown in Table 1.
実施例３
被覆するポリエチレングリコールの平均分子量を２０００とした以外は実施例１と同様の操作を実施した。測定結果を表１に示す。
Example 3
The same operation as in Example 1 was performed except that the average molecular weight of polyethylene glycol to be coated was 2000. The measurement results are shown in Table 1.
実施例４
被覆するポリエチレングリコールの平均分子量を２００００とした以外は実施例１と同様の操作を実施した。測定結果を表１に示す。
Example 4
The same operation as in Example 1 was carried out except that the average molecular weight of polyethylene glycol to be coated was 20000. The measurement results are shown in Table 1.
実施例５
被覆後加熱空気の温度を８５℃に保ち流動させながら、１８０分間の加熱を行った以外は、実施例１と同様に行った。測定結果を表１に示す。
Example 5
The same procedure as in Example 1 was performed except that heating was performed for 180 minutes while keeping the temperature of the heated air after coating at 85 ° C. and flowing. The measurement results are shown in Table 1.
比較例１
ポリエチレングリコールを被覆しなかった以外は、実施例１と同様に行った。測定結果を表１に示す。
Comparative Example 1
The same procedure as in Example 1 was performed except that polyethylene glycol was not coated. The measurement results are shown in Table 1.
比較例２
加熱しなかった以外は、実施例１と同様に行った。測定結果を表１に示す。
Comparative Example 2
The same operation as in Example 1 was performed except that heating was not performed. The measurement results are shown in Table 1.
比較例３
被覆後加熱空気の温度を４０℃に保ち流動させながら、１８０分間の加熱を行った以外は、実施例１と同様に行った。測定結果を表１に示す。
Comparative Example 3
The same procedure as in Example 1 was performed except that heating was performed for 180 minutes while keeping the temperature of the heated air after coating at 40 ° C. and flowing. The measurement results are shown in Table 1.
比較例４
被覆後加熱空気の温度を１２５℃に保ち流動させながら２０分間の加熱を行った以外は、実施例１と同様に行った。測定結果を表１に示す。
Comparative Example 4
The same procedure as in Example 1 was conducted except that the heating air after coating was kept at 125 ° C. and heated for 20 minutes while flowing. The measurement results are shown in Table 1.
比較例５
被覆するポエチレングリコールの平均分子量が６００とした以外は実施例１と同様の操作を実施した。測定結果を表１に示す。
Comparative Example 5
The same operation as in Example 1 was performed except that the average molecular weight of the polyethylene glycol to be coated was 600. The measurement results are shown in Table 1.
比較例６
被覆するポエチレングリコールの平均分子量が５０００００を用いたが水に対する溶解性が小さく、被覆が出来なかった。
Comparative Example 6
Although the average molecular weight of the polyethylene glycol to be coated was 500,000, the solubility in water was small and the coating could not be performed.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004322310A JP4506962B2 (en) | 2004-11-05 | 2004-11-05 | Sodium percarbonate particles with excellent foam solubility |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004322310A JP4506962B2 (en) | 2004-11-05 | 2004-11-05 | Sodium percarbonate particles with excellent foam solubility |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006131455A true JP2006131455A (en) | 2006-05-25 |
| JP4506962B2 JP4506962B2 (en) | 2010-07-21 |
Family
ID=36725332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004322310A Expired - Fee Related JP4506962B2 (en) | 2004-11-05 | 2004-11-05 | Sodium percarbonate particles with excellent foam solubility |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4506962B2 (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52117897A (en) * | 1976-03-29 | 1977-10-03 | Air Liquide | Novel sodium peroxide and process for preparing same |
| JPS5874508A (en) * | 1981-10-24 | 1983-05-06 | Mitsubishi Gas Chem Co Inc | Manufacture of sodium percarbonate |
| JPS59195505A (en) * | 1983-04-18 | 1984-11-06 | Kao Corp | Manufacture of floating expandable sodium percarbonate |
| JPS63147804A (en) * | 1986-12-11 | 1988-06-20 | Nippon Peroxide Co Ltd | Production of sodium percarbonate |
| JPH06107401A (en) * | 1991-02-26 | 1994-04-19 | Topy Jitsugyo Kk | Oxygen generating agent |
| JPH06157010A (en) * | 1992-11-20 | 1994-06-03 | Central Glass Co Ltd | Stabilized sodium percarbonate composition and its production |
| JPH07500805A (en) * | 1991-09-03 | 1995-01-26 | デグツサ アクチエンゲゼルシヤフト | Shelf-stable encapsulated sodium percarbonate and its manufacturing method |
| JPH0977505A (en) * | 1995-09-11 | 1997-03-25 | Lion Corp | Production of granulated bleach-activating agent |
| JP2002167203A (en) * | 2000-09-19 | 2002-06-11 | Nippon Peroxide Co Ltd | Coated sodium percarbonate with high stability and solubility, and its manufacturing method |
-
2004
- 2004-11-05 JP JP2004322310A patent/JP4506962B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52117897A (en) * | 1976-03-29 | 1977-10-03 | Air Liquide | Novel sodium peroxide and process for preparing same |
| JPS5874508A (en) * | 1981-10-24 | 1983-05-06 | Mitsubishi Gas Chem Co Inc | Manufacture of sodium percarbonate |
| JPS59195505A (en) * | 1983-04-18 | 1984-11-06 | Kao Corp | Manufacture of floating expandable sodium percarbonate |
| JPS63147804A (en) * | 1986-12-11 | 1988-06-20 | Nippon Peroxide Co Ltd | Production of sodium percarbonate |
| JPH06107401A (en) * | 1991-02-26 | 1994-04-19 | Topy Jitsugyo Kk | Oxygen generating agent |
| JPH07500805A (en) * | 1991-09-03 | 1995-01-26 | デグツサ アクチエンゲゼルシヤフト | Shelf-stable encapsulated sodium percarbonate and its manufacturing method |
| JPH06157010A (en) * | 1992-11-20 | 1994-06-03 | Central Glass Co Ltd | Stabilized sodium percarbonate composition and its production |
| JPH0977505A (en) * | 1995-09-11 | 1997-03-25 | Lion Corp | Production of granulated bleach-activating agent |
| JP2002167203A (en) * | 2000-09-19 | 2002-06-11 | Nippon Peroxide Co Ltd | Coated sodium percarbonate with high stability and solubility, and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4506962B2 (en) | 2010-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH086118B2 (en) | Method for producing aggregate containing diperoxide decanedioic acid | |
| JPH05309255A (en) | Production of salt granule | |
| CN114774206A (en) | Composite detergent particles and laundry detergent composition comprising the same | |
| CN105431513B (en) | Method for producing detergent particles, detergent particles and the detergent composition for including the particle | |
| JP2009126885A (en) | Method for modifying surface of particle | |
| JP4596132B2 (en) | Sodium percarbonate particles with excellent solubility and particle strength | |
| JP4506962B2 (en) | Sodium percarbonate particles with excellent foam solubility | |
| JP4176595B2 (en) | Cleaning composition | |
| JP2006137925A (en) | Method for producing single uncleus detergent particles | |
| CN106715662B (en) | Structured detergent particles and granular detergent compositions comprising the same | |
| WO2000077148A1 (en) | Granules for carrying surfactant and method for producing the same | |
| JPWO2004094313A1 (en) | Surface-treated water-soluble inorganic compound particles, production method thereof, and granular detergent composition | |
| JP2001003094A (en) | Detergent composition | |
| JP4143853B2 (en) | Particles containing water-soluble inorganic substances | |
| JP4379592B2 (en) | Method for producing sodium percarbonate particles having excellent solubility | |
| JP2007308826A (en) | Slipperiness improving agent granulate for washing | |
| JP3004546B2 (en) | Method for producing granulated bleach activator and granulated bleach activator | |
| JP4381505B2 (en) | Washing method | |
| JP4102989B2 (en) | Coated particles and detergent composition | |
| JP4237532B2 (en) | Surfactant-supporting granules | |
| JP2006070267A (en) | Production process of mononuclear detergent particle group | |
| JP5612808B2 (en) | Detergent particles | |
| JP4667730B2 (en) | Method for treating crystalline alkali metal silicate | |
| JP2010254504A (en) | Method for producing foamable and floatable sodium percarbonate particle excellent in storage stability | |
| JP2659698B2 (en) | Continuous production method of high-density powder detergent with excellent fluidity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071002 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20091124 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091202 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100115 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100407 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100420 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130514 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130514 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130514 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140514 Year of fee payment: 4 |
|
| LAPS | Cancellation because of no payment of annual fees |