JP4102989B2 - Coated particles and detergent composition - Google Patents

Description

（式中、Ｒ¹⁹はそれぞれ独立に炭素数７以上のアルキル基又はアルケニル基、Ｐｈはフェニレン基、Ｍはそれぞれ独立に塩形成カチオン又は水素を示す。）
【００８２】
Ｒ¹⁹は、炭素数７以上のアルキル基又はアルケニル基であり、炭素数７〜１７のアルキル基又はアルケニル基、特に直鎖状アルキル基が好ましく、より好ましくは炭素数９〜１５の直鎖状アルキル基である。また、Ｍは塩形成カチオン又は水素であり、ナトリウム、カリウム等のアルカリ金属、アンモニウム、アルカノールアミン等のアミン類が挙げられる。この中で水素、アルカリ金属が好ましい。上記一般式中、ＳＯ₃Ｍ基やＣＯＯＭ基は、オルト、メタ又はパラ位をとることができ、パラ位が好ましい。
【００８３】
洗浄剤粒子群においては、これらの漂白活性化剤を１種を単独で又は２種以上の混合物として用いることができる。これらの漂白活性化剤は、通常の製造方法により約１００〜１０００μｍの板状結晶で得られるので、必要に応じて常法により平均粒子径が８００μｍより小さくなるように、好ましくは２５０〜７５０μｍ程度となるように粉砕する。さらに、保存安定性向上と溶解性向上の点から、ＰＥＧ＃３０００〜＃２００００のような常温で固体のポリエチレングリコールを加熱溶融した中に漂白活性化剤を分散後、押し出して直径１ｍｍ程度のヌードル状の漂白活性化剤造粒物を製造し、その後長さ１〜３ｍｍ程度に軽く粉砕してから用いてもよい。
【００８４】
漂白活性化剤の含有量は、洗浄剤粒子群全量に対し０．５〜１５質量％が好ましく、１〜１０質量％が特に好ましい。
【００８５】
また、上記洗浄剤粒子単独、各種粒子及び必要に応じて液状の添加剤を混合した混合物に賦香してもよい。
また、場合によっては被覆粒子と洗浄剤粒子群を混合した後、賦香してもよい。用いられる香料としては、脂肪族炭化水素、テルペン炭化水素、芳香族炭化水素等の炭化水素類、脂肪族アルコール、テルペンアルコール、芳香族アルコール等のアルコール類、脂肪族エーテル、芳香族エーテル等のエーテル類、脂肪族オキサイド、テルペン類のオキサイド等のオキサイド類、脂肪族アルデヒド、テルペン系アルデヒド、水素化芳香族アルデヒド、チオアルデヒド、芳香族アルデヒド等のアルデヒド類、脂肪族ケトン、テルペンケトン、水素化芳香族ケトン、脂肪族環状ケトン、非ベンゼン系芳香族ケトン、芳香族ケトン等のケトン類、アセタール類、ケタール類、フェノール類、フェノールエーテル類、脂肪酸、テルペン系カルボン酸、水素化芳香族カルボン酸、芳香族カルボン酸等の酸類、酸アマイド類、脂肪族ラクトン、大環状ラクトン、テルペン系ラクトン、水素化芳香族ラクトン、芳香族ラクトン等のラクトン類、脂肪族エステル、フラン系カルボン酸族エステル、脂肪族環状カルボン酸エステル、シクロヘキシルカルボン酸族エステル、テルペン系カルボン酸エステル、芳香族カルボン酸エステル等のエステル類、ニトロムスク類、ニトリル、アミン、ピリジン類、キノリン類、ピロール、インドール等の含窒素化合物等々の合成香料及び動物、植物からの天然香料、天然香料及び／又は合成香料を含む調合香料の１種又は２種以上を混合し使用することができる。例えば、１９９６年化学工業日報社刊印藤元一著「合成香料化学と商品知識」、１９６９年ＭＯＮＴＣＬＡＩＲ，Ｎ．Ｊ．刊ＳＴＥＦＦＥＮ ＡＲＣＴＡＮＤＥＲ著“Ｐｅｒｆｕｍｅ ａｎｄ Ｆｌａｖｏｒ Ｃｈｅｍｉｃａｌｓ”等に記載の香料が使用できる。以下に主な香料名を示す。
【００８６】
アルデヒドＣ６〜Ｃ１２、アニスアルデヒド、アセタールＲ、アセトフェノン、アセチルセドレン、アドキサール、アリルアミルグリコレート、アリルシクロヘキサンプロピオネート、アルファダマスコン、ベータダマスコン、デルタダマスコン、アンブレットリッド、アンブロキサン、アミルシンナミックアルデヒド、アミルシンナミックアルデヒドジメチルアセタール、アミルバレリアネート、アミルサリシレート、イソアミルアセテート、イソアミルサリシレート、オウランチオール、アセチルユゲノール、バクダノール、ベンジルアセテート、ベンジルアルコール、ベンジルサリシレート、ベルガミールアセテート、ボルニルアセテート、ブチルブチレート、パラターシャリーブチルシクロヘキサノール、パラターシャリーブチルシクロヘキシルアセテート、オルトターシャリーブチルシクロヘキサノール、オルトーターシャリーブチルシクロヘキシルアセテート、ベンツアルデヒド、ベンジルフォーメート、カリオフィレン、カシュメラン、カルボン、セドロアンバー、セドリルアセテート、セドロール、セレストリッド、シンナミックアルコール、シンナミックアルデヒド、シスジャスモン、シトラール、シトラールジメチルアセタール、シトラサール、シトロネラール、シトロネロール、シトロネリルアセテート、シトロネリルフォーメート、シトロネリルニトリル、シクラセット、シクラメンアルデヒド、シクラプロップ、キャロン、クマリン、シンナミルアセテート、デルタＣ６〜Ｃ１３ラクトン、ジメチルベンジルカービノール、ジヒドロジャスモン、ジヒドロリナロール、ジヒドロミルセノール、ジメトール、ジミルセトール、ジフェニルオキサイド、エチルワニリン、ユゲノール、フルイテート、フェンチールアルコール、フェニルエチルフェニルアセテート、ガラキソリッド、ガンマーＣ６〜１３ラクトン、α−ピネン、β−ピネン、リモネン、ミルセン、β−カリオフィレン、ゲラニオール、ゲラニルアセテート、ゲラニルフォーメート、ゲラニルニトリル、ヘディオン、ヘリオナール、ヘリオトロピン、シス−３−ヘキセノール、シス−３−ヘキセニールアセテート、シス−３−ヘキセニールサリシレート、トリプラール、ヘキシルシンナミックアルデヒド、ヘキシルサリシレート、ヒヤシンスジメチルアセタール、ハイドロトロピックアルコール、ヒドロキシシトロネラール、インドール、イオノン、イソボルニルアセテート、イソシクロシトラール、イソＥスーパー、イソユゲノール、イソノニルアセテート、イソブチルキノリン、ジャスマール、ジャスモラクトン、ジャスモフィラン、コアボン、リグストラール、リリアール、ライムオキサイド、リナロール、リナロールオキサイド、リナリルアセテート、リラール、マンザネート、マイヨール、メンサニールアセテート、メンソネート、メチルアンスラニレート、メチルユゲノール、メントール、アルファメチルイオノン、ベータメチルイオノン、ガンマメチルイオノン、メチルイソユゲノール、メチルラベンダーケトン、メチルサリシレート、ミューゲアルデヒド、ムゴール、ムスクＴＭ−ＩＩ、ムスク７８１、ムスクＣ１４、ムスコン、シベトン、シクロペンタデカノン、シクロヘキサデセノン、シクロペンタデカノリド、アンブレットリド、シクロヘキサデカノリド、１０−オキサヘキサデカノリド、１１−オキサヘキサデカノリド、１２−オキサヘキサデカノリド、エチレンブラシレート、エチレンドデカンジオエート、オキサヘキサデセン−２−オン、１４−メチル−ヘキサデセノリド、１４−メチル−ヘキサデカノリド、ムスクケトン、ムスクチベチン、ノピルアルコール、ノピルアセテート、ネリルアセテート、ネロール、メチルフェニルアセテート、ミラックアルデヒド、ネオベルガメート、オークモスＮｏ，１、オリボン、オキシフェニロン、パラクレジールメチルエーテル、ペンタリッド、フェニルエチルアルコール、フェニルエチルアセテート、アルファピネン、ルバフラン、ダマセノン、ラズベリーケトン、ジメチルベンジルカルビニルアセテート、ジャスマサイクレン、メチルナフチルケトン、ローズフェノン、ローズオキサイド、サンダロア、サンデラ、サンタレックス、スチラリールアセテート、スチラリールプロピオネート、ターピネオール、ターピニルアセテート、テトラハイドロリナロール、テトラハイドロリナリールアセテート、テトラハイドロゲラニオール、テトラハイドロゲラニールアセテート、トナリッド、トラセオライド、トリプラール、チモール、ワニリン、ベルドックス、ヤラヤラ、アニス油、ベイ油、ボアドローズ油、カナンガ油、カルダモン油、カシア油、シダーウッド油、オレンジ油、マンダリン油、タンジェリン油、バジル油、ナツメグ油、シトロネラ油、クローブ油、コリアンダー油、エレミ油、ユーカリ油、フェンネル油、ガルバナム油、ゼラニウム油、ヒバ油、桧油、ジャスミン油、ラバンジン油、ラベンダー油、レモン油、レモングラス油、ライム油、ネロリ油、オークモス油、オコチア油、パチュリ油、ペパーミント油、ペリラ油、プチグレン油、パイン油、ローズ油、ローズマリー油、しょう脳油、芳油、クラリーセージ油、サンダルウッド油、スペアミント油、スパイクラベンダー油、スターアニス油、タイム油、トンカ豆チンキ、テレピン油、ワニラ豆チンキ、ベチバー油、イランイラン油、グレープフルーツ油、ゆず油、ベンゾイン、ペルーバルサム、トルーバルサム、チュベローズ油、オークモスアブソリュート、ファーバルサム、ムスクチンキ、カストリウムチンキ、シベットチンキ、アンバーグリスチンキが挙げられる。
【００８７】
香料の溶剤又は保留剤としてジエチルフタレート、ジプロピレングリコール、ベンジルベンゾエート、イソプロピルミリステート、ハーコリン、イソペンタン、オレンジテルペン等を使用することができる。なお、香料は実施例の香料に限定されない。
【００８８】
本発明において被覆粒子と洗浄剤粒子群は任意に混合して用いることができるが、その比率（質量比）として被覆粒子／洗浄剤粒子群＝３／９７〜９７／３が好ましく、５／９５〜９５／５がより好ましく、１０／９０〜９０／１０がさらに好ましい。
【００８９】
その混合方法としては、乾式混合が好適に用いられる。使用する混合機は、各種粒子同士が十分に混合できる限りいかなる混合機を用いてもよいが、水平円筒型、二重円錐型、Ｖ型、自転・公転型等の混合機が好適に利用できる。また、撹拌造粒機、転動造粒機を用いてもよい。好ましくは、水平円筒型又は二重円錐型を用い、温度０〜５０℃、Ｆｒ数０．０１〜０．２（算出式は上述した通り）で混合する。このとき、各種粒子やそれ以外の成分の添加順序は特に問わない。
【００９０】
最終的に被覆粒子と洗浄剤粒子群を混合して得られた粒状洗剤組成物の物性値は、特に制限されるものではないが、嵩密度は、通常０．３ｇ／ｍＬ以上、好ましくは０．５〜１．２ｇ／ｍＬ、より好ましくは０．６〜１．１ｇ／ｍＬである。また、平均粒子径は、好ましくは２００〜１５００μｍ、より好ましくは３００〜１０００μｍである。平均粒子径が２００μｍ未満になると粉塵が発生し易くなる場合があり、一方、１５００μｍを超えると本発明が目的とする溶解性が得られ難くなる場合がある。さらに、洗剤組成物の流動性は、安息角として６０°以下、特に５０°以下が好適である。６０°を超えると取扱性が悪化する場合がある。
【００９１】
被覆粒子と洗浄剤粒子群を混合して得られた洗剤組成物はそのまま粒状洗浄剤として利用することはもちろん、さらに崩壊剤等を混合した後圧縮成形して、タブレット洗浄剤やブリケット洗浄剤等の圧縮成形洗浄剤として利用することもできる。
【００９２】
【発明の効果】
本発明によれば、長期保存時の水中での凝集による溶解性の低下がなく、分散性に優れ、さらには、造粒機への付着性も防止された被覆粒子及び洗剤組成物を提供することができる。
【００９３】
【実施例】
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において特に明記のない場合は、％は質量％、比率は質量比を示し、表中の各成分の量は純分換算した量である。
【００９４】
被覆粒子の製造方法▲１▼（撹拌造粒）
下記表２〜６に示す組成のうち、水溶性無機塩（温度２５℃）を鋤刃状ショベルを装備し、ショベル−壁面間クリアランスが５ｍｍのレーディゲミキサー（（株）マツボー製、Ｍ２０型）に投入し（充填率３０容量％）、主軸２００ｒｐｍの撹拌を開始した（チョッパーは停止）。撹拌開始後１０秒後に塩感応性高分子を３０秒で添加し、添加終了後、塩感応性高分子を感応せしめる塩（以下、高分子感応性塩）を液体の場合は３０秒間で滴下添加し、粉体の場合は一括添加し３０秒撹拌した。最後に必要に応じて流動性改善剤を添加し、３０秒間撹拌を続け造粒物を得た。
【００９５】
得られた造粒物を目開き２０００μｍの篩を用いて分級し、目開き２０００μｍの篩を通過する粒子を被覆粒子とした。なお、比較例においては高分子感応性塩の添加は行わなかった。
【００９６】
被覆粒子の製造方法▲２▼（転動造粒）
下記表２〜６に示す組成のうち、水溶性無機塩（温度２５℃）を水平円筒型転動混合機（円筒直径５８５ｍｍ、円筒長さ４９０ｍｍ、容器１３１．７Ｌのドラム内部壁面に内部壁面とのクリアランス２０ｍｍ、高さ４５ｍｍの邪魔板を２枚有するもの）に投入し（充填率２０容量％）、回転数２２ｒｐｍ、２５℃の条件で転動操作を開始した。転動開始後３０秒後に塩感応性高分子を噴霧角度７０°の２流体ホローコーンノズルを用いて１００ｇ／ｍｉｎで噴霧添加し、添加終了後、高分子感応性塩を液体の場合は１００ｇ／ｍｉｎで噴霧添加し、粉体の場合は一括添加し６０秒転動混合した。最後に必要に応じて流動性改善剤を添加し、６０秒間転動操作を続け造粒物を得た。
【００９７】
得られた造粒物を目開き２５０μｍ及び目開き２０００μｍの篩を用いて分級し、目開き２５０μｍを通過せず、目開き２０００μｍの篩を通過する粒子を被覆粒子とした。なお、比較例においては高分子感応性塩の添加は行わなかった。
【００９８】
被覆粒子の製造方法▲３▼（流動層造粒）
表２〜６に示す組成のうち、水溶性無機塩（温度２５℃）を流動層（（株）パウレックス製、Ｇｌａｔｔ−ＰＯＷＲＥＸ、型番ＦＤ−ＷＲＴ−２０）に、静置時の粉体層厚が２００ｍｍになる重量を添加した。その後、２０℃の風（空気）を流動層内に送り、粉体が流動化したことを確認した後に塩感応性高分子を流動化している粉体層に向け上部より噴霧した。流動層内風速は流動化状態を確認しながら０．２〜１０．０ｍ／ｓの範囲で調整しながら造粒・被覆（コーティング）操作を行った。
【００９９】
塩感応性高分子は５０℃で噴霧を行い、噴霧するためのノズルは噴霧角度７０°の２流体ホローコーンノズルを使用した。噴霧速度は約１００ｇ／ｍｉｎで行った。塩感応性高分子の噴霧終了後、溶液状の高分子感応性塩を添加する場合は同様のノズルを用いて噴霧速度は約１００ｇ／ｍｉｎでさらに噴霧添加した。粉体の高分子感応性塩を添加する場合は流動層より造粒物を排出し、転動ドラム（直径０．６ｍ、長さ０．４８ｍ、厚さ１ｍｍ×幅１２ｃｍ×長さ４８ｃｍの邪魔板４枚付き、回転数２０ｒｐｍ）内で造粒物と高分子感応性塩を６０秒間混合した。
【０１００】
得られた造粒物を目開き２０００μｍの篩を用いて分級し、目開き２０００μｍの篩を通過する粒子を被覆粒子とした。なお、比較例においては高分子感応性塩の添加は行わなかった。
【０１０１】
なお、上記被覆粒子の製造方法▲１▼〜▲３▼の分級工程で発生した被覆粒子として用いない篩上品の粗粒子は該粒子に対して５％相当量の微粉亜硫酸ナトリウムと共にフィッツミル（ホソカワミクロン（株）製、ＤＫＡ−３）を用いて粉砕し（スクリーン穴径２ｍｍ、回転数：全段４７００ｒｐｍ）、次の造粒時に水溶性無機塩と共に造粒機に投入し再利用した。また、分級操作によって被覆粒子として用いない篩下品の微粒子が発生する際には微粒子も次の造粒時に水溶性無機塩と共に造粒機に投入し再利用した。
【０１０２】
洗浄剤粒子群Ａの製造方法
（Ａ−１）洗浄剤粒子の造粒
下記表１に示すＡ組成のうち、ノニオン界面活性剤、３．２％相当量（対各洗浄剤粒子、以下同様）の粉砕助剤用及び１．５％相当量の表面被覆用のＡ型ゼオライト、酵素、色素及び香料を除く成分を水に溶解もしくは分散させた水分３８％のスラリーを調製した後、向流式噴霧乾燥塔を用いて熱風温度３００℃の条件で噴霧乾燥し、水分３％の噴霧乾燥粒子を得た。この乾燥粒子と共に、ノニオン界面活性剤３．５％相当量及び水を連続ニーダー（（株）栗本鐵工所製、ＫＲＣ−Ｓ４型）に投入し、捏和能力１２０ｋｇ／ｈ、温度６０℃の条件で捏和し、不定形固形洗剤を得た。この不定形固形洗剤を穴径１０ｍｍのダイスを装備したペレッターダブル（不二パウダル（株）製、ＥＸＤＦＪＳ−１００型）を用いて押し出しつつ、カッターで切断し（カッター周速は５ｍ／ｓ）、長さ５〜３０ｍｍ程度のペレット状固形洗剤を得た。
【０１０３】
次いで、得られた固形洗剤に粉砕助剤としての粒子状Ａ型ゼオライト（平均粒子径１８０μｍ）を４．２％相当量添加し、冷風（１０℃、１５ｍ／ｓ）下で直列３段に配置したフィッツミル（ホソカワミクロン（株）製、ＤＫＡ−３）を用いて粉砕した（スクリーン穴径：１段目／２段目／３段目＝１２ｍｍ／６ｍｍ／３ｍｍ、回転数：全段４７００ｒｐｍ）。最後に水平円筒型転動混合機（円筒直径５８５ｍｍ、円筒長さ４９０ｍｍ、容器１３１．７Ｌのドラム内部壁面に内部壁面とのクリアランス２０ｍｍ、高さ４５ｍｍの邪魔板を２枚有するもの）で、充填率３０容量％、回転数２２ｒｐｍ、２５℃の条件で０．５％相当量の微粉Ａ型ゼオライト加え、０．５％相当量のノニオン界面活性剤を噴霧しつつ、２分間転動し表面改質して洗浄剤粒子を得た。
【０１０４】
（Ａ−２）洗浄剤粒子の賦香
水平円筒型転動混合機（円筒直径５８５ｍｍ、円筒長さ４９０ｍｍ、容器１３１．７Ｌのドラム内部壁面に内部壁面とのクリアランス２０ｍｍ、高さ４５ｍｍの邪魔板を２枚有するもの）で、充填率３０容量％、回転数２２ｒｐｍ、２５℃の条件で（Ａ−２）で得られた洗浄剤粒子を混合しつつ、０．１４％相当量の香料を噴霧して洗浄剤粒子に賦香した。
【０１０５】
（Ａ−３）洗浄剤粒子の着色
得られた賦香後の洗浄剤粒子の一部を着色するために、洗浄剤粒子をベルトコンベアで０．５ｍ／ｓの速度で移送しつつ（ベルトコンベア上の洗浄剤粒子層高３０ｍｍ、層幅３００ｍｍ）その表面に青色色素溶液を噴霧した。洗浄剤粒子Ａ（平均粒子径５００μｍ、嵩密度０．８０ｇ／ｍＬ）を得た。
【０１０６】
（Ａ−４）その他粒子との混合
水平円筒型転動混合機（円筒直径５８５ｍｍ、円筒長さ４９０ｍｍ、容器１３１．７Ｌのドラム内部壁面に内部壁面とのクリアランス２０ｍｍ、高さ４５ｍｍの邪魔板を２枚有するもの）で、充填率３０容量％、回転数２２ｒｐｍ、２５℃の条件で、着色後の洗浄剤粒子に、酵素粒子０．７２％相当量、漂白剤粒子４．０％相当量及び漂白活性化剤粒子１．３％相当量を５分間混合して、洗浄剤粒子群Ａ（平均粒子径５００μｍ、嵩密度０．８０ｇ／ｍＬ）を得た。
【０１０７】
洗浄剤粒子群Ｂの製造方法
洗浄剤粒子群Ａの製造方法と同様の製造法で表１に示したＢ組成の洗浄剤粒子群Ｂ（平均粒子径４８０μｍ、嵩密度０．８０ｇ／ｍＬ）を得た。ただし、表１のＢ組成に示したとおり、漂白剤粒子及び漂白活性化剤粒子は混合されていない。
【０１０８】
洗浄剤粒子群Ｃの製造方法
（Ｃ−１）流動層によるドライ中和
表１に示したＣ組成の内、炭酸カリウム及び炭酸ナトリウム粉砕品を含む粉体原料（コーティング剤は除く）を流動層（（株）パウレックス製、Ｇｌａｔｔ−ＰＯＷＲＥＸ、型番ＦＤ−ＷＲＴ−２０）に静置時の粉体層厚が２００ｍｍになる重量を添加した。その後、２０℃の風（空気）を流動層内に送り、粉体が流動化したことを確認した後にα−ＳＦ−Ｈ（α−スルホ脂肪酸アルキルエステル）を流動化している粉体層に向け、上部より噴霧した。流動層内風速は流動化状態を確認しながら０．２〜２．０ｍ／ｓの範囲で調整しながら造粒操作を行った。
【０１０９】
α−ＳＦ−Ｈは６０℃で噴霧を行い、噴霧するためのノズルは噴霧角度７０°の２流体ホローコーンノズルを使用した。噴霧速度は約４００ｇ／ｍｉｎで行った。α−ＳＦ−Ｈの噴霧終了後、さらに２０℃の風（空気）を流動層内に送り、２４０秒間熟成を行った。さらに、流動層より造粒物を排出し、転動ドラム（直径０．６ｍ、長さ０．４８ｍ、厚さ１ｍｍ×幅１２ｃｍ×長さ４８ｃｍの邪魔板４枚付き、回転数２０ｒｐｍ）内でゼオライト４．５％相当量をコーティングした。
【０１１０】
（Ｃ−２）漂白
その後、得られた粒子に過酸化水素水溶液を転動ドラム（直径０．６ｍ、長さ０．４８ｍ、厚さ１ｍｍ×幅１２ｃｍ×長さ４８ｃｍの邪魔板４枚付き、回転数２０ｒｐｍ）内で噴霧し、流動性改善のために、さらにゼオライト５．０％相当量をコーティングした。こうして洗浄剤粒子Ｃ（平均粒子径３８０μｍ、嵩密度０．５０ｇ／ｍＬ）を得た。
【０１１１】
洗浄剤粒子群Ｄの製造方法
（Ｄ−１）洗浄剤粒子の造粒
下記表１に示すＤ組成のうち、ノニオン界面活性剤、４．０％相当量の粉砕助剤用及び２．０％相当量の表面被覆用のＡ型ゼオライト、モンモリロナイト、ホワイトカーボン、酵素、色素及び香料を除く成分を水に溶解もしくは分散させた水分４０％のスラリーを調製した後、向流式噴霧乾燥塔を用いて熱風温度３００℃の条件で噴霧乾燥し水分３％の噴霧乾燥粒子を得た。この乾燥粒子と共に、ノニオン界面活性剤及び水を連続ニーダー（（株）栗本鐵工所製、ＫＲＣ−Ｓ４型）に投入し、捏和能力１２０ｋｇ／ｈ、温度６０℃の条件で捏和し、不定形固形洗剤を得た。この不定形固形洗剤を穴径１０ｍｍのダイスを装備したペレッターダブル（不二パウダル（株）製、ＥＸＤＦＪＳ−１００型）を用いて押し出しつつ、カッターで切断し（カッター周速は５ｍ／ｓ）長さ５〜３０ｍｍ程度のペレット状固形洗剤を得た。
【０１１２】
次いで、得られた固形洗剤に粉砕助剤としての粒子状Ａ型ゼオライト（平均粒子径１８０μｍ）を４．２％相当量添加し、冷風（１０℃、１５ｍ／ｓ）下で直列３段に配置したフィッツミル（ホソカワミクロン（株）製、ＤＫＡ−３）を用いて粉砕した（スクリーン穴径：１段目／２段目／３段目＝８ｍｍ／６ｍｍ／３ｍｍ、回転数：全段３７６０ｒｐｍ）。最後に水平円筒型転動混合機（円筒直径５８５ｍｍ、円筒長さ４９０ｍｍ、容器１３１．７Ｌのドラム内部壁面に内部壁面とのクリアランス２０ｍｍ、高さ４５ｍｍの邪魔板を２枚有するもの）で、充填率３０容量％、回転数２２ｒｐｍ、２５℃の条件で０．５％相当量の微粉Ａ型ゼオライトを加え、２分間転動し表面改質した。
【０１１３】
（Ｄ−２）洗浄剤粒子の賦香
洗浄剤粒子群Ａの場合と同様の方法で洗浄剤粒子を賦香した。
【０１１４】
（Ｄ−３）その他粒子との混合
水平円筒型転動混合機（円筒直径５８５ｍｍ、円筒長さ４９０ｍｍ、容器１３１．７Ｌのドラム内部壁面に内部壁面とのクリアランス２０ｍｍ、高さ４５ｍｍの邪魔板を２枚有するもの）で、充填率３０容量％、回転数２２ｒｐｍ、２５℃の条件で、得られた賦香後の洗浄剤粒子と酵素粒子１．０％相当量を５分間混合して、洗浄剤粒子群Ｃ（平均粒子径５６０μｍ、嵩密度０．８１ｇ／ｍＬ）を得た。
【０１１５】
洗浄剤粒子群Ｅの製造方法
水平円筒型転動混合機（円筒直径５８５ｍｍ、円筒長さ４９０ｍｍ、容器１３１．７Ｌのドラム内部壁面に内部壁面とのクリアランス２０ｍｍ、高さ４５ｍｍの邪魔板を２枚有するもの）で、充填率３０容量％、回転数２２ｒｐｍ、２５℃の条件で、洗浄剤粒子群Ａと洗浄剤粒子群Ｃを質量比１：１で５分間混合して、洗浄剤粒子群Ｅ（平均粒子径５３０μｍ、嵩密度０．８１ｇ／ｍＬ）を得た。
【０１１６】
【表１】

【０１１７】
被覆粒子と洗浄剤粒子群との混合
得られた被覆粒子と洗浄剤粒子群を水平円筒型転動混合機（円筒直径５８５ｍｍ、円筒長さ４９０ｍｍ、容器１３１．７Ｌのドラム内部壁面に内部壁面とのクリアランス２０ｍｍ、高さ４５ｍｍの邪魔板を２枚有するもの）で、充填率３０容量％、回転数２２ｒｐｍ、２５℃の条件で、表２〜６に示した比率で混合し、洗剤組成物を得た。なお、被覆粒子と洗浄剤粒子群Ｃとを混合する際には混合と同時に混合物に対して０．２％相当量となるように香料を噴霧した。
【０１１８】
実施例中で用いた原料を下記に示す。
ＬＡＳ−Ｋ：ライポンＬＨ−２００（ライオン（株）製）のカリウム塩
α−ＳＦ−Ｎａ：炭素数１４：炭素数１６＝１８：８２のα−スルホ脂肪酸メチルエステルナトリウム（ＡＩ＝７０％、残部は未反応脂肪酸メチルエステル、硫酸ナトリウム、メチルサルフェート、過酸化水素、水等）
α−ＳＦ−Ｈ：α−スルホ脂肪酸アルキルエステル（メチルエステル（パステルＭ−１４、パステルＭ−１６（ライオンオレオケミカル（株）製）を２：８で混合したもの）を特開２００１−６４２４８号公報の実施例１で開示されている方法に準拠してスルホン化し、エステル化工程後に抜き出しα−スルホ脂肪酸アルキルエステルとしたもの）
石鹸：Ｃ１２：Ｃ１８ Ｆ１＝１：１の脂肪酸ナトリウム（純分６８％の水性ペースト）
ノニオン界面活性剤Ａ：ダイアドール１３（三菱化学（株）製）の酸化エチレン平均１５モル付加体（純分９０％）
ノニオン界面活性剤Ｂ：パステルＭ−１８１（ライオンオレオケミカル（株）製）の酸化エチレン平均１５モル付加体
Ａ型ゼオライト：シルトンＢ（水沢化学（株）製）（純分８０％）
アクリル酸／マレイン酸コポリマーＮａ▲１▼：アクアリックＴＬ−４００（日本触媒（株）製）（純分４０％水溶液）
アクリル酸／マレイン酸コポリマーＮａ▲２▼：アクアリックＴＬ−４００（日本触媒（株）製）を純分２０％となるように水で希釈したもの
ポリアクリル酸Ｎａ：アクアリックＤＬ−４０（日本触媒（株）製）（純分４０％水溶液）
アルギン酸Ｎａ：ダックアルギンＮＳＰＬＬ（（株）紀文フードケミファ製）の純分４％水溶液
カルボキシメチルセルロースＮａ：ＣＭＣダイセル１１０５（ダイセル化学工業（株）製）の純分５％水溶液
ポリビニルアルコール：クラレポバールＰＶＡ−１０５（（株）クラレ製）の純分５％水溶液
炭酸ナトリウム：粒灰（旭硝子（株）製）
微粉炭酸ナトリウム：粒灰（旭硝子（株）製）を卓上型微粉砕機（スタッドミル６３Ｃ型、アルピネ社製）で平均粒子径３０μｍに粉砕したもの
炭酸カリウム：炭酸カリウム（粉末）（旭硝子（株）製）
重炭酸ナトリウム：純正化学（株）製の試薬一級品
硫酸ナトリウム：中性無水芒硝（日本化学工業（株）製）
硫酸カリウム：硫酸加里（上野製薬（株）製）
亜硫酸ナトリウム：無水亜硫酸曹達（神州化学（株）製）
微粉亜硫酸ナトリウム：無水亜硫酸曹達（神州化学（株）製）を卓上型微粉砕機（スタッドミル６３Ｃ型、アルピネ社製）で平均粒子径２５μｍまで微粉砕したもの
塩化カルシウム（液）：セントラル硝子製、３５％水溶液
塩化カルシウム（粉）▲１▼：塩化カルシウム無水物（純正化学（株）製）の試薬一級品
塩化カルシウム（粉）▲２▼：塩化カルシウム２水和物（粒状）（セントラル硝子（株）製）を卓上型微粉砕機（スタッドミル６３Ｃ型、アルピネ社製）で微粉砕したもの
塩化マグネシウム（粉）：塩化マグネシウム無水物（純正化学（株）製）の試薬一級品
硝酸カルシウム（液）：硝酸カルシウム４水和物（純正化学（株）製）の試薬一級品の純分５０％水溶液
塩化アルミニウム（粉）：塩化アルミニウム無水物（純正化学（株）製）の試薬一級品
硫酸マグネシウム（液）硫酸マグネシウム無水物（純正化学（株）製）の試薬一級品の純分３０％水溶液
酸化カルシウム（粉）：酸化カルシウム（純正化学（株）製）の試薬一級品
四ホウ酸ナトリウム（粉）：四ホウ酸ナトリウム無水物（純正化学（株）製）の試薬一級品
ホワイトカーボン：シリカの微粉末（（株）トクヤマ製、トクシールＮ）
モンモリロナイト：モンモリロナイト（ＳＵＤ ＣＨＥＭＩＥ社製ラウンドロジル）
蛍光剤：チノパールＣＢＳ−Ｘ（チバスペシャリティケミカルズ）
色素：青色色素溶液（群青）３５％溶液（大日精化（株）製）
香料：デカナール０．５％、オクタナール０．３％、ヘキシルシンナミックアルデヒド１０．０％、ジメチルベンジルカルビニルアセテート８．０％、レモン油３．０％、リリアール６．０％、リラール２．０％、リナロール５．０％、フェニルエチルアルコール７．５％、トナリド２．０％、ｏ−ｔｅｒｔ−ブチルシクロヘキシルアセテート３．０％、ガラクソリド ＢＢ＊２．０％、リナスコール２．５％、ゲラニオール１．０％、シトロネロール２．０％、ジャスモランジ２．０％、メチルジヒドロジャスモネート５．０％、ターピネオール１．０％、メチルヨノン３．０％、アセチルセドレン５．０％、レモニトリル１．０％、フルイテート１．０％、オリボン１．５、ベンゾイン１．０％、シス−３−ヘキセノール０．５％、クマリン２．０％、ダマセノン０．２％、ダマスコン０．３％、ヘリオナール１．５％、ヘリオトロピン１．５％、アニスアルデヒド２．５％、ガンマーウンデカラクトン０．８％、バグダノール１．２％、トリプラール０．５％、スチラリルアセテート１．５％、キャロン０．１％、ペンタリド３．０％、オキサヘキサデセン−２−オン２．９％、エチレンブラシレート６．２％。なお、ＢＢはベンジルベンゾエート、香料成分の％は香料組成物中の％を示す。
過酸化水素水：純正化学（株）製、一級試薬、過酸化水素３５％含有水溶液
酵素粒子：サビナーゼ１８Ｔ（ノボ・ノルディスクバイオインダストリー製）
漂白剤粒子：過炭酸ナトリウム（三菱瓦斯化学（株）製、ＳＰＣ−Ｄ）
漂白活性化剤粒子：下記製造方法によって得られた粒子
【０１１９】
（漂白活性化剤粒子の製造方法）
ホソカワミクロン（株）製エクストルード・オーミックスＥＭ−６型に４−デカノイルオキシ安息香酸（試薬グレード）６９．４％（対漂白活性化剤粒子、以下同じ）、ポリエチレングリコール２０．９％及びＡＯＳ−Ｎａ（α−オレフィンスルホン酸ナトリウム）４．７％を投入し、６５℃の条件で混練押し出しすることにより径が０．８ｍｍφのヌードル状の押し出し品を得た。この押し出し品を、コミニューターＦＸＢ型（不二パウダル株式会社）により、混練押出し造粒物を導入するのと同じ方向から１５℃の冷風を導入し、また助剤としてＡ型ゼオライト粉末５．０％を同様にして供給し粉砕して漂白活性化剤粒子を得た。
【０１２０】
［実施例１〜３０、比較例１〜３］
表２〜６に示す組成となるように、表中に示す上記方法で被覆粒子を調製した。得られた被覆粒子と上記で得られた洗浄剤粒子を用いて上記方法で洗剤組成物を得た。得られた被覆粒子について、下記方法に基づいて平均粒子径、嵩密度を測定し、装置付着性を評価した。洗剤組成物について、平均粒子径、嵩密度を測定し、長期保存後の溶解性を評価した。結果を表２〜６に併記する。
【０１２１】
（１）平均粒子径の測定
目開き１６８０μｍ、１４１０μｍ、１１９０μｍ、１０００μｍ、７１０μｍ、５００μｍ、３５０μｍ、２５０μｍ、１４９μｍ、の９段の篩と受け皿を用いて分級操作を行なった。分級操作は、受け皿に目開きの小さな篩から目開きの大きな篩の順に積み重ね、最上部の１６８０μｍの篩の上から１００ｇ／回のベースサンプルを入れ、蓋をしてロータップ型ふるい振盪機（（株）飯田製作所製、タッピング：１５６回／分、ローリング：２９０回／分）に取り付け、１０分間振動させた後、それぞれの篩及び受け皿上に残留したサンプルを篩目ごとに回収する操作を行った。
【０１２２】
この操作を繰すことによって１４１０〜１６８０μｍ（１４１０μｍ．ｏｎ）、１１９０〜１４１０μｍ（１１９０μｍ．ｏｎ）、１０００〜１１９０μｍ（１０００μｍ．ｏｎ）、１０００〜７１０μｍ（７１０μｍ．ｏｎ）５００〜７１０μｍ（５００μｍ．ｏｎ）、３５０〜５００μｍ（３５０μｍ．ｏｎ）、２５０〜３５０μｍ（２５０μｍ．ｏｎ）、１４９〜２５０μｍ（１４９μｍ．ｏｎ）、皿〜１４９μｍ（１４９μｍ．ｐａｓｓ）の各粒子径の分級サンプルを得、重量頻度（％）を算出した。
【０１２３】
次に、算出した重量頻度が５０％以上となる最初の篩の目開きをａμｍとし、またａμｍよりも一段大きい篩の目開きをｂμｍとし、受け皿からａμｍの篩までの重量頻度の積算をｃ％、またａμｍの篩上の重量頻度をｄ％として、次式によって平均粒子径（重量５０％）を求めた。
【０１２４】
【数１】

【０１２５】
（２）嵩密度の測定
嵩密度はＪＩＳ Ｋ３３６２に準じて測定した。
【０１２６】
（３）装置付着性評価
各被覆粒子を製造後、被覆粒子を造粒した装置内壁の付着物の形成状況を下記基準に基づいて評価した。
◎：ほとんど付着物が無い
○：付着物があるが問題ないレベル
△：付着物が目立つ
×：ほぼ全面に付着物がある。
【０１２７】
（４）長期保存後溶解性評価
▲１▼外側からコートボール紙（坪量：３５０ｇ／ｍ²）、ワックスサンド紙（坪量：３０ｇ／ｍ²）、クラフトパルプ紙（坪量：７０ｇ／ｍ²）の３層からなる紙を用いて、長さ１５ｃｍ×巾９．３ｃｍ×高さ１８．５ｃｍの箱を作製した。この箱に被覆粒子と洗浄剤粒子群の混合物１．２ｋｇを入れ、４０℃、８５％ＲＨの恒温恒湿室中に３０日間保存して、溶解性試験用サンプルを得た。
▲２▼二槽式洗濯機（三菱電機（株）製、ＣＷ−Ｃ３０Ａ１−Ｈ）に、５℃の水道水３０Ｌを張り、綿肌シャツ７枚、ポリエステルシャツ２枚、アクリルシャツ２枚で浴比２０倍に調整し、それらを折り畳んで水面に浮かべた。その中心に長期保存後の溶解性試験用サンプル３０ｇを乗せ、布ごと２分間浸漬後、弱水流で５分間撹拌した。排水後、布を１分間脱水し、布上と洗濯機中にある溶け残りを拾い出し、目視にて溶け残り量を下記評価基準に基づいて評価した。
◎：溶け残りがほとんどない
○：溶け残りがやや見られるが問題ないレベル
△：溶け残りが目立つ
×：溶け残りが著しく見られる
家庭における使用性を考慮すると、洗剤組成物としては○以上の評価が好ましい。
【０１２８】
【表２】

【０１２９】
【表３】

【０１３０】
【表４】

【０１３１】
【表５】

【０１３２】
【表６】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to coated particles and a detergent composition excellent in solubility, dispersibility, and apparatus adhesion prevention after long-term storage.
[0002]
[Prior art]
Conventionally, by granulating powder using water-soluble polymer or coating particles, the obtained particles can be given appropriate solubility and disintegration, and various types of particles can be generated when the particles are dissolved. It is known that this problem can be solved (see, for example, Patent Document 1: Japanese Patent Laid-Open No. 3-53000, 2: Japanese Patent Laid-Open No. 2001-293354).
[0003]
In particular, the problem that detergent particles containing a surfactant gel and deteriorate solubility when they come into contact with water is a big problem in designing a detergent composition. A method for coating the surface with a water-soluble polymer has also been proposed (see, for example, Patent Document 3: JP-A-7-242899). In addition, in order to impart various characteristics and functions to granular detergents, a technique for blending various particles has been proposed, but there are also problems such as degradation in solubility due to the interaction between the blended particles. It was. In particular, when a water-soluble inorganic salt is used in a dry blend with detergent particles, the phenomenon that the solubility of the detergent composition deteriorates due to the hydration phenomenon that occurs when the water-soluble inorganic salt comes into contact with water has been a problem. . Studies have been made to solve such problems. For example, in order to improve the solubility of a detergent composition in which an alkali metal carbonate is dry-blended with the detergent particles, the detergent particles are coated with a nonionic surfactant. And the technique which coat | covers an alkali metal carbonate with a water-soluble organic substance solution and / or solid powder is proposed (for example, refer patent document 4: Unexamined-Japanese-Patent No. 2002-266000).
[0004]
However, in the above technique, when the particles are coated with a water-soluble polymer, many deposits are generated in the granulator, the strength of the coating film is somewhat weak, and sufficient solubility can be maintained after long-term storage. It was difficult. In addition, a technique for drying particles after coating in order to prevent adhesion in the apparatus during coating has also been proposed (see, for example, Patent Document 5: Japanese Patent Laid-Open No. 3-111497). This complicates the manufacturing process and increases energy consumption, which is not preferable.
[0005]
On the other hand, as a method of coating particles with a sufficient film strength, a method of increasing the film strength by coating with a salt-sensitive polymer and then crosslinking the salt-sensitive polymer with a metal salt is known. Yes. For example, a granular material obtained by granulating a water-insoluble powder with a water-soluble polymer having a sensitive group that reacts with a polyvalent metal ion is contacted with the polyvalent metal ion so that the water-soluble polymer is polyvalent. A technique for crosslinking with metal ions has been proposed (see, for example, Patent Document 6: Japanese Patent Laid-Open No. 63-130522). In addition, a technique has been proposed in which a granulated product of a bleach activator is coated with alginic acid and then crosslinked with an alkaline earth metal ion (see, for example, Patent Document 7: Japanese Patent Publication No. 11-514402). However, these techniques are aimed at improving the shape retention of water-insoluble powder granules in water and improving the environmental stability of organic compounds, and mention is made of the hydration-inhibiting effect of water-soluble inorganic substances. Absent.
[0006]
[Patent Document 1]
JP-A-3-53000 (pages 5-7)
[Patent Document 2]
JP 2001-293354 A (2nd page)
[Patent Document 3]
JP-A-7-242899 (pages 1 to 3)
[Patent Document 4]
JP 2002-266000 A (page 2)
[Patent Document 5]
Japanese Patent Laid-Open No. 3-111497 (2nd page)
[Patent Document 6]
JP-A-63-130522 (pages 1 and 2)
[Patent Document 7]
JP 11-514402 (pages 17-18)
[0007]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, there is no decrease in solubility due to agglomeration in water even after long-term storage, excellent dispersibility, and furthermore, adhesion to a granulator can be prevented. It is an object to provide coated particles and detergent compositions.
[0008]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the present inventor has found that the granulated product in which the surface of the water-soluble inorganic salt core particles is coated with a salt-sensitive polymer is used to make the salt-sensitive polymer sensitive. The present inventors have found that coated particles and a detergent composition capable of achieving the above-described object can be obtained by treating with fine powder and / or an aqueous solution, and have led to the present invention.
[0009]
Therefore, the present invention treats a granulated product in which the surface of a water-soluble inorganic salt core particle is coated with a salt-sensitive polymer with a salt fine powder and / or an aqueous solution that makes the salt-sensitive polymer sensitive. Coated particles and a detergent composition containing the coated particles are provided.
[0010]
Hereinafter, the present invention will be described in more detail.
For the coated particles of the present invention, a granulated product in which the surface of water-soluble inorganic salt core particles is coated with a salt-sensitive polymer is used.
[0011]
The water-soluble inorganic salt in the present invention is an inorganic salt having a solubility in water at 5 ° C. of 1 g / 100 g or more, preferably 2 g / 100 g or more, more preferably 3 g / 100 g or more (edited by Chemical Society of Japan, “Chemical Handbook”). Etc.). Any inorganic salt can be suitably used as long as it is such a water-soluble inorganic salt, but preferred inorganic salts include those generally used as a cleaning builder.
[0012]
In the present invention, by using a water-soluble inorganic salt as a core particle, and coating and treating the core particle as described later, the inorganic salt particle is prevented from agglomerating in water, and the solubility is lowered after long-term storage. Can be prevented.
[0013]
Examples of water-soluble inorganic salts include carbonates such as sodium carbonate and potassium carbonate, bicarbonates such as sodium bicarbonate and potassium bicarbonate, sesqui carbonates such as sodium sesquicarbonate, sodium sulfate, potassium sulfate and magnesium sulfate. Sulfates such as sodium sulfite, sodium sulfite, sulfites such as potassium sulfite, nitrates such as sodium nitrate, potassium nitrate, calcium nitrate and magnesium nitrate, nitrites such as sodium nitrite and potassium nitrite, sodium chloride, potassium chloride, calcium chloride, Examples thereof include chlorides such as magnesium chloride, silicates such as sodium silicate, phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, and phytate.
[0014]
When a water-soluble inorganic salt causes a problem in solubility in water, it usually causes aggregation under standing conditions in water, and this is thought to involve hydration of the water-soluble inorganic salt. It is done. Therefore, the inorganic salt used in the present invention is preferably a substance that can have water of crystallization at less than 20 ° C. from the viewpoint of easily obtaining the effect. As such a substance, for example, substances described in “Chemical Handbook” edited by the Chemical Society of Japan can be suitably used. Of these, alkaline inorganic salts such as sodium carbonate and potassium carbonate are most preferred. One kind of water-soluble inorganic salt may be used alone, or two or more kinds may be used in appropriate combination, and two or more kinds are preferably combined.
[0015]
The average particle diameter of the water-soluble inorganic salt core particles is usually 100 to 1500 μm, preferably 200 to 1000 μm. When the average particle size is less than 100 μm, coating with a polymer may be difficult, and when it exceeds 1500 μm, the solubility of the inorganic salt itself may be lowered.
[0016]
The water-soluble inorganic salt core particles may contain a small amount of a water-soluble substance as an impurity in addition to the water-soluble inorganic salt.
[0017]
The salt-sensitive polymer in the present invention refers to a polymer that increases its viscosity in response to salt and gels or forms a film. Such a polymer preferably has an anionic sensitive group such as a carboxyl group or a sulfate group, and crosslinks by reacting with a polyvalent metal ion. Examples of such salt-sensitive polymers include acrylic acid polymers, maleic acid polymers, acrylic acid / maleic acid copolymers, carboxymethyl cellulose, alginic acid, carrageenan, cellulose sulfide, and alkali metal salts thereof. And the like, and polymers of monoalkali metal salts of ethylene group-containing alkyl phosphates. Examples of the polymer having no anionic sensitive group include polyvinyl alcohol that is sensitive to sodium tetraborate and gels.
[0018]
A salt sensitive polymer can be used individually by 1 type or in combination of 2 or more types as appropriate. When coating the core particles, the salt-sensitive polymer is used in the form of an aqueous solution, and the concentration of the polymer in the aqueous solution is usually 0.1 to 90% by mass, preferably 0.5 to 80% by mass, and more preferably. 1 to 60% by mass. The viscosity of the polymer solution is 0.001 to 100 Pa · s, preferably 0.0005 to 50 Pa · s.
[0019]
The salt-sensitive polymer is used as a coating agent for the water-soluble inorganic salt, and the coated salt-sensitive polymer amount is preferably 0.1 to 10% by mass, and 0.5 to 8% by mass with respect to the total amount of the coated particles. Particularly preferred. If the coating salt-sensitive high molecular weight is less than 0.1% by mass, the effect of coating may be difficult to obtain, whereas if it exceeds 10% by mass, the amount of water-soluble inorganic salt may be reduced.
[0020]
The granulated product of the present invention is obtained by coating the surface of water-soluble inorganic salt core particles with a salt-sensitive polymer. The production method will be described later.
[0021]
The coated particles of the present invention are obtained by treating the above-mentioned granulated product with a fine salt powder and / or an aqueous solution that makes a salt-sensitive polymer sensitive. By performing such a treatment, the long-term storage stability of the coated particles is improved.
[0022]
The salt for sensitizing the salt-sensitive polymer in the present invention refers to a salt that increases the viscosity of the salt-sensitive polymer used as a coating agent for the water-soluble inorganic salt, gels it, or forms a film. A preferable example of such a salt is a polyvalent metal salt when a polymer having an anionic sensitive group such as a carboxyl group or a sulfate group is used as the polymer. Preferred examples of the polyvalent metal salt include polyvalent chlorides such as calcium chloride, magnesium chloride and aluminum chloride, polyvalent sulfates such as magnesium sulfate and aluminum sulfate, polyvalent nitrates such as calcium nitrate and magnesium nitrate, and calcium acetate. And polyvalent organic acid salts such as calcium citrate, calcium oxide, calcium hydroxide and the like. Moreover, when using the polyvinyl alcohol which is a polymer | macromolecule which does not have an anionic sensitive group, sodium tetraborate etc. which gelatinize this are mentioned. The salt which sensitizes a salt sensitive polymer can be used individually by 1 type or in combination of 2 or more types.
[0023]
The salt for sensitizing the salt-sensitive polymer is used in the form of fine powder and / or aqueous solution. When a salt that sensitizes a salt-sensitive polymer is used as a fine powder, the average particle size is usually 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 1 to 30 μm. When the average particle size is less than 0.1 μm, the dust generation property may be deteriorated. On the other hand, when the average particle size is more than 100 μm, it may be difficult to obtain the effect of sensitizing the polymer. In addition, when the salt that sensitizes the salt-sensitive polymer is used in the form of an aqueous solution, the concentration of the salt in the aqueous solution varies depending on the solubility of the salt used, but is usually 1% by mass or more, preferably 5 to 60% by mass. .
[0024]
When the granulated product is treated with a fine salt powder and / or an aqueous solution that sensitizes the salt-sensitive polymer, the fine salt powder and / or aqueous solution that sensitizes the salt-sensitive polymer to the granulated product is added and sprayed. , Mixing by stirring or the like, and forming a coating film with a salt-sensitive polymer and a salt that sensitizes the salt-sensitive polymer.
[0025]
The amount of treatment is not particularly limited as long as it is sufficient to sensitize the salt-sensitive polymer and form a sufficient coating film on the water-soluble inorganic salt particles that are the core particles. As 0.1 to 10% by mass, preferably 0.5 to 8% by mass, based on the total amount of the coated particles. If the treatment amount is less than 0.1% by mass, the effect of coating may be difficult to obtain. On the other hand, if it exceeds 10% by mass, the blending amount of the inorganic salt may be reduced.
[0026]
The physical property value of the coated particle of the present invention is not particularly limited, but the bulk density is usually 0.3 g / mL or more, preferably 0.5 to 1.2 g / mL, more preferably 0.6. ~ 1.1 / mL. When the bulk density is too small or too large, it becomes easy to classify when used by mixing with other particles. Moreover, the average particle diameter is preferably 200 to 1500 μm, more preferably 300 to 1000 μm. If the average particle size is less than 200 μm, the specific surface area is too large, and it may be difficult to obtain the effect of suppressing hydration. On the other hand, if it exceeds 1500 μm, the solubility of the coated particles may be deteriorated. Furthermore, the angle of repose is preferably 70 ° or less, particularly 50 ° or less. When the angle of repose exceeds 70 °, the handleability of the particles may deteriorate. The angle of repose can be measured by a so-called angle-of-repose angle of repose measurement method that measures the angle formed by the horizontal surface of the slip surface formed when particles filled in the container flow out.
[0027]
The coated particles of the present invention can be obtained by the following method. Agitation granulation method in which salt-sensitive polymer is added to water-soluble inorganic salt particles and agitated with a stirring blade to granulate and coat (coating), salt-sensitive polymer is sprayed while rolling water-soluble inorganic salt particles Rolling granulation method to granulate and coat (coating), fluidized bed granulation method to spray and granulate and coat (coat) salt-sensitive polymer while fluidizing water-soluble inorganic salt particles Can be mentioned. Further, fine powder of salt and / or an aqueous solution to which the salt-sensitive polymer is sensitized are added and mixed to the obtained granulated material using an arbitrary machine such as a mixer, a granulator or a fluidized bed. By doing so, coated particles can be obtained.
Below, each method, a manufacturing apparatus, conditions, etc. are demonstrated.
[0028]
1. Agitation granulation method
Any type of agitation granulator can be used in the agitation granulation method. Among these, it is preferable to have a structure having a stirring shaft provided with a stirring blade in the center and forming a clearance between the stirring blade and the vessel wall when the stirring blade rotates. The clearance is preferably 1 to 30 mm, more preferably 3 to 10 mm. If the clearance is less than 1 mm, the mixer tends to be overpowered by the adhesion layer. If it exceeds 30 mm, the consolidation efficiency is lowered, so the particle size distribution is broad, and the granulation time is lengthened, which may reduce the productivity. Examples of the stirring granulator having such a structure include, for example, Henschel mixer [manufactured by Mitsui Miike Chemical Co., Ltd.], high speed mixer [manufactured by Fukae Kogyo Co., Ltd.], vertical granulator [manufactured by Paulek Co., Ltd.], etc. Apparatus. Particularly preferred is a mixer of a horizontal type mixing tank having a stirring shaft at the center of a cylinder and mixing the powder by attaching a stirring blade to this shaft. For example, a Redige mixer [manufactured by Matsubo Co., Ltd.] Share mixer [manufactured by Taihei Kiko Co., Ltd.].
[0029]
Preferable granulation conditions in the stirring granulation method are shown below.
(1) Fluid number (Fr number)
In the stirring granulation method, the fluid number defined by the following formula is preferably 1 to 16, and more preferably 2 to 9. When the Froude number is less than 1, fluidization is insufficient, so that coating with a polymer may be insufficient. On the other hand, if it exceeds 16, the shearing force on the particles becomes too strong, and the coating film may be broken.
Fr = V ² / (R × g)
V: peripheral speed at the tip of the stirring blade (m / s)
R: Rotating radius of stirring blade (m)
g: Gravitational acceleration (m / s ² )
[0030]
(2) Chopper rotation speed
In the agitation granulation method, the agitation granulator used is equipped with a chopper that rotates at a high speed in order to promote compaction of the granulated material and coarse powder crushing. The rotation speed of the chopper is preferably such that the coating film is not broken. The chopper tip speed (circumferential speed) is preferably 0 to 30 m / s, and more preferably 0 to 20 m / s.
[0031]
(3) Granulation time
In the stirring granulation method, the granulation time in batch granulation and the average residence time in continuous granulation for obtaining a suitable granulated product are preferably 0.5 to 20 minutes, and preferably 3 to 10 minutes. More preferred. If the granulation time (average residence time) is less than 0.5 minutes, the time is too short and it becomes difficult to control granulation to obtain a suitable average particle size and bulk density, and the particle size distribution may become broad. On the other hand, if it exceeds 20 minutes, the time may be too long and the productivity may decrease.
[0032]
(4) Filling rate of water-soluble inorganic salt
In the stirring granulation method, the filling rate (preparation amount) of the water-soluble inorganic salt into the granulator is preferably 70% by volume or less of the total internal volume of the mixer, and more preferably 15 to 40% by volume. If the filling rate (preparation amount) exceeds 70% by volume, the mixing efficiency of the detergent raw material in the mixer may decrease, and granulation may not be performed appropriately.
[0033]
2. Rolling granulation method
Any type of rolling granulator can be used in the rolling granulation method. Among them, a drum-shaped cylinder that rotates and processes is preferable, and a drum equipped with a baffle plate having an arbitrary shape is particularly preferable. As a drum type granulator, in addition to a horizontal cylindrical granulator, a conical drum type granulator described in the first edition of the granulation handbook edited by the Japan Powder Technology Association, a multistage conical drum type granulator, Examples thereof include a drum type granulator with a stirring blade.
[0034]
Suitable granulation conditions in the rolling granulation method are shown below.
(1) Processing time
The treatment time for increasing the bulk density in the batch system and the average residence time defined by the following formula in the continuous system are 5 to 120 minutes, preferably 10 to 90 minutes, and particularly preferably 10 to 40 minutes. When the time is less than 5 minutes, the bulk density may not be sufficiently increased. On the other hand, when it exceeds 120 minutes, the productivity may be lowered or the detergent granule particles may be collapsed.
Tm = (m / Q) × 60
Tm: Average residence time (s)
m: Retained amount of detergent granules in the container rotating mixer (kg)
Q: Capacity in continuous operation (kg / hr)
[0035]
(2) Froude number (Fr)
As the Froude number defined by the following formula, it is preferable to select a condition of 0.01 to 0.8. As conditions, 0.05-0.7 are more preferable and 0.1-0.65 are further more preferable.
When the fluid number is less than 0.01, uniform and high bulk density detergent particles may not be obtained. On the other hand, when the fluid number exceeds 0.8, detergent granules may be used in the case of a drum-type mixer. Particles may scatter and normal shear mixing may not occur.
Fr = V ² / (R × g)
V: peripheral speed (m / s) at the outermost periphery of the container rotating type mixer
R: Radius (m) from the rotation center on the outermost periphery of the container rotation type mixer
g: Gravitational acceleration (m / s ² )
[0036]
(3) Volume filling rate (X)
It is preferable to select a condition in which the volume filling rate defined by the following formula is 15 to 50%. More preferably, 20 to 45% and 25 to 40% are still more preferable. When the volume filling rate is less than 15%, productivity may be poor, while when it exceeds 50%, good shear mixing may not occur.
Volume filling rate (X) = (M / ρ) / V × 100
M: Amount of detergent granulated particles charged into the container rotating mixer (g)
ρ: Bulk density (g / L) of detergent granulated particles
V: Volume of container rotation type mixer (L)
[0037]
3. Fluidized bed granulation method
In the fluidized bed granulation method, it is possible to use any type of fluidized bed granulator composed of a fluidized bed main body, a current plate, a blower, an intake filter, an air heater and a cooler, a spray device, a dust collector, a blower and the like. it can. For example, batch type fluidized bed granulators (top spray type, side spray type, bottom spray type, etc.), jet fluidized bed granulators, jets, etc. Fluidized bed granulators, semi-continuous fluidized bed granulators (dispersed plate reverse discharge type, lower discharge type, side wall discharge type, etc.) continuous fluidized bed granulators (horizontal multi-chamber type, cylindrical type, etc.) It can be suitably used. Specific examples of the use of the apparatus include batch-type fluidized bed granulator Glatt-POWREX series [manufactured by Paulex Corporation], flow coater series [manufactured by Okawara Seisakusho Co., Ltd.], and continuous fluidized bed granulator MIXGRAD. Series [manufactured by Okawara Seisakusho Co., Ltd.] and the like.
[0038]
As granulation conditions in fluidized bed granulation, the average thickness of the raw material powder layer at the time of standing is preferably about 50 to 500 mm. Thereafter, air is sent to the fluidized bed to fluidize the powder, and then spraying of the salt-sensitive polymer solution is started. As a spray nozzle, in addition to a normal pressure nozzle, it is also preferable to use a two-fluid nozzle in order to improve the spray-like body. The average droplet diameter at this time is preferably about 5 to 500 μm. As the spraying progresses, the granulation progresses and the particle diameter increases, so granulation is performed while adjusting the wind speed in order to maintain the fluidized state. The wind speed is adjusted in the range of 0.2 to 4.0 m / s, and the wind temperature is 5 to 70 ° C, preferably 7 to 65 ° C. The fine particles adhering to the bag filter are preferably produced while being periodically dropped with pulsed air.
[0039]
The granulated product coated with the salt-sensitive polymer obtained by the above-described method is treated by adding and mixing a fine powder of salt and / or an aqueous solution that makes the salt-sensitive polymer sensitive. As a method for addition and mixing, the granulation machine used for granulation may add or mix a salt that makes the salt-sensitive polymer sensitive after the granulation and coating operation, or other granulation described above. After the granulated product is transferred to the granulator, a salt for sensitizing the salt-sensitive polymer may be added and mixed. The operation of each granulator at the time of adding and mixing the salt for sensitizing the salt-sensitive polymer is within the range of the operating conditions of the granulation operation described above.
[0040]
The coated particles granulated by the above-described method can be classified as necessary, and only the coated particles having a desired particle size can be used for the product. Any classifier generally known can be used as the classifier, and a sieve can be particularly preferably used. Among these, a gyro screen, a flat screen, and a vibrating screen are preferable. A gyro-type sieve is a sieve that gives a horizontal circular motion to a slightly inclined plane sieve. A plane sieve is a sieve that gives a reciprocating motion to a slightly inclined plane sieve substantially parallel to the surface. The vibrating sieve is a sieve that gives a rapid vibration in a direction substantially perpendicular to the sieve surface. The time for the sieving is preferably 5 seconds or more, and it is also preferable to use a tapping ball in order to improve the sieving efficiency. Specific examples of such a sieve include a gyro shifter (manufactured by Tokuju Kogakusho Co., Ltd.), a rotex screener (manufactured by Seishin Enterprise Co., Ltd.), and a Dalton vibrating sieve (manufactured by Dalton Co., Ltd.). The vibration by the sieve is suitably given by vibration of 60 to 3000 times / minute, preferably 100 to 2500 times / minute, more preferably 150 to 2000 times / minute. If the frequency of the sieve is less than 60 times / minute, the classification effect may be deteriorated, while if it exceeds 3000 times / minute, dust generation may increase.
[0041]
Of the coated particles other than the desired particle size generated when classified by the classification method, it is preferable that the fine powder is again put into a granulator together with the water-soluble inorganic salt and subjected to granulation and coating (coating) operations. The coarse powder is pulverized to the same particle size as that of the water-soluble inorganic salt before granulation / coating (coating), and then put into the granulator together with the water-soluble inorganic salt for granulation / coating (coating). It is preferable to use for operation. At this time, a pulverizer for pulverizing the coarse powder is preferably a model having a classification screen and a rotating blade. Examples of such a pulverizer include Fitzmill (manufactured by Hosokawa Micron Corporation), New Speed Mill (manufactured by Okada Seiko Co., Ltd.), and Feather Mill (manufactured by Hosokawa Micron Corporation). Moreover, it can also grind | pulverize by flowing cold air in a grinder and cooling. It is possible to classify the cold air and the pulverized product with a cyclone and classify the fine powder at that time. Furthermore, the particle size distribution becomes sharper by multistage grinding. The tip peripheral speed of the blade of the pulverizer is preferably 15 to 90 m / s, more preferably 20 to 80 m / s, and even more preferably 25 to 70 m / s. If the tip peripheral speed is less than 15 m / s, the crushing ability may be insufficient, and if it exceeds 90 m / s, it may be easily pulverized.
[0042]
The coated particles of the present invention can be used as they are as a detergent composition, but are preferably used as a detergent composition containing coated particles and a surfactant. The detergent composition can be obtained by mixing with the coated particles and optionally the detergent particles. The detergent particle group is usually composed of detergent particles containing a surfactant and a cleaning builder, enzyme particles, bleaching agent particles, bleaching activator particles, and the like. Hereinafter, the cleaning agent particle group will be described in detail.
[0043]
1. Detergent particles
The detergent particles are composed of a surfactant, a cleaning builder, and other additives. Examples of other additives include oil-absorbing carriers, viscosity minerals, dissolution accelerators, and swellable water-insoluble substances.
(1) Surfactant
Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
[0044]
The anionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various anionic surfactants can be used. For example, the following can be mentioned.
(1) A linear or branched alkylbenzene sulfonate having an alkyl group having 8 to 16 carbon atoms.
(2) Alkyl sulfate (AS) or alkenyl sulfate having 10 to 20 carbon atoms.
(3) An α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(4) Alkanesulfonate having 10 to 20 carbon atoms.
(5) Alkyl ether added with ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 moles or less Sulfate (AES) or alkenyl ether sulfate.
(6) Alkyl ether added with ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 moles or less Carboxylate or alkenyl ether carboxylate.
(7) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(8) A higher fatty acid salt having 10 to 20 carbon atoms.
(9) C8-20 saturated or unsaturated α-sulfo fatty acid (α-SF) salt or methyl, ethyl or propyl ester thereof.
[0045]
An anionic surfactant can be used individually by 1 type or in combination of 2 or more types as appropriate. Examples of the anionic surfactant include alkali metal salts of linear alkylbenzene sulfonic acid (LAS) (for example, sodium or potassium salt), alkali metal salts of AOS, α-SF, AES (for example, sodium or potassium salt), Alkali metal salts of higher fatty acids (such as sodium or potassium salts) are preferred.
[0046]
Examples of nonionic surfactants include the following.
(1) Polyoxyalkylene alkyl (or alkenyl) obtained by adding an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. As the aliphatic alcohol used here, a primary alcohol or a secondary alcohol is used. The alkyl group may have a branched chain. As a preferable aliphatic alcohol, a primary alcohol is used.
[0047]
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate represented by the following formula, for example, having an alkylene oxide added between the ester bonds of a long-chain fatty acid alkyl ester.
R ¹ CO (OA) _n OR ² ... (1)
(Wherein R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, OA represents an addition unit of alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide, n represents the average number of moles of alkylene oxide added and is generally from 3 to 30, preferably from 5 to 20. R ² Represents a lower alkyl group which may have a substituent having 1 to 3 carbon atoms. )
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.
[0048]
Among the above nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ether having a melting point of 40 ° C. or lower and an HLB of 9 to 16, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, ethylene oxide is added to the fatty acid methyl ester. Preferred examples include fatty acid methyl ester ethoxylates added, fatty acid methyl ester ethoxypropoxylates obtained by adding ethylene oxide and propylene oxide to fatty acid methyl esters, and the like. Moreover, you may use these nonionic surfactants individually by 1 type or in mixture of 2 or more types.
[0049]
The cationic surfactant is not particularly limited as long as it is conventionally used in detergents, and various cationic surfactants can be used. Examples of the cationic surfactant include the following.
[0050]
(1) Dilong chain alkyldishort chain alkyl type quaternary ammonium salt
[R ^Three R ^Four R ^Five R ⁶ N] ⁺ ・ X ^- ... (2)
(Wherein R ^Three And R ^Four Usually represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms. R ^Five And R ⁶ Represents an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, a benzyl group, a hydroxyalkyl group usually having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, or a polyoxyalkylene group. X is halogen, CH _Three SO _Four , C ₂ H _Five SO _Four , 1 / 2SO _Four , OH, HSO _Four , CH _Three CO ₂ Or CH _Three -C ₆ H _Four -SO _Three Indicates. )
[0051]
Specific examples of the dilong chain alkyldishort chain alkyl type quaternary ammonium salt represented by the general formula (2) include distearyldimethylammonium salt, dihydrogenated beef tallow alkyldimethylammonium salt, and dihydrogenated beef tallow. Examples include alkylbenzene methylammonium salt, distearylmethylbenzylammonium salt, distearylmethylhydroxyethylammonium salt, distearylmethylhydroxypropylammonium salt, distearyldihydroxyethylammonium salt, dioleyldimethylammonium salt, dicoconutalkyldimethylammonium salt, etc. It is done. Specific examples of the halogen as X include a chlorine atom and a bromine atom.
[0052]
(2) Mono long chain alkyl tri-short chain alkyl type quaternary ammonium salt
[R ⁷ R ⁸ R ⁹ R ^Ten N] ⁺ ・ X ^- ... (3)
(Wherein R ⁷ Usually represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms. R ⁸ , R ⁹ And R ^Ten Usually represents an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, a benzyl group, a hydroxyalkyl group usually having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, or a polyoxyalkylene group. X is halogen, CH _Three SO _Four , C ₂ H _Five SO _Four , 1 / 2SO _Four , OH, HSO _Four , CH _Three CO ₂ Or CH _Three -C ₆ H _Four -SO _Three Indicates. )
[0053]
Specific examples of the mono long chain alkyl trishort chain alkyl type quaternary ammonium salt represented by the general formula (3) include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, hydrogenated beef tallow alkyl trimethyl ammonium salt, Examples include hydrogenated beef tallow alkylbenzene dimethyl ammonium salt, stearyl dimethyl benzyl ammonium salt, stearyl dimethyl hydroxyethyl ammonium salt, stearyl dimethyl hydroxypropyl ammonium salt, stearyl trihydroxyethyl ammonium salt, oleyl trimethyl ammonium salt, coconut alkyl trimethyl ammonium salt, and the like. Specific examples of the halogen as X include a chlorine atom and a bromine atom.
[0054]
(3) Tetra short chain alkyl type quaternary ammonium salt
[R ¹¹ R ¹² R ¹³ R ¹⁴ N] ⁺ ・ X ^- (4)
(Wherein R ¹¹ , R ¹² , R ¹³ And R ¹⁴ Usually represents an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, a benzyl group, usually a hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, or a polyoxyalkylene group. X is halogen, CH _Three SO _Four , C ₂ H _Five SO _Four , 1 / 2SO _Four , OH, HSO _Four , CH _Three CO ₂ Or CH _Three -C ₆ H _Four -SO _Three Indicates. )
[0055]
Specific examples of the tetra short chain alkyl type quaternary ammonium salt represented by the general formula (4) include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydroxide, tetrabutylammonium. Examples thereof include hydrogen sulfate, benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, benzyltriethylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium chloride, and trimethylphenylammonium chloride.
[0056]
(4) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt
[R ¹⁵ R ¹⁶ R ¹⁷ R ¹⁸ N] ⁺ ・ X ^- ... (5)
(Wherein R ¹⁵ , R ¹⁶ And R ¹⁷ Usually represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms. R ¹⁸ Usually represents an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, a benzyl group, and usually a hydroxyalkyl group or polyoxyalkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. X is halogen, CH _Three SO _Four , C ₂ H _Five SO _Four , 1 / 2SO _Four , OH, HSO _Four , CH _Three CO ₂ Or CH _Three -C ₆ H _Four -SO _Three Indicates. )
[0057]
Specific examples of the tri long chain alkyl mono short chain alkyl type quaternary ammonium salt represented by the general formula (5) include trilauryl methyl ammonium chloride, tristearyl methyl ammonium chloride, trioleyl methyl ammonium chloride, Coconut alkyl methyl ammonium chloride etc. are mentioned. Moreover, you may use these cationic surfactants individually by 1 type or in mixture of 2 or more types.
[0058]
Examples of amphoteric surfactants include amphoteric surfactants such as imidazolines and amide betaines. Particularly preferred amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauric acid amidopropyl betaine, and the like.
[0059]
Content of surfactant is 5-80 mass% normally in detergent particle | grains, Preferably it is 10-60 mass%, Most preferably, it is 20-45 mass%.
[0060]
(2) Cleaning builder
Examples of the cleaning builder blended in the cleaning agent particles include inorganic and organic builders. Examples of the inorganic builder include alkaline salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, sodium silicate, crystalline layered sodium silicate, and amorphous layered sodium silicate, and neutral salts such as sodium sulfate. , Orthophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, phosphates such as phytate, the following general formula (6)
x ¹ (M ₂ O) ・ Al ₂ O _Three ・ Y ¹ (SiO ₂ ) ・ W ¹ (H ₂ O) (6)
(Wherein M is an alkali metal atom such as sodium or potassium, x ¹ , Y ¹ And w ¹ Indicates the number of moles of each component, generally x ¹ Is 0.7-1.5, y ¹ Is a number from 0.8 to 6, w ¹ Indicates an arbitrary positive number. )
A crystalline aluminosilicate represented by the following general formulas (7), (8)
x ² (M ₂ O) ・ Al ₂ O _Three ・ Y ² (SiO ₂ ) ・ W ² (H ₂ O) (7)
(Wherein M is an alkali metal atom such as sodium or potassium, x ² , Y ² And w ² Indicates the number of moles of each component, generally x ² Is 0.7 to 1.2, y ² 1.6-2.8, w ² Represents 0 or any positive number. )
x ^Three (M ₂ O) ・ Al ₂ O _Three ・ Y ^Three (SiO ₂ ) ・ Z ^Three (P ₂ O _Five ) ・ W ^Three (H ₂ O) ... (8)
(Wherein M is an alkali metal atom such as sodium or potassium, x ^Three , Y ^Three , Z ^Three And w ^Three Indicates the number of moles of each component, generally x ^Three Is 0.2 to 1.1, y ^Three Is 0.2-4.0, z ^Three Is 0.001-0.8, w ^Three Represents 0 or any positive number. )
Amorphous aluminosilicate represented by the following. Among the inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, sodium tripolyphosphate, and sodium aluminosilicate are preferable.
[0061]
Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyiminodia Hydroxyaminocarboxylates such as succinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzoate Cyclocarboxylates such as polycarboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; poly Acrylic acid polymers and copolymers such as crylic acid, acrylic acid-allyl alcohol copolymer, acrylic acid-maleic acid copolymer, hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer; maleic acid, itacon Polymers or copolymers of acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid, aspartic acid, etc .; polysaccharide oxides such as starch, cellulose, amylose, pectin and polysaccharides such as carboxymethyl cellulose; Non-dissociative polymer compounds such as polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone and the like can be mentioned.
[0062]
Of these organic builders, citrates, aminocarboxylates, polyacrylates, and acrylic acid-maleic acid copolymers are preferred. The said builder is normally used individually or in mixture of 2 or more types.
[0063]
The content of the builder is preferably 10 to 80% by mass and particularly preferably 20 to 50% by mass in the detergent particles from the viewpoint of imparting sufficient detergency.
[0064]
(3) Oil-absorbing carrier
As the oil-absorbing carrier, an oil-absorbing substance having an oil absorption amount of 80 mL / 100 g or more, preferably 150 to 600 mL / 100 g, represented by the JIS-K5101 test method is suitably used. As such an oil-absorbing carrier, for example, as a silicate compound, Toxeal N [manufactured by Tokuyama Co., Ltd., oil absorption 280 mL / 100 g], nip seal NS-K [manufactured by Nippon Silica Co., Ltd., oil absorption 320 mL / 100 g] , Amorphous water-containing amorphous silicic acid such as Silicia # 310 [Fuji Silysia Chemical Co., Ltd., oil absorption 340 mL / 100 g], spherical shape such as Silex H-52 [Asahi Glass Co., Ltd., oil absorption 260 mL / 100 g] Amorphous anhydrous amorphous silicic acid such as porous hydrous amorphous silicic acid, Aerosil # 300 [manufactured by Nippon Aerosil Co., Ltd., oil absorption 350 mL / 100 g], Florite R [manufactured by Tokuyama Co., Ltd., oil absorption 600 mL / 100 g ] Acicular water-containing amorphous silicic acid such as petal-like water-containing amorphous calcium silicate, zonotlite [Ube Chemical Co., Ltd., oil absorption 220 mL / 100 g] Calcium, amorphous aluminosilicate [Mizusawa Chemical Co., Ltd., oil absorption 170 mL / 100 g], and the like magnesium silicate [oil absorption of 180 mL / 100 g]. Further, as carbonate compounds, magnesium carbonate [manufactured by Tokuyama Co., Ltd., oil absorption 150 mL / 100 g], calcium carbonate [manufactured by Shiraishi Kogyo Co., Ltd., oil absorption 110 mL / 100 g], and other compounds, ultrafine particle spinel [Sumitomo Cement Co., Ltd., oil absorption 600 mL / 100 g], ultrafine cordierite [Sumitomo Cement Co., Ltd. oil absorption 600 mL / 100 g], ultrafine mullite [Sumitomo Cement Co., Ltd. oil absorption 560 mL / 100 g] , Modified starch pineflo-S [manufactured by Matsutani Chemical Co., Ltd., oil absorption 130 mL / 100 g] and the like.
[0065]
These oil-absorbing carriers can be used alone or in combination of two or more. The content of the oil-absorbing carrier is usually 0.1 to 25% by mass, preferably 0.5 to 20% by mass, and particularly preferably 1 to 15% by mass in the detergent particles.
[0066]
(4) Clay mineral
As the clay mineral blended in the detergent particles, those belonging to the smectite group and having a crystal structure of a dioctahedral trilayer structure or a trioctahedral trilayer structure are particularly preferable. The clay mineral preferably has an oil absorption of less than 80 mL / 100 g, more preferably 30 to 70 mL / 100 g, and a bulk density of preferably 0.1 g / mL or more, particularly preferably 0.2 to 1.5 g / mL. It is. Specific examples of such clay minerals include, for example, montmorillonite (oil absorption: 50 mL / 100 g, bulk density: 0.3 g / mL), nontronite (oil absorption: as a clay mineral having a dioctahedral three-layer structure. 40 mL / 100 g, bulk density: 0.5 g / mL), beiderite (oil absorption: 62 mL / 100 g, bulk density: 0.55 g / mL), pyrophyllite (oil absorption: 70 mL / 100 g, bulk density: 0.63 g) On the other hand, as clay minerals having a trioctahedral three-layer structure, saponite (oil absorption: 73 mL / 100 g, bulk density: 0.15 g / mL), hectorite (oil absorption: 72 mL) / 100 g, bulk density: 0.7 g / mL), stevensite (oil absorption: 30 mL / 100 g, bulk density 1.2 g / mL), talc (oil absorption: 7 mL / 100 g, the bulk density: 0.1 g / mL), and the like.
[0067]
Content of clay mineral is 0.1-30 mass% normally in detergent particle | grains, Preferably it is 0.5-20 mass%, Most preferably, it is 1-10 mass%. The raw material components (1) to (4) above may be spray-dried and then used as a dry powder after blending into the slurry.
[0068]
(5) Dissolution promoter
Examples of the dissolution accelerator blended in the detergent particles include inorganic carbonates such as potassium carbonate, ammonium sulfate, and ammonium chloride, sodium benzoate, sodium benzenesulfonate, sodium p-toluenesulfonate, and sodium xylenesulfonate. Water-soluble substances such as sodium chloride, citric acid, D-glucose, urea, and sucrose.
(6) Swellable water-insoluble substances
Specific examples of swellable water-insoluble substances to be incorporated in the detergent particles include powdered cellulose, crystalline cellulose, low etherification degree carboxymethylcellulose, crosslinked carboxymethylcellulose, carboxymethylcellulose calcium, hydroxypropylcellulose and the like. Examples thereof include cellulose derivatives, starch such as corn starch, starch derivatives such as hydroxypropyl starch, cross-linked polyvinyl pyrrolidone, and low-etherification polyvinyl alcohol.
[0069]
Specific examples of the components blended in the other detergent particles include the following.
(7) Fluorescent agent: bis (triazinylamino) stilbene disulfonic acid derivative, bis (sulfostyryl) biphenyl salt [Tinopearl CBS] and the like.
(8) Antistatic agent: Cationic surfactant such as dialkyl type quaternary ammonium salt.
(9) Recontamination inhibitor: Cellulose derivatives such as carboxymethylcellulose.
(10) Bulking agent: sodium sulfate, potassium sulfate, sodium hydrochloride and the like.
(11) Reducing agent: sodium sulfite, potassium sulfite and the like.
[0070]
The average particle size of the detergent particles is preferably 200 to 1500 μm, more preferably 300 to 1000 μm. The bulk density is preferably 0.4 to 1.2 g / mL, and more preferably 0.5 to 1.0 g / mL.
[0071]
The detergent particles can be obtained by the following granulation method. Detergent ingredient powder and binder components (surfactant, water, liquid polymer component, etc.) are kneaded and kneaded, then extruded and granulated by extrusion, kneaded and kneaded, and then the solid obtained A kneading and crushing granulation method that crushes and granulates the detergent, a stirring granulation method in which the binder component is added to the raw material powder and stirred and granulated with a stirring blade, and the binder component is sprayed while rolling the raw material powder And a fluidized bed granulation method in which a liquid binder is sprayed and granulated while fluidizing the raw material powder. Specific apparatuses and conditions that can be used in these granulation methods are as described in Japanese Patent Application No. 2001-299007, Japanese Patent Application No. 2002-77254, edited by Japan Powder Technology Association, and the first edition of the Granulation Handbook. .
[0072]
2. Fluorescent brightener particles
When the fluorescent whitening agent is added as independent particles in the cleaning agent particle group, for example, granular white carbonate, fine powder A-type zeolite, a fluorescent whitening agent powder together with a binder is rolled or stirred and granulated, or clay After mixing mineral and fluorescent brightener powder, water can be added, extruded and granulated, added after drying in a fluidized bed or the like.
[0073]
The particle size of the fluorescent brightener particles is preferably 250 to 1000 μm, particularly preferably 250 to 750 μm. The fluorescent brightening agent is preferably 0.05 to 2% by mass, more preferably 0.1 to 1% by mass, based on the total amount of the detergent particle group, as a pure component.
[0074]
3. Enzyme particles
As the enzyme in the enzyme particles, commercially available enzyme particles that are currently used in granular laundry detergents can be used as they are. Specifically, there are sabinase 18T, cannase 12T, lipolase ultra 50T, everase 8T (above, manufactured by Novo Nordisk), maxacar 45G, maxapem 30G, properase 1000E (above, manufactured by Dienencore), and the like.
[0075]
The content of the enzyme particles is preferably 0.1 to 5% by mass, and preferably 0.3 to 2% by mass with respect to the total amount of the cleaning agent particle group.
[0076]
The detergent particles, fluorescent brightener particles and enzyme particles can be used after the surface is colored with a dye or pigment. At this time, dyes and pigments used for coloring are those that do not cause dyeing to clothing during washing. Examples of such dyes and pigments include ultramarine blue, coranyl green CG-130 (CI number: 74260), food dye red No. 102, and acid dye Acid Yellow 141. After these dyes and pigments are made into aqueous solutions and dispersions, the above particles are added while stirring and rolling in the same agitation granulator or tumbling granulator as the granulator of the detergent particles. Can be colored with. Further, the particles can be colored by spraying the aqueous solution or dispersion on the particles while the particles are being transferred by a belt conveyor. As a coloring amount, 0.01-1 mass% is preferable with respect to the particle | grains to color.
[0077]
4). Bleach particles
As the bleaching agent in the cleaning agent particle group, sodium percarbonate can be suitably used. As the sodium percarbonate, a coated one can also be used. The coated sodium percarbonate can be granulated by spraying sodium percarbonate particles separately with an aqueous boric acid solution and an alkali metal silicate salt. In this case, the spraying may be performed separately, simultaneously or sequentially from two or more spray nozzles. The solvent of the boric acid solution and the alkali metal silicate is preferably water from the viewpoint of solubility, safety, and cost. As boric acid as the coating agent, orthoboric acid, metaboric acid, tetraboric acid or the like is used. In addition, as the alkali metal silicate, one kind of sodium metasilicate, sodium orthosilicate, sodium salt of water glass No. 1, No. 2, No. 3, potassium metasilicate, potassium orthosilicate, etc. may be used alone or in combination of two or more kinds. Can be used. Among these, water glass No. 1, No. 2, and No. 3 are liquid and are preferable from the viewpoint of convenience in use.
[0078]
In addition to the coating agent, a conventionally known stabilizer such as a chelating agent may be used in combination with the coating agent. The particle diameter of the coated sodium percarbonate particles is preferably 100 to 2000 μm, more preferably 200 to 1000 μm, from the viewpoint of the stability and solubility of the sodium percarbonate particles.
[0079]
The content of the bleaching agent is preferably 1 to 30% by mass and more preferably 2 to 20% by mass with respect to the total amount of the cleaning agent particle group.
[0080]
5. Bleach activator particles
Examples of the bleach activator in the cleaning agent particle group include tetraacetylethylenediamine, alkanoyloxybenzenesulfonic acid having 8 to 12 carbon atoms, alkanoyloxybenzenecarboxylic acid having 8 to 12 carbon atoms, and salts thereof. Among these, those represented by the following general formula (9) or (10) are preferable.
[0081]
[Chemical 1]

(Wherein R ¹⁹ Are each independently an alkyl group or alkenyl group having 7 or more carbon atoms, Ph is a phenylene group, and M is each independently a salt-forming cation or hydrogen. )
[0082]
R ¹⁹ Is an alkyl group or alkenyl group having 7 or more carbon atoms, preferably an alkyl group or alkenyl group having 7 to 17 carbon atoms, particularly a linear alkyl group, more preferably a linear alkyl group having 9 to 15 carbon atoms. It is. M is a salt-forming cation or hydrogen, and examples thereof include alkali metals such as sodium and potassium, and amines such as ammonium and alkanolamine. Of these, hydrogen and alkali metals are preferred. In the above general formula, SO _Three The M group and the COOM group can be in the ortho, meta, or para position, and the para position is preferred.
[0083]
In the detergent particle group, these bleach activators can be used alone or as a mixture of two or more. Since these bleaching activators are obtained as plate-like crystals of about 100 to 1000 μm by a normal production method, they are preferably about 250 to 750 μm so that the average particle diameter is smaller than 800 μm by a conventional method as necessary. Grind to make Furthermore, from the viewpoint of improving storage stability and solubility, after dispersing the bleach activator in a solid polyethylene glycol such as PEG # 3000 to # 20000 heated and melted at room temperature, the noodles with a diameter of about 1 mm are extruded. A granular bleach activator granulated product may be produced, and then lightly pulverized to a length of about 1 to 3 mm.
[0084]
The content of the bleach activator is preferably 0.5 to 15% by mass, particularly preferably 1 to 10% by mass with respect to the total amount of the detergent particle group.
[0085]
Moreover, you may perfume the mixture which mixed the said cleaning agent particle | grains independent, various particles, and the liquid additive as needed.
In some cases, the coated particles and the detergent particles may be mixed and then fragranced. As the fragrance used, hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, ethers such as aliphatic ethers and aromatic ethers Oxides, aliphatic oxides, terpene oxides, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, aldehydes such as thioaldehydes, aromatic aldehydes, aliphatic ketones, terpene ketones, hydrogenated aromatics Ketones such as aromatic ketones, aliphatic cyclic ketones, non-benzene aromatic ketones, aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, Acids such as aromatic carboxylic acids, acid amides, aliphatic lactates , Macrocyclic lactone, terpene lactone, hydrogenated aromatic lactone, lactone such as aromatic lactone, aliphatic ester, furan carboxylic acid ester, aliphatic cyclic carboxylic acid ester, cyclohexyl carboxylic acid ester, terpene carboxylic acid Synthetic fragrances such as acid esters, esters such as aromatic carboxylic acid esters, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, indoles, etc., natural fragrances from animals and plants, natural fragrances and One or two or more kinds of blended fragrances containing synthetic fragrances can be mixed and used. For example, in 1996, Chemical Industry Daily published by Motoichi Into, “Synthetic Fragrance Chemistry and Product Knowledge”, 1969 MONTCLAIR, N. J. et al. Fragrances described in “Perfume and Flavor Chemicals” by STEFEN Arctander can be used. The main fragrance names are shown below.
[0086]
Aldehyde C6-C12, anisaldehyde, acetal R, acetophenone, acetyl cedrene, adoxal, allyl amyl glycolate, allyl cyclohexane propionate, alpha damascon, beta damascon, delta damascon, ambret lid, ambrox lid, amyl Cinnamic aldehyde, amyl cinnamaldehyde dimethyl acetal, amyl valericate, amyl salicylate, isoamyl acetate, isoamyl salicylate, uranium thiol, acetyl eugenol, bacdanol, benzyl acetate, benzyl alcohol, benzyl salicylate, bergamyl acetate, bornyl acetate, Butyl butyrate, para tertiary butyl cyclohexanol, para tertiary butyl Rohexyl acetate, ortho-tertiary butyl cyclohexanol, ortho-tertiary butyl cyclohexyl acetate, benzaldehyde, benzyl formate, caryophyllene, cachemelan, carvone, cedro amber, cedryl acetate, cedrol, celestolide, cinnamic alcohol, cinnamic aldehyde , Cisjasmon, citral, citral dimethyl acetal, citrusal, citronellal, citronellol, citronellyl acetate, citronellyl formate, citronellil nitrile, cyclaset, cyclamenaldehyde, cyclaprop, caron, coumarin, cinnamyl acetate, delta C6-C13 Lactone, dimethylbenzyl carbinol, dihydrojasmon, dihydr Linalool, dihydromyrsenol, dimethol, dimyrcetol, diphenyl oxide, ethyl vanillin, eugenol, fluitate, fenthyl alcohol, phenylethylphenyl acetate, galakisolid, gamma C6-13 lactone, α-pinene, β-pinene, limonene, myrcene, β -Caryophyllene, geraniol, geranyl acetate, geranyl formate, geranyl nitrile, hedion, helional, heliotropin, cis-3-hexenol, cis-3-hexenyl acetate, cis-3-hexenyl salicylate, tripral, hexylcin Namic aldehyde, hexyl salicylate, hyacinth dimethyl acetal, hydrotropic alcohol, hydroxy citronellal, indole, Ionone, isobornyl acetate, isocyclocitral, iso-E super, isoyugenol, isononyl acetate, isobutyl quinoline, jasmar, jasmolactone, jasmofilan, coabon, ligustral, lyial, lime oxide, linalool, linalool oxide, linalyl acetate , Lilal, Manzanate, Mayol, Mensanil Acetate, Mentsonate, Methylanthranilate, Methyl Yugenol, Menthol, Alpha Methyl Ionone, Beta Methyl Ionone, Gamma Methyl Ionone, Methyl Iso Yugenol, Methyl Lavender Ketone, Methyl Salicylate , Mugealdehyde, mugor, musk TM-II, musk 781, musk C14, muscone, sibeton, cyclopentadecano , Cyclohexadecenone, cyclopentadecanolide, ambletlide, cyclohexadecanolide, 10-oxahexadecanolide, 11-oxahexadecanolide, 12-oxahexadecanolide, ethylene brushate, ethylene Dodecandioate, oxahexadecen-2-one, 14-methyl-hexadecenolide, 14-methyl-hexadecanolide, musk ketone, musk tibetine, nopylic alcohol, nopylacetate, neryl acetate, nerol, methylphenyl acetate, miracaldehyde, neoberga Mate, Oak moss No. 1, Oligorib, Oxyphenylone, Paracresyl methyl ether, Pentalid, Phenyl ethyl alcohol, Phenyl ethyl acetate, Alpha pinene, Rubafuran, Damasenone Raspberry Ketone, Dimethylbenzyl Carvinyl Acetate, Jasma Cyclen, Methyl Naphthyl Ketone, Rosephenone, Rose Oxide, Sandaroa, Sandera, Santa Rex, Stila Reel Acetate, Stila Reel Propionate, Terpineol, Terpinyl Acetate, Tetrahydro Linalol, tetrahydrolinalyl acetate, tetrahydrogeraniol, tetrahydrogeranylacetate, tonalid, traseolide, triplar, thymol, crocodile, belladox, yarayara, anise oil, bay oil, boadrose oil, cananga oil, cardamom oil, cassia oil , Cedarwood oil, orange oil, mandarin oil, tangerine oil, basil oil, nutmeg oil, citronella oil, clove oil, coriander oil, oil Remy oil, Eucalyptus oil, Fennel oil, Galvanum oil, Geranium oil, Hiba oil, Straw oil, Jasmine oil, Lavandin oil, Lavender oil, Lemon oil, Lemongrass oil, Lime oil, Neroli oil, Oak moss oil, Ocotia oil, Patchouli Oil, peppermint oil, perilla oil, petitgren oil, pine oil, rose oil, rosemary oil, camphor oil, melamine oil, clary sage oil, sandalwood oil, spearmint oil, spike lavender oil, star anise oil, thyme oil, tonka Bean tincture, turpentine oil, vanilla bean tincture, vetiver oil, ylang-ylang oil, grapefruit oil, yuzu oil, benzoin, peruvian balsam, trubal sum, tuberose oil, oak moss absolute, far balsam, mustin tincture, castrium tincture, civet tincture, amber Gristin And the like.
[0087]
Diethyl phthalate, dipropylene glycol, benzyl benzoate, isopropyl myristate, hercoline, isopentane, orange terpene and the like can be used as a solvent or a retaining agent for the fragrance. In addition, a fragrance | flavor is not limited to the fragrance | flavor of an Example.
[0088]
In the present invention, the coating particles and the cleaning agent particle group can be arbitrarily mixed and used, but the ratio (mass ratio) is preferably covering particle / cleaning agent particle group = 3/97 to 97/3. -95/5 is more preferable, and 10 / 90-90 / 10 is more preferable.
[0089]
As the mixing method, dry mixing is preferably used. As the mixer to be used, any mixer may be used as long as various particles can be sufficiently mixed. However, a horizontal cylindrical type, a double cone type, a V type, a rotation / revolution type, or the like can be suitably used. . Moreover, you may use a stirring granulator and a rolling granulator. Preferably, a horizontal cylindrical type or a double cone type is used and mixed at a temperature of 0 to 50 ° C. and an Fr number of 0.01 to 0.2 (the calculation formula is as described above). At this time, the order of addition of various particles and other components is not particularly limited.
[0090]
The physical property value of the granular detergent composition finally obtained by mixing the coated particles and the detergent particle group is not particularly limited, but the bulk density is usually 0.3 g / mL or more, preferably 0. 0.5 to 1.2 g / mL, more preferably 0.6 to 1.1 g / mL. Moreover, the average particle diameter is preferably 200 to 1500 μm, more preferably 300 to 1000 μm. If the average particle size is less than 200 μm, dust may be easily generated, while if it exceeds 1500 μm, the solubility desired by the present invention may not be obtained. Furthermore, the fluidity of the detergent composition is preferably 60 ° or less, particularly 50 ° or less as an angle of repose. If it exceeds 60 °, the handleability may deteriorate.
[0091]
The detergent composition obtained by mixing the coated particles and the detergent particles can be used as a granular detergent as it is, and further mixed with a disintegrant and then compression molded to form a tablet detergent or briquette detergent. It can also be used as a compression molding detergent.
[0092]
【The invention's effect】
According to the present invention, there are provided coated particles and a detergent composition that are not deteriorated in solubility due to agglomeration in water during long-term storage, have excellent dispersibility, and further prevent adhesion to a granulator. be able to.
[0093]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified,% indicates mass%, the ratio indicates mass ratio, and the amount of each component in the table is an amount converted into a pure component.
[0094]
Production method of coated particles (1) (stir granulation)
Of the compositions shown in Tables 2 to 6 below, a water-soluble inorganic salt (temperature: 25 ° C.) equipped with a blade-shaped excavator and a shovel-wall clearance of 5 mm is a Ladige mixer (manufactured by Matsubo, M20 type). ) (Filling rate 30% by volume), and stirring of the main shaft 200 rpm was started (the chopper was stopped). 10 seconds after the start of stirring, the salt-sensitive polymer is added in 30 seconds, and after the addition is completed, a salt that sensitizes the salt-sensitive polymer (hereinafter referred to as a polymer-sensitive salt) is added dropwise over 30 seconds in the case of a liquid. In the case of powder, it was added all at once and stirred for 30 seconds. Finally, a fluidity improver was added as necessary, and stirring was continued for 30 seconds to obtain a granulated product.
[0095]
The obtained granulated material was classified using a sieve having an opening of 2000 μm, and particles passing through the sieve having an opening of 2000 μm were used as coated particles. In the comparative example, the addition of the polymer sensitive salt was not performed.
[0096]
Manufacturing method of coated particles (2) (Rolling granulation)
Among the compositions shown in Tables 2 to 6 below, a water-soluble inorganic salt (temperature: 25 ° C.) is mixed with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L and inner wall surface). (Having two baffle plates having a clearance of 20 mm and a height of 45 mm) (filling rate: 20% by volume), and the rolling operation was started under the conditions of a rotational speed of 22 rpm and 25 ° C. 30 seconds after the start of rolling, the salt-sensitive polymer was sprayed and added at 100 g / min using a two-fluid hollow cone nozzle with a spray angle of 70 °. After the addition was completed, the polymer-sensitive salt was 100 g / in the case of a liquid. Spray addition was performed at min, and in the case of powder, it was added all at once and mixed by rolling for 60 seconds. Finally, a fluidity improver was added as necessary, and the rolling operation was continued for 60 seconds to obtain a granulated product.
[0097]
The obtained granulated material was classified using a sieve having an opening of 250 μm and an opening of 2000 μm, and particles passing through the sieve having an opening of 2000 μm without passing through the opening of 250 μm were used as coated particles. In the comparative example, the addition of the polymer sensitive salt was not performed.
[0098]
Production method of coated particles (3) (fluidized bed granulation)
Among the compositions shown in Tables 2 to 6, a water-soluble inorganic salt (temperature: 25 ° C.) was placed in a fluidized bed (Paulex Co., Ltd., Glatt-POWREX, model number FD-WRT-20), and a powder layer at rest Weight was added to a thickness of 200 mm. Thereafter, wind (air) at 20 ° C. was sent into the fluidized bed, and after confirming that the powder was fluidized, the salt-sensitive polymer was sprayed from above onto the fluidized powder layer. The granulation and coating (coating) operation was performed while adjusting the fluid velocity in the fluidized bed in the range of 0.2 to 10.0 m / s while confirming the fluidized state.
[0099]
The salt-sensitive polymer was sprayed at 50 ° C., and a two-fluid hollow cone nozzle with a spray angle of 70 ° was used as the nozzle for spraying. The spray rate was about 100 g / min. After the completion of spraying of the salt-sensitive polymer, a solution-like polymer-sensitive salt was added by spraying at a spray rate of about 100 g / min using the same nozzle. When adding a polymer sensitive salt of powder, the granulated material is discharged from the fluidized bed, and a rolling drum (diameter 0.6 m, length 0.48 m, thickness 1 mm × width 12 cm × length 48 cm) The granulated product and the polymer-sensitive salt were mixed for 60 seconds with 4 plates and a rotation speed of 20 rpm.
[0100]
The obtained granulated material was classified using a sieve having an opening of 2000 μm, and particles passing through the sieve having an opening of 2000 μm were used as coated particles. In the comparative example, the addition of the polymer sensitive salt was not performed.
[0101]
The coarse particles of the sieved product not used as the coated particles generated in the classification steps (1) to (3) of the coated particles described above are Fitzmill (Hosokawa Micron) together with fine sodium sulfite equivalent to 5% of the particles. The product was pulverized using a DKA-3 manufactured by Co., Ltd. (screen hole diameter: 2 mm, rotation speed: 4700 rpm in all stages), and was put into a granulator together with a water-soluble inorganic salt at the next granulation and reused. In addition, when fine particles of an unsieved product that was not used as coated particles were generated by the classification operation, the fine particles were also put into a granulator together with a water-soluble inorganic salt at the next granulation and reused.
[0102]
Method for producing cleaning agent particle group A
(A-1) Granulation of detergent particles
Of the A composition shown in Table 1 below, nonionic surfactant, A type for grinding aid of 3.2% equivalent amount (vs. each detergent particle, the same applies hereinafter) and 1.5% equivalent amount for surface coating After preparing a slurry with a water content of 38% in which components other than zeolite, enzymes, pigments and fragrances are dissolved or dispersed in water, the slurry is spray-dried at a hot air temperature of 300 ° C. using a countercurrent spray drying tower, % Spray-dried particles were obtained. Along with these dry particles, a nonionic surfactant equivalent to 3.5% and water were put into a continuous kneader (manufactured by Kurimoto Seiko Co., Ltd., KRC-S4 type), and the kneading capacity was 120 kg / h and the temperature was 60 ° C. It was kneaded under conditions to obtain an amorphous solid detergent. This unshaped solid detergent was extruded with a pelleter double equipped with a die with a hole diameter of 10 mm (EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.) and cut with a cutter (cutter peripheral speed was 5 m / s) A pellet-shaped solid detergent having a length of about 5 to 30 mm was obtained.
[0103]
Next, 4.2% equivalent amount of particulate A-type zeolite (average particle size 180 μm) as a grinding aid is added to the obtained solid detergent, and arranged in three stages in series under cold air (10 ° C., 15 m / s). The Fitzmill (made by Hosokawa Micron Corporation, DKA-3) was pulverized (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation speed: 4700 rpm for all stages). Finally, filled with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, the inner wall surface of the drum of the container 131.7L has two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Rolling for 2 minutes while spraying non-ionic surfactant equivalent to 0.5% while adding 0.5% equivalent of fine powder A-type zeolite under the conditions of rate 30 volume%, rotation speed 22rpm, 25 ° C To obtain detergent particles.
[0104]
(A-2) Perfume of cleaning agent particles
Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) While mixing the detergent particles obtained in (A-2) under the conditions of volume%, rotational speed 22 rpm, and 25 ° C., a perfume equivalent to 0.14% was sprayed to perfume the detergent particles.
[0105]
(A-3) Coloring of detergent particles
In order to color a part of the obtained detergent particles after perfume, the detergent particles are transported at a speed of 0.5 m / s on the belt conveyor (the height of the detergent particle layer on the belt conveyor is 30 mm, the layer The blue pigment solution was sprayed on the surface (width 300 mm). Cleaning agent particles A (average particle size 500 μm, bulk density 0.80 g / mL) were obtained.
[0106]
(A-4) Mixing with other particles
Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) Under the conditions of volume%, rotational speed 22 rpm, 25 ° C., the coloring agent particles are equivalent to 0.72% enzyme particles, 4.0% bleach particles, and 1.3% bleach activator particles. The amount was mixed for 5 minutes to obtain cleaning agent particle group A (average particle size 500 μm, bulk density 0.80 g / mL).
[0107]
Manufacturing method of cleaning agent particle group B
A cleaning agent particle group B (average particle size 480 μm, bulk density 0.80 g / mL) having the composition B shown in Table 1 was obtained by the same manufacturing method as that for cleaning particle group A. However, as shown in the composition B in Table 1, the bleaching agent particles and the bleaching activator particles are not mixed.
[0108]
Method for producing cleaning agent particle group C
(C-1) Dry neutralization by fluidized bed
Of the C composition shown in Table 1, a powder raw material (excluding the coating agent) containing potassium carbonate and sodium carbonate pulverized product is a fluidized bed (made by Paulex, Glatt-POWREX, model number FD-WRT-20) The weight that the powder layer thickness at the time of standing was 200 mm was added. Thereafter, 20 ° C. wind (air) is sent into the fluidized bed, and after confirming that the powder is fluidized, α-SF-H (α-sulfo fatty acid alkyl ester) is directed toward the fluidized powder layer. Sprayed from the top. The granulation operation was performed while adjusting the fluid velocity in the fluidized bed within the range of 0.2 to 2.0 m / s while confirming the fluidized state.
[0109]
α-SF-H was sprayed at 60 ° C., and a two-fluid hollow cone nozzle having a spray angle of 70 ° was used as the nozzle for spraying. The spray rate was about 400 g / min. After the spraying of α-SF-H, 20 ° C. wind (air) was further sent into the fluidized bed, and aging was performed for 240 seconds. Further, the granulated material is discharged from the fluidized bed, and within a rolling drum (diameter 0.6 m, length 0.48 m, thickness 1 mm × width 12 cm × length 48 cm with baffle plates, rotation speed 20 rpm) An amount equivalent to 4.5% of zeolite was coated.
[0110]
(C-2) Bleaching
Thereafter, an aqueous hydrogen peroxide solution is put on the obtained particles in a rolling drum (diameter 0.6 m, length 0.48 m, thickness 1 mm × width 12 cm × length 48 cm with baffle plates, rotation speed 20 rpm). Spraying was performed, and an additional amount corresponding to 5.0% of zeolite was further coated to improve fluidity. In this way, detergent particles C (average particle size 380 μm, bulk density 0.50 g / mL) were obtained.
[0111]
Method for producing cleaning agent particle group D
(D-1) Granulation of detergent particles
Of the D composition shown in Table 1 below, nonionic surfactant, type A zeolite for pulverizing aid equivalent to 4.0% and surface coating equivalent to 2.0%, montmorillonite, white carbon, enzyme, dye And a slurry with 40% moisture dissolved or dispersed in water, and then spray-dried at a hot air temperature of 300 ° C. using a countercurrent spray drying tower to produce 3% moisture-dried particles. Obtained. Along with these dry particles, a nonionic surfactant and water were added to a continuous kneader (manufactured by Kurimoto Seiko Co., Ltd., KRC-S4 type), and kneaded under conditions of a kneading capacity of 120 kg / h and a temperature of 60 ° C. An amorphous solid detergent was obtained. This unshaped solid detergent was extruded with a pelleter double equipped with a die with a hole diameter of 10 mm (EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.) and cut with a cutter (cutter peripheral speed was 5 m / s) A pellet-shaped solid detergent having a length of about 5 to 30 mm was obtained.
[0112]
Next, 4.2% equivalent amount of particulate A-type zeolite (average particle size 180 μm) as a grinding aid is added to the obtained solid detergent, and arranged in three stages in series under cold air (10 ° C., 15 m / s). The Fitzmill (made by Hosokawa Micron Corporation, DKA-3) was pulverized (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 8 mm / 6 mm / 3 mm, rotation speed: 3760 rpm in all stages). Finally, filled with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, the inner wall surface of the drum of the container 131.7L has two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) A 0.5% equivalent amount of finely divided A-type zeolite was added under the conditions of a rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C., and rolled for 2 minutes to effect surface modification.
[0113]
(D-2) Perfume of cleaning agent particles
The cleaning agent particles were scented by the same method as in the case of the cleaning agent particle group A.
[0114]
(D-3) Mixing with other particles
Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) The obtained detergent particles after perfume and enzyme particles equivalent to 1.0% were mixed for 5 minutes under the conditions of volume%, rotational speed 22 rpm, and 25 ° C. to obtain detergent particle group C (average particle diameter 560 μm, A bulk density of 0.81 g / mL) was obtained.
[0115]
Manufacturing method of cleaning agent particle group E
Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) The cleaning agent particle group A and the cleaning agent particle group C were mixed at a mass ratio of 1: 1 for 5 minutes under the conditions of volume%, rotation speed 22 rpm, and 25 ° C. to obtain a cleaning agent particle group E (average particle size 530 μm, bulk density). 0.81 g / mL) was obtained.
[0116]
[Table 1]

[0117]
Mixing of coated particles and detergent particles
The obtained coated particles and detergent particles are mixed into a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, baffle plate having a clearance of 20 mm between the inner wall surface of the drum and the inner wall surface of the container 131.7 L, and a height of 45 mm. 2) and mixed at the ratios shown in Tables 2 to 6 under the conditions of a filling rate of 30% by volume, a rotation speed of 22 rpm, and 25 ° C. to obtain a detergent composition. When mixing the coated particles and the cleaning agent particle group C, the fragrance was sprayed so as to be equivalent to 0.2% of the mixture simultaneously with the mixing.
[0118]
The raw materials used in the examples are shown below.
LAS-K: Potassium salt of Raipon LH-200 (manufactured by Lion Corporation)
α-SF-Na: carbon number 14: sodium α-sulfo fatty acid methyl ester having carbon number 16 = 18: 82 (AI = 70%, the balance is unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate, hydrogen peroxide, water etc)
α-SF-H: α-sulfo fatty acid alkyl ester (methyl ester (Pastel M-14, Pastel M-16 (manufactured by Lion Oleochemical Co., Ltd.) mixed at 2: 8)) is disclosed in JP-A No. 2001-64248. Sulfonated according to the method disclosed in Example 1 of the publication, extracted after the esterification step and made into α-sulfo fatty acid alkyl ester)
Soap: C12: C18 F1 = 1: 1 fatty acid sodium (68% pure aqueous paste)
Nonionic surfactant A: Diador 13 (Mitsubishi Chemical Co., Ltd.) ethylene oxide average 15 mol adduct (90% pure)
Nonionic surfactant B: 15 mol of ethylene oxide average adduct of pastel M-181 (manufactured by Lion Oleochemical Co., Ltd.)
Type A zeolite: Shilton B (manufactured by Mizusawa Chemical Co., Ltd.) (80% pure)
Acrylic acid / maleic acid copolymer Na (1): AQUALIC TL-400 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40% aqueous solution)
Acrylic acid / maleic acid copolymer Na (2): Aqualic TL-400 (manufactured by Nippon Shokubai Co., Ltd.) diluted with water to a pure content of 20%
Polyacrylic acid Na: Aqualic DL-40 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40% aqueous solution)
Alginic acid Na: pure 4% aqueous solution of Duck Algin NSPLL (manufactured by Kibun Food Chemifa Co., Ltd.)
Carboxymethylcellulose Na: Pure 5% aqueous solution of CMC Daicel 1105 (manufactured by Daicel Chemical Industries, Ltd.)
Polyvinyl alcohol: 5% pure water solution of Kuraray Poval PVA-105 (manufactured by Kuraray Co., Ltd.)
Sodium carbonate: grain ash (Asahi Glass Co., Ltd.)
Fine powdered sodium carbonate: Granulated ash (made by Asahi Glass Co., Ltd.) crushed to an average particle size of 30 μm by a desktop fine pulverizer (stud mill 63C, manufactured by Alpine)
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd.)
Sodium bicarbonate: A first grade reagent manufactured by Pure Chemical Co., Ltd.
Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.)
Potassium sulfate: Kali sulfate (manufactured by Ueno Pharmaceutical Co., Ltd.)
Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.)
Fine powder sodium sulfite: Anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.) was pulverized to an average particle size of 25 μm with a tabletop fine pulverizer (stud mill 63C, manufactured by Alpine)
Calcium chloride (liquid): Central Glass, 35% aqueous solution
Calcium chloride (powder) (1): First grade reagent of calcium chloride anhydride (manufactured by Pure Chemical Co., Ltd.)
Calcium chloride (powder) {circle around (2)}: Calcium chloride dihydrate (granular) (manufactured by Central Glass Co., Ltd.) finely pulverized with a tabletop pulverizer (stud mill 63C, manufactured by Alpine)
Magnesium chloride (powder): Magnesium chloride anhydride (manufactured by Junsei Chemical Co., Ltd.) reagent first grade product
Calcium nitrate (liquid): A 50% pure aqueous solution of calcium nitrate tetrahydrate (manufactured by Pure Chemical Co., Ltd.)
Aluminum chloride (powder): Aluminum chloride anhydrous (made by Pure Chemical Co., Ltd.) reagent first grade product
Magnesium sulfate (liquid) Magnesium sulfate anhydride (manufactured by Junsei Chemical Co., Ltd.) reagent first grade pure 30% aqueous solution
Calcium oxide (powder): First grade reagent of calcium oxide (manufactured by Pure Chemical Co., Ltd.)
Sodium tetraborate (powder): Sodium tetraborate anhydrous (manufactured by Junsei Chemical Co., Ltd.) reagent first grade product
White carbon: fine silica powder (Tokuyama, Tokuyama Co., Ltd.)
Montmorillonite: Montmorillonite (SUD CHEMIE round rosyl)
Fluorescent agent: Chino Pearl CBS-X (Ciba Specialty Chemicals)
Dye: Blue dye solution (Ultramarine) 35% solution (manufactured by Dainichi Seika Co., Ltd.)
Fragrance: Decanal 0.5%, Octanal 0.3%, Hexylcinnamic aldehyde 10.0%, Dimethylbenzylcarbinyl acetate 8.0%, Lemon oil 3.0%, Lilyal 6.0%, Lyral 2.0 %, Linalool 5.0%, phenylethyl alcohol 7.5%, tonalide 2.0%, o-tert-butylcyclohexyl acetate 3.0%, galaxolide BB * 2.0%, linascol 2.5%, geraniol 1 0.0%, citronellol 2.0%, jasmolange 2.0%, methyl dihydrojasmonate 5.0%, terpineol 1.0%, methyl ionone 3.0%, acetyl cedrene 5.0%, remonitrile 1.0 %, Fluitate 1.0%, olivine 1.5, benzoin 1.0%, cis-3-hexenol 0.5%, Kumari 2.0%, Damasenone 0.2%, Damascon 0.3%, Helional 1.5%, Heliotropin 1.5%, Anisaldehyde 2.5%, Gamma-undecalactone 0.8%, Bagdanol 2%, tripral 0.5%, styryl acetate 1.5%, caron 0.1%, pentalide 3.0%, oxahexadecen-2-one 2.9%, ethylene brush rate 6.2%. BB represents benzyl benzoate, and% of the fragrance component represents% in the fragrance composition.
Hydrogen peroxide solution: Pure Chemical Co., Ltd., first grade reagent, aqueous solution containing 35% hydrogen peroxide
Enzyme particles: Sabinase 18T (Novo Nordisk Bioindustry)
Bleaching agent particles: sodium percarbonate (manufactured by Mitsubishi Gas Chemical Co., Inc., SPC-D)
Bleach activator particles: particles obtained by the following production method
[0119]
(Method for producing bleach activator particles)
Hosokawa Micron Co., Ltd. Extrude Ohmic EM-6 type 4-decanoyloxybenzoic acid (reagent grade) 69.4% (for bleach activator particles, the same applies hereinafter), polyethylene glycol 20.9% and AOS -Na (sodium α-olefin sulfonate) (4.7%) was added and kneaded and extruded at 65 ° C. to obtain a noodle-like extruded product having a diameter of 0.8 mmφ. From this extruded product, cold air at 15 ° C. was introduced from the same direction as the kneaded extrudate granulated product by Comminator FXB type (Fuji Powder Co., Ltd.), and A type zeolite powder 5.0 as an auxiliary agent. % Was supplied in the same manner and pulverized to obtain bleach activator particles.
[0120]
[Examples 1-30, Comparative Examples 1-3]
The coated particles were prepared by the above method shown in the table so as to have the compositions shown in Tables 2-6. A detergent composition was obtained by the above method using the obtained coated particles and the detergent particles obtained above. About the obtained covering particle | grains, the average particle diameter and the bulk density were measured based on the following method, and apparatus adhesiveness was evaluated. About a detergent composition, the average particle diameter and the bulk density were measured, and the solubility after long-term storage was evaluated. The results are also shown in Tables 2-6.
[0121]
(1) Measurement of average particle size
Classification operation was performed using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm and a tray. In the classification operation, a sieve with a small opening is stacked in the order of a sieve with a large opening, a base sample of 100 g / time is placed on the top of the top 1680 μm sieve, a lid is put on, and a low-tap sieve shaker (( Attached to Iida Seisakusho Co., Ltd., Tapping: 156 times / minute, Rolling: 290 times / minute) After shaking for 10 minutes, the sample remaining on each sieve and tray is collected for each sieve. It was.
[0122]
By repeating this operation, 1410 to 1680 μm (1410 μm.on), 1190 to 1410 μm (1190 μm.on), 1000 to 1190 μm (1000 μm.on), 1000 to 710 μm (710 μm.on) 500 to 710 μm (500 μm.on) , 350 to 500 μm (350 μm.on), 250 to 350 μm (250 μm.on), 149 to 250 μm (149 μm.on), dish to 149 μm (149 μm.pass), and classification samples with respective particle diameters were obtained. ) Was calculated.
[0123]
Next, the opening of the first sieve with a calculated weight frequency of 50% or more is set to a μm, the opening of the sieve that is one step larger than a μm is set to b μm, and the cumulative weight frequency from the tray to the sieve of a μm is calculated as c %, And the weight frequency on a μm sieve was d%, and the average particle diameter (weight 50%) was determined by the following formula.
[0124]
[Expression 1]

[0125]
(2) Measurement of bulk density
The bulk density was measured according to JIS K3362.
[0126]
(3) Equipment adhesion evaluation
After the production of each coated particle, the formation of deposits on the inner wall of the apparatus where the coated particles were granulated was evaluated based on the following criteria.
A: Almost no deposits
○: Level with no deposits but no problem
Δ: Deposits are conspicuous
X: There are deposits on almost the entire surface.
[0127]
(4) Solubility evaluation after long-term storage
(1) Coated cardboard from the outside (basis weight: 350 g / m ² ), Wax sand paper (basis weight: 30 g / m ² ), Kraft pulp paper (basis weight: 70 g / m ² ) Was used to produce a box having a length of 15 cm, a width of 9.3 cm, and a height of 18.5 cm. A 1.2 kg mixture of coated particles and detergent particles was placed in this box and stored in a constant temperature and humidity chamber at 40 ° C. and 85% RH for 30 days to obtain a sample for solubility test.
(2) A 2-tank washing machine (CW-C30A1-H, manufactured by Mitsubishi Electric Corporation) is filled with 30 L of tap water at 5 ° C. and bathed with 7 cotton shirts, 2 polyester shirts, and 2 acrylic shirts. The ratio was adjusted to 20 times, and they were folded and floated on the water surface. In the center, 30 g of the sample for solubility test after long-term storage was placed, immersed in the cloth for 2 minutes, and then stirred for 5 minutes with a weak water flow. After draining, the cloth was dehydrated for 1 minute, the undissolved residue on the cloth and in the washing machine was picked up, and the undissolved amount was visually evaluated based on the following evaluation criteria.
A: Almost no undissolved residue
○: A level at which no undissolved residue is seen but is a problem
Δ: Undissolved residue is noticeable
×: Unmelted residue is noticeable
In consideration of usability at home, the detergent composition preferably has a rating of ◯ or higher.
[0128]
[Table 2]

[0129]
[Table 3]

[0130]
[Table 4]

[0131]
[Table 5]

[0132]
[Table 6]

Claims (5)

A granulated product in which the surface of a water-soluble inorganic salt core particle is coated with a salt-sensitive polymer is treated with a fine powder of salt and / or an aqueous solution that makes the salt-sensitive polymer sensitive. Coated particles. The coated particle according to claim 1, wherein the coated salt-sensitive high molecular weight is 0.1 to 10% by mass based on the total amount of the coated particle. The coated particle according to claim 1 or 2, wherein the water-soluble inorganic salt is a substance capable of having crystal water at less than 20 ° C. The coated particle according to any one of claims 1 to 3, wherein the salt-sensitive polymer is a polymer having a carboxyl group. A detergent composition comprising the coated particles according to any one of claims 1 to 4 and a surfactant.