JP2004323733A - Granular detergent product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent product the granular detergent composition of which is contained in a container composed of a box body with an opening on the top face, a sealing material to seal the opening and a free-to-open-and-shut capping which covers the opening from the outside of the sealing material, the granular detergent composition does not solidify without leaching its component and does not reduce washing power for a bulky clothing when the product is kept in an environment of high temperature and high humidity after the sealing material is opened. <P>SOLUTION: When this detergent product, in such a state where the sealing material is opened and the capping is shut, is consecutively exposed for 14 days to a shelf test process for 24 hrs consisting of a process of standing in an environment of temperature of 45°C and humidity of 85% for 16 hr and a process of standing in an environment of temperature of 25°C and humidity of 65% for 8 hr, increased mass of the granular detergent composition is 5 mass% or less based on the mass of the granular detergent composition before the sealing material is opened. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００９４】
＜洗剤「Ｃ−１」および「Ｃ−２」の製造＞
洗剤「Ｃ−１」および「Ｃ−２」を製造した。これらの組成を表２に示す。これらの組成のうち、ノニオン界面活性剤、２．０質量％の捏和時添加用のＡ型ゼオライト、３．２質量％の粉砕助剤用Ａ型ゼオライト、１．５質量％の表面被覆用のＡ型ゼオライト、酵素、色素及び香料を除いた残りの成分を水に溶解若しくは分散させて、水分を３８質量％有するスラリーを調製した。その後、このスリラーを、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質量％の噴霧乾燥粒子を得た。
この乾燥粒子と共に、２．０質量％のＡ型ゼオライト、０．５質量％の噴霧添加用のノニオン界面活性剤を除いた残りの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。
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３．２質量％添加し、冷風（１０℃、１５ｍ／ｓ）共存下で直列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：１段目／２段目／３段目いずれも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％、回転数２２ｒｐｍ、２５℃の条件で１．５質量％の微粉Ａ型ゼオライト加え、０．５質量％のノニオン界面活性剤と香料を噴霧しつつ、１分間転動し表面改質して、洗剤粒子を得た。得られた洗剤粒子にその他必要な成分（過炭酸塩、漂白活性化剤造粒物、漂白活性化触媒造粒物、酵素等）を任意に添加した。
また、得られた洗剤粒子の一部を着色するために、洗剤「Ａ−１」〜「Ａ−５」の製造と同様な方法で色素の２０％水溶液を噴霧し、洗剤「Ｃ−１」および「Ｃ−２」（平均粒径５４０μｍ、嵩密度０．８４ｇ／ｍＬ）を得た。
【００９５】
＜洗剤「Ｄ−１」および「Ｄ−２」の製造＞
洗剤「Ｄ−１」および「Ｄ−２」を製造した。これらの組成を表２に示す。以下の手順で洗剤粒子群「Ｄ−１」および「Ｄ−２」を製造した。
まず、撹拌装置を装備したジャケット付き混合槽に水を入れ、温度を５０℃に調整した。ここに硫酸ナトリウム、蛍光増白剤を添加し、１０分間撹拌した。続いて、炭酸ナトリウムを添加した後にアクリル酸系ポリマーを添加し、さらに１０分間撹拌した後、塩化ナトリウムおよび粉末Ａ型ゼオライトの一部を添加した。そして、さらに３０分間撹拌して噴霧乾燥用スラリーを調製した。
得られた噴霧乾燥用スラリーの温度は５０℃であった。このスラリーを、圧力噴霧ノズルを具備した向流式噴霧乾燥装置で噴霧乾燥を行い、揮発分（１０５℃、２時間の減量）が３質量％、嵩密度が５００ｇ／Ｌ、平均粒径が２５０μｍの噴霧乾燥粒子を得た。
これとは別に、ノニオン界面活性剤、ポリエチレングリコール、石鹸、およびアニオン界面活性剤（ＬＡＳ−Ｎａ等）を、８０℃の温度条件で混合して、水分含有量１０質量％の界面活性剤組成物を調製した。ＬＡＳ−Ｎａは水酸化ナトリウム水溶液で中和した溶液状で使用した。
そして、前記で得られた噴霧乾燥粒子を、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（充填率５０％）し、ジャケットには８０℃の温水を１０Ｌ／分の流量で流しながら、主軸（１５０ｒｐｍ）とチョッパー（４０００ｒｐｍ）の撹拌を開始した。そこに上記で調製した界面活性剤組成物を２分間かけて投入し、その後に５分間撹拌した後、層状珪酸塩（ＳＫＳ−６、平均粒径５μｍ）及び粉末Ａ型ゼオライトの一部（１０質量％）を投入して２分間撹拌することによって、洗剤粒子を得た。
得られた洗剤粒子と、粉末Ａ型ゼオライトの一部（２質量％）をＶブレンダーで混合し、その他必要な成分（過炭酸塩、漂白活性化剤造粒物、漂白活性化触媒造粒物、酵素等）を添加後、香料を噴霧した。また、洗剤粒子の一部を着色するために、洗剤「Ａ−１」〜「Ａ−５」の製造と同様な方法で色素の２０％水溶液を噴霧し、洗剤「Ｄ−１」および「Ｄ−２」（平均粒径３００μｍ、嵩密度０．７５ｇ／ｍＬ）を得た。
【００９６】
＜洗剤「Ｅ−１」の製造＞
洗剤「Ｅ−１」を製造した。この組成を表２に示す。これらの組成のうち、ノニオン界面活性剤、５．０質量％の表面被覆用のＡ型ゼオライト、層状珪酸塩、酵素、色素及び香料を除いた残りの成分を水に溶解若しくは分散させて、水分を３８質量％有するスラリーを調製した。その後、このスリラーを、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質量％の噴霧乾燥粒子を得た。
この噴霧乾燥粒子を、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（充填率５０％）し、主軸２００ｒｐｍ、チョッパー２００ｒｐｍの撹拌を開始した。撹拌開始後３０秒後にノニオン界面活性剤及び水（温度６０℃）を２分間かけて添加して、ジャケット温度３０℃の条件で撹拌造粒を平均粒径４００μｍになるまで継続した。
最後に層状珪酸塩（ＳＫＳ−６、平均粒径５μｍ）及び５．０質量％の微粉Ａ型ゼオライトを添加して１分間撹拌して表面改質し香料を噴霧して洗剤粒子を得た。この得られた洗剤粒子にその他必要な成分（過炭酸塩、漂白活性化剤造粒物、漂白活性化触媒造粒物、酵素等）を任意に添加した。
得られた洗剤粒子の一部を着色するために、洗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剤粒子層高３０ｍｍ、層幅３００ｍｍ）その表面に青色色素溶液を噴霧し、洗剤「Ｅ−１」（平均粒径４００μｍ、嵩密度０．７８ｇ／ｍＬ）を得た。
【００９７】
＜洗剤「Ｆ−１」の製造＞
洗剤「Ｆ−１」を製造した。この組成を表２に示す。これらの組成のうち、ノニオン界面活性剤、表面被覆に用いる５．０質量％のＰ型ゼオライト、色素、酵素、香料を除いた残りすべての原料（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（充填率５０％）し、主軸２００ｒｐｍ、チョッパー２００ｒｐｍの撹拌を開始した。
撹拌開始後３０秒後にノニオン界面活性剤及び水（温度６０℃）を２分間かけて添加して、ジャケット温度３０℃の条件で撹拌造粒を平均粒径４００μｍになるまで継続した。最後に５．０質量％のＰ型ゼオライトを添加して３０秒撹拌して表面改質し香料を噴霧して洗剤粒子を得た。この洗剤粒子にその他必要な成分（酵素等）を任意に添加した。
また、得られた洗剤粒子の一部を着色するために、洗剤「Ａ−１」〜「Ａ−５」の製造と同様な方法で色素の２０％水溶液を噴霧し、洗剤「Ｆ−１」（平均粒径４００μｍ、嵩密度０．８０ｇ／ｍＬ）を得た。
【００９８】
【表２】

【００９９】
ここで、表１および表２中に略称で示した成分について説明する。
・ 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のナトリウム塩（ライオン（株）製）
・ ＬＡＳ−Ｋ：直鎖アルキル（炭素数１０〜１４）ベンゼンスルホン酸（ライオン（株）製ライポンＬＨ−２００（ＬＡＳ−Ｈ純分９６％））を界面活性剤組成物製造時に４８％水酸化カリウム水溶液で中和する。表１および表２中の配合量は、ＬＡＳ−Ｋとしての質量％を示す。
・ ＬＡＳ−Ｎａ：直鎖アルキル（炭素数１０〜１４）ベンゼンスルホン酸（ライオン（株）製ライポンＬＨ−２００（ＬＡＳ−Ｈ純分９６％））を界面活性剤組成物製造時に４８％水酸化ナトリウム水溶液で中和する。表１および表２中の配合量は、ＬＡＳ−Ｎａとしての質量％を示す。
・ ＡＯＳ−Ｋ：炭素数１４〜１８のアルキル基をもつα−オレフィンスルホン酸カリウム（ライオン（株）製）
・ ＡＯＳ−Ｎａ：炭素数１４〜１８のアルキル基をもつα−オレフィンスルホン酸カリウム（ライオン（株）製）
・ ＡＳ−Ｎａ：炭素数１０〜１８のアルキル基を持つアルキル硫酸ナトリウム塩（三洋化成工業（株）製 サンデットＬＮＭ）
・ 石鹸：炭素数１２〜１８の脂肪酸ナトリウム（ライオン（株）製、純分：６７％、タイター：４０〜４５℃、脂肪酸組成：Ｃ_１２：１１．７％、Ｃ_１４：０．４％、Ｃ_１６：２９．２％、Ｃ_１８０（ステアリン）：０．７％、Ｃ_１８１（オレイン）：５６．８％、Ｃ_１８２（リノール）：１．２％、分子量：２８９）
・ ノニオン界面活性剤Ａ：ＥＣＯＲＯＬ２６（ＥＣＯＧＲＥＥＮ社製）の酸化エチレン１５モル付加体（ライオン（株）製）
・ ノニオン界面活性剤Ｂ：ＥＣＯＲＯＬ２６（ＥＣＯＧＲＥＥＮ社製）の酸化エチレン７モル付加体（ライオン（株）製）
・ ＰＥＧ６０００：ポリエチレングリコール（ライオン（株）製、ＰＥＧ＃６０００Ｍ）
・ 蛍光増白剤Ａ：チノパールＣＢＳ−Ｘ（チバ・スペシャルティ・ケミカルズ）
・ 蛍光増白剤Ｂ：チノパールＡＭＳ−ＧＸ（チバ・スペシャルティ・ケミカルズ）
・ 珪酸ナトリウム：ＪＩＳ１号珪酸ナトリウム（日本化学（株）製）
・ 硫酸ナトリウム：中性無水芒硝（四国化成工業（株）製）
・ 塩化ナトリウム：日精のやき塩Ｃ（日本製塩（株）製）
・ 炭酸カリウム：炭酸カリウム（旭硝子（株）製）
・ ゼオライトＡ：Ａ型ゼオライト （水澤化学（株）製）
・ ゼオライトＢ：Ｐ型ゼオライト（ＩＮＥＯＳ Ｓｉｌｉｃａｓ社製、Ｄｏｕｃｉｌ Ａ２４）
・ 層状珪酸塩：結晶性層状ケイ酸ナトリウム （クラリアントトクヤマ社製、ＳＫＳ−６）
・ アクリル酸系ポリマーＡ：アクリル酸／マレイン酸共重合体のナトリウム塩、商品名ソカランＣＰ７（ＢＡＳＦ）
・ アクリル酸系ポリマーＢ：ポリアクリル酸ナトリウム、商品名ソカランＰＡ３０（ＢＡＳＦ）
・ 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）
・ 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）
・ 過炭酸塩Ａ：被覆化過炭酸ナトリウム（三菱瓦斯化学（株）製、ＳＰＣ−Ｄ）、過炭酸ナトリウム含量約８５質量％、平均粒径７６０μｍ
・ 漂白活性化剤造粒物Ａ：特願２００２−３７８４０９号公報、表１〜２に示す漂白活性化剤造粒物Ａ
・ 漂白活性化剤造粒物Ｂ：特願２００２−３７８４０９号公報、表１〜２に示す漂白活性化剤造粒物Ｂ
・ 漂白活性化剤造粒物Ｃ：特願２００２−３７８４０９号公報、表１〜２に示す漂白活性化剤造粒物Ｃ
・ 漂白活性化触媒造粒物Ａ：特願２００２−２５０７３４号公報、表９に示す造粒物４
・ 酵素Ａ：エバラーゼ８Ｔ（ノボザイムズ製）／ＬＩＰＥＸ５０Ｔ（ノボザイムズ製）／ターマミル６０Ｔ（ノボザイムズ製）／セルザイム０．７Ｔ（ノボザイムズ製）＝５／２／１／２（質量比）の混合物
・ 酵素Ｂ：カンナーゼ１２Ｔ（ノボザイムズ製）／ＬＩＰＥＸ５０Ｔ（ノボザイムズ製）／ターマミル６０Ｔ（ノボザイムズ製）／セルザイム０．７Ｔ（ノボザイムズ製）＝５／２／１／２（質量比）の混合物
・ 香料Ａ：特開２００２−１４６３９９号公報、表１１〜１８に示す香料組成物Ａ
・ 香料Ｂ：特開２００２−１４６３９９号公報、表１１〜１８に示す香料組成物Ｂ
・ 香料Ｃ：特開２００２−１４６３９９号公報、表１１〜１８に示す香料組成物Ｃ
・ 香料Ｄ：特開２００２−１４６３９９号公報、表１１〜１８に示す香料組成物Ｄ
・ 色素Ａ：群青（大日精化工業製、Ｕｌｔｒａｍａｒｉｎｅ Ｂｌｕｅ）
・ 色素Ｂ：Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ ７（大日精化工業製）
・ 炭酸ナトリウム：重質炭酸ナトリウム（旭硝子（株）製、ソーダ灰）
【０１００】
＜洗剤組成物の質量増加測定＞
つぎに、これらの洗剤を容器Ａ〜容器Ｅにそれぞれ充填し、製品とした（実施例１〜実施例１５、比較例１および比較例２）。これらの蓋部を一度開封して、インナーシール等の封緘材を開封除去した後に、蓋部を再度閉じた。そして、温度４５℃で湿度８５％の環境下に１６時間、温度２５℃で湿度６５％の環境下に８時間放置する２４時間放置工程を１４日間継続した。その後、洗剤組成物の質量を測定し、封緘材開封前の洗剤組成物の質量に対しての質量増加を求めた。結果を表３および表４に示す。
ここで、
・ 容器Ａ：図１に示した容器（コハゼ掛けの係合部あり・箱本体にヒンジ片あり）
・ 容器Ｂ：図３に示した容器（コハゼ掛けの係合部あり・蓋にヒンジ板あり）
・ 容器Ｃ：図４に示した容器（コハゼ掛けの係合部なし・箱本体にヒンジ片あり）
・ 容器Ｄ：図５に示した容器（コハゼ掛けの係合部なし・蓋にヒンジ板あり）
・ 容器Ｅ：特開平０９−２７８０３０号公報の図−１に示す容器
・ 洗剤Ｇ−１：特開２００２−０１２９００号公報の表１記載の実施例２の洗剤
・ ＬＡＳ量：直鎖アルキルベンゼンスルホン酸塩の質量％
・ ノニオン量：ノニオン界面活性剤の質量％
・ 微粉量：１００μｍ以下の微分の量（質量％）
をそれぞれ表す。
【０１０１】
＜固化性試験（スプーンでの取り出し易さ）＞
製造した各粒状洗剤組成物１０００ｇを、前記の容器Ａ〜容器Ｅに充填し、前記２４時間放置工程を１４日間継続した。その後、蓋部を開き、洗剤用スプーンにて洗剤をすくうときの抵抗感を、２０〜４０代の女性１０人により判断し、以下の基準に基づいて採点した。
◎：「スプーンで抵抗なくすくえた」と答えた人が１０人中１０人
○：「スプーンで抵抗なくすくえた」と答えた人が１０人中６〜９人
△：「スプーンで抵抗なくすくえた」と答えた人が１０人中１〜５人
×：「スプーンで抵抗なくすくえた」と答えた人が１０人中０人
結果を表３および表４に示す。
【０１０２】
＜しみだし試験＞
製造した各洗剤組成物１０００ｇを前記の容器Ａ〜容器Ｅに充填し、前記２４時間放置工程を１４日間継続した。その後、洗剤組成物を取り出してから容器内壁を２０〜４０代の女性１０人により目視にて判断し、以下の基準に基づいて採点した。
◎：「しみだしを不快に感じる」と答えた人が１０人中０人
○：「しみだしを不快に感じる」と答えた人が１０人中１〜５人
△：「しみだしを不快に感じる」と答えた人が１０人中６〜９人
×：「しみだしを不快に感じる」と答えた人が１０人中１０人
結果を表３および表４に示す。
【０１０３】
＜洗浄力の評価＞
１． 汚染布の調整
洗浄力を評価するため、特開２００１−６４６９４号公報の実施例の記載に従い、人工汚垢布を調整した。
２． 洗浄方法
試験布１０枚を一組として、フリース衣料１枚に縫い付け、さらにフリース衣類１枚、綿長袖シャツ１４枚、アクリルジャージ長袖シャツ７枚（合計３．５ｋｇ）を全自動洗濯機（ＭＡＷ−Ｖ８ＱＰ、三菱電機（株）製）に入れた。その上に、前記２４時間放置工程を１４日間継続した各洗剤をスプーンですくって衣類上に振りかけ、１５℃の水道水を注水して通常コースにて洗浄を行った。
３． 評価方法
特開２００１−６４６９４号公報の実施例の記載に従い、洗浄率を求め、以下の基準で評価した。
◎：洗浄率９０％以上
○：洗浄率７５％以上９０％未満
△：洗浄率６０％以上７５％未満
×：洗浄率６０％未満
結果を表３および表４に示す。
【０１０４】
【表３】

【０１０５】
【表４】

【０１０６】
その結果、洗剤組成物の質量増加が５質量％以下の洗剤は良好な品質であった。また、質量増加が４質量％以下のものはより洗浄率が向上し、３質量％以下のものはさらに洗浄率が向上し、大変良好な品質であった。
【０１０７】
【発明の効果】
以上、詳細に説明したように、本発明の洗剤製品は、封緘材を開封した後、製品を高温高湿度な環境下に放置しても、粒状洗剤組成物の固化や成分のしみ出しが生じず、嵩張る衣類の洗浄力が低下しないものである。
【図面の簡単な説明】
【図１】第１の実施形態に係る容器Ａの分解斜視図である。
【図２】第１の実施形態に係る容器Ａのヒンジ機構部分の拡大断面図である。
【図３】第２の実施形態に係る容器Ｂの分解斜視図である。
【図４】第３の実施形態に係る容器Ｃの分解斜視図である。
【図５】第４の実施形態に係る容器Ｄの分解斜視図である。
【符号の説明】
１ 箱本体
１Ａ 正面板
１Ｂ 背面板
２ 上面開口部
３ 蓋部
３Ａ 天面板
３Ｂ 前板
３Ｃ 側板
３Ｄ、３Ｅ 後板
４Ａ 正面フラップ
４Ｂ 背面フラップ
５ 係合穴
５Ａ 係合穴の上縁部
７ 折り罫線
８ 表半切り線
１１、３１ つまみ片
１２ 係合片
１３ 切断線
１４ 折り罫線
１５ ヒンジ片
１６ 切断線
１７、２７ 折り罫線
１８ 突片
１９ 切断線
２０ ヒンジ板
２８ 接合部[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a granular detergent composition comprising a box body having an opening on an upper surface, a sealing material for sealing the opening, and an openable / closable lid for covering the opening from outside the sealing material. The present invention relates to a detergent product stored in a container to be cleaned.
[0002]
[Prior art]
Since the high bulk density granular detergent composition has a high surfactant content and a high bulk density, it has a problem in that when it is stored in a closed manner in a paper container or the like for a long period of time, it solidifies due to moisture absorption.
[0003]
There is also a problem that moisture and liquid components held in the detergent composition move to the surface of the particles and exude to the outside of the container. The exudation not only impairs the appearance of the detergent product, but also causes a problem of contaminating the floor on which the container is placed. When such a moisture-absorbed and solidified detergent is used, there is a problem that the detergency decreases.
[0004]
In order to improve this seepage, for example, it has been proposed to store the granular detergent composition in a composite material container integrally formed from a plastic molded body and a paper sheet (see Patent Document 1). .
[0005]
Alternatively, a granular detergent composition that prevents oozing and solidification by combining a specific nonionic surfactant with a specific alkali metal salt of a linear alkylbenzene sulfonic acid has also been proposed (see Patent Document 2).
[0006]
[Patent Document 1]
Japanese Patent No. 2542521
[Patent Document 2]
JP-A-2002-12900
[0007]
[Problems to be solved by the invention]
However, even if these proposals are used, exudation and solidification cannot be prevented after the lid for covering the opening of the container box body is opened to use the detergent. In addition, when fleece clothes are washed using these detergents, there is a problem that the washing power is reduced. For example, in the case of a fully automatic washing machine that detects the mass of clothes and sets the water level, in light and bulky clothes such as fleece clothing, the water level in the washing machine is near the upper surface of the clothes, and the granular detergent is difficult to dissolve. In addition, in the case of products that have been open for a long time since the lid covering the opening of the container box body is opened, the detergent is not solidified, but the particles are coagulated, and the detergent particles are sufficiently dissolved in the washing machine. Because it does not.
[0008]
The present invention has been made in view of the problems of the prior art described above, after opening the sealing material, even if the product is left in a high-temperature and high-humidity environment, solidification of the granular detergent composition and exudation of components do not occur, An object of the present invention is to provide a detergent product that does not reduce the detergency of bulky clothing.
[0009]
[Means for Solving the Problems]
The present invention provides a granular detergent composition comprising a box body having an opening on an upper surface, a sealing material for sealing the opening, and an openable / closable lid for covering the opening from outside the sealing material. In the detergent product stored in the container to be opened, the sealing material is opened, the lid is closed, and the temperature is 45 ° C. and the humidity is 85% for 16 hours, and the temperature is 25 ° C. and the humidity is 65%. When the 24-hour standing step of leaving for 8 hours in the environment is continued for 14 days, the increase in the mass of the granular detergent composition is 5% by mass or less based on the mass of the granular detergent composition before opening the sealing material. A detergent product characterized by the following.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
The detergent product of the present invention comprises a granular detergent composition and a container containing the composition. First, the granular detergent composition will be described.
[0011]
The granular detergent composition of the detergent product of the present invention is obtained by opening a sealing material such as an inner seal that seals the opening of the container box body, and then closing the lid to obtain an environment having a temperature of 45 ° C. and a humidity of 85%. When the 24-hour leaving process of leaving the container for 16 hours under an environment of a temperature of 25 ° C. and a humidity of 65% for 8 hours is continued for 14 days, the increase in the mass of the granular detergent composition increases the granular detergent composition before opening the sealing material. 5% by mass or less based on the mass of
[0012]
Such a mass increase is preferably at most 4% by mass, more preferably at most 3% by mass. If the mass increase is more than 5% by mass, the detergent particles condense and hardly dissolve in the washing machine, so that the detergency decreases.
[0013]
Specifically, the amount of the linear alkylbenzene sulfonate (LAS) in the detergent particles is set to 20% by mass or less, the amount of the nonionic surfactant is set to 2% by mass or more, and the amount of fine powder having a particle size of 100 μm or less is set to 4% by mass. % Or less, low hygroscopic detergent particles whose mass increase is 5% by mass or less can be obtained.
[0014]
This is considered to be because the nonionic surfactant in the detergent particles functions to suppress the property that the linear alkylbenzene sulfonate (LAS) easily absorbs water due to retention of bound water. Further, it is considered that when there are many fine powder particles having a particle size of 100 μm or less, the surface area of the particles increases and the amount of moisture absorbed by the detergent increases.
[0015]
<Components of detergent composition>
The components of the granular detergent composition have surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and have a capability of capturing a hardness component in a washing solution and an alkali ability. Oil-absorbing carriers for supporting liquid components such as various inorganic and organic builders and nonionic surfactants, granulation aids such as clay minerals, enzymes such as protease, lipase, cellulase and amylase, sodium percarbonate and perboric acid A bleaching agent (inorganic peroxide) such as soda, a bleaching activator, a bleaching activation catalyst, a fluorescent agent, a fragrance or other components are included.
[0016]
(Anionic surfactant)
Examples of the anionic surfactant contained in the granular detergent composition include the following.
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) An alkane sulfonate having 10 to 20 carbon atoms.
(3) α-olefin sulfonate having 10 to 20 carbon atoms (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) Either ethylene oxide, propylene oxide or butylene oxide having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average mole number of 0.5 to 10 mol alone or ethylene oxide / Propylene oxide = alkyl ether sulfate or alkenyl ether sulfate (AES) mixed and added at a mass ratio of 0.1 / 9.9 to 9.9 / 0.1.
(6) Either ethylene oxide, propylene oxide or butylene oxide having a straight-chain or branched-chain alkylphenyl or alkenylphenyl group having 10 to 20 carbon atoms and having an average mole number of 3 to 30 moles alone or ethylene oxide / Propylene oxide = alkyl phenyl ether sulfate or alkenyl phenyl ether sulfate mixed and added at a mass ratio of 0.1 / 9.9 to 9.9 / 0.1.
(7) Either ethylene oxide, propylene oxide or butylene oxide having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average mole number of 0.5 to 10 mol alone or ethylene oxide / Propylene oxide = alkyl ether carboxylate or alkenyl ether carboxylate mixed and added at a mass ratio of 0.1 / 9.9 to 9.9 / 0.1.
(8) An alkyl polyhydric alcohol ether sulfate such as an alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(9) A saturated or unsaturated α-sulfofatty acid salt having 8 to 20 carbon atoms or a methyl, ethyl or propyl ester thereof (α-SF or MES).
(10) Long-chain monoalkyl, dialkyl or sesquialkyl phosphates.
(11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphates.
(12) Higher fatty acid salts having 10 to 20 carbon atoms (soap).
[0017]
These anionic surfactants can be used as an alkali metal salt such as sodium or potassium, an amine salt or an ammonium salt. These anionic surfactants may be used alone or in combination of two or more.
[0018]
Among them, preferred anionic surfactants include alkali metal salts of linear alkylbenzene sulfonic acid (LAS) (eg, sodium or potassium salts), α-olefin sulfonates (AOS), and α-sulfo fatty acid salts (α -SF), an alkali metal salt of alkenyl ether sulfate (AES) (eg, sodium or potassium salt) or an alkali metal salt of higher fatty acid (eg, sodium or potassium salt). Among them, α-sulfofatty acid salt (α-SF) or soap is more preferably used as the main surfactant. The content of these anionic surfactants is preferably 1 to 30% by mass, more preferably 1 to 20% by mass in the detergent particles.
[0019]
(Nonionic surfactant)
Examples of the nonionic surfactant contained in the granular detergent composition include the following.
(1) A polyoxyalkylene alkyl (or alkenyl) ether obtained by adding an alkyl alcohol having 2 to 4 carbon atoms having an average mole number of 3 to 30 moles to an aliphatic alcohol having 6 to 22 carbon atoms. Among them, preferred aliphatic alcohols have 8 to 18 carbon atoms. The preferred average number of moles of the alkylene oxide is 4 to 20 moles, more preferably 5 to 17 moles.
[0020]
Among these compounds, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. In addition, as the type of the aliphatic alcohol, a primary alcohol or a secondary alcohol is preferable, and a primary alcohol is more preferable. Further, the alkyl group of the aliphatic alcohol may have a branched chain.
[0021]
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) Fatty acid alkyl ester alkoxylates represented by the following general formula (I) in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
[0022]
R₁CO (OA)_nOR₂  … (I)
Where R₁  CO: a fatty acid residue having 6 to 22 carbon atoms, among which preferably those having 8 to 18 carbon atoms,
OA: an additional unit of an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, among which preferably those having 2 to 3 carbon atoms;
n: the average number of moles of alkylene oxide added, generally 3 to 30 mol, preferably 5 to 20 mol,
R₂  : Represents a lower alkyl group having a substituent having 1 to 3 carbon atoms.
[0023]
(4) Polyoxyethylene sorbitan fatty acid esters.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid esters.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.
(9) fatty acid alkanolamides.
(10) Polyoxyethylene alkylamine.
(11) alkyl glycosides.
(12) Alkylamine oxide.
[0024]
Among the above nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ethers having a melting point of 40 ° C. or less and a hydrophilic / lipophilic balance value (HLB) of 9 to 16, and polyoxyethylene polyoxypropylene alkyl (or Preferred are alkenyl) ethers, fatty acid methyl ester ethoxylates obtained by adding ethylene oxide to fatty acid methyl esters, and fatty acid methyl ester ethoxypropoxylates obtained by adding ethylene oxide and propylene oxide to fatty acid methyl esters. These nonionic surfactants may be used alone or in combination of two or more. The content of these nonionic surfactants is preferably 2 to 30% by mass in the detergent particles, and more preferably 2 to 20% by mass.
[0025]
(Cationic surfactant)
Examples of the cationic surfactant contained in the granular detergent composition include the following.
(1) Di long chain alkyl di short chain alkyl type quaternary ammonium salt.
[R₁R₂  R₃  R₄  N]⁺・ X⁻
Where R₁And R₂: An alkyl group having 12 to 26 carbon atoms, among which an alkyl group having preferably 14 to 18 carbon atoms;
R₃  And R₄  : An alkyl group or a benzyl group having 1 to 4 carbon atoms, among which a group having 1 to 2 carbon atoms or a hydroxyalkyl group or a polyoxyalkylene group having 2 to 4 carbon atoms, and particularly preferably a carbon group Those with a few numbers,
X: halogen, CH₃SO₄, C₂H₅SO₄, 1 / 2SO₄, OH, HSO₄, CH₃CO₂Or CH₃-C₆H₄-SO₃Are respectively shown.
[0026]
Such di-long-chain alkyl di-short-chain alkyl type quaternary ammonium salts include, for example, distearyl dimethyl ammonium salt, di-hydrogenated tallow alkyl dimethyl ammonium salt, di-hydrogenated tallow alkyl benzene methyl ammonium salt, distearyl methyl benzyl ammonium salt , Distearylmethylhydroxyethylammonium salt, distearylmethylhydroxypropylammonium salt, distearyldihydroxyethylammonium salt, dioleyldimethylammonium salt or dicoconut alkyldimethylammonium salt. Examples of the halogen represented by X include a chlorine atom and a bromine atom.
[0027]
(2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salts.
[R₁  R₂  R₃  R₄  N]⁺・ X⁻
Where R₁: An alkyl group having 12 to 26 carbon atoms, among which an alkyl group having preferably 14 to 18 carbon atoms;
R₂  , R₃  And R₄: An alkyl group or a benzyl group having 1 to 4 carbon atoms, among which a group having 1 to 2 carbon atoms or a hydroxyalkyl group or a polyoxyalkylene group having 2 to 4 carbon atoms, and particularly preferably a carbon group Those with a few numbers,
X: halogen, CH₃SO₄, C₂H₅SO₄, 1 / 2SO₄, OH, HSO₄, CH₃CO₂Or CH₃-C₆H₄-SO₃Are respectively shown.
[0028]
Examples of such a mono-long-chain alkyltri-short-chain alkyl type quaternary ammonium salt include lauryltrimethylammonium salt, stearyltrimethylammonium salt, hydrogenated tallow alkyltrimethylammonium salt, hydrogenated tallowalkylbenzenebenzene ammonium salt, stearyldimethylbenzyl Ammonium salt, stearyldimethylhydroxyethylammonium salt, stearyldimethylhydroxypropylammonium salt, stearyltrihydroxyethylammonium salt, oleyltrimethylammonium salt or coconut alkyltrimethylammonium salt. Examples of the halogen represented by X include a chlorine atom and a bromine atom.
[0029]
(3) Tetra short chain alkyl type quaternary ammonium salts.
[R₁  R₂  R₃  R₄  N]⁺・ X⁻
Where R₁  , R₂  , R₃  And R₄: An alkyl group or benzyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, or a hydroxyalkyl group or polyoxyalkylene group having 2 to 4 carbon atoms, and particularly preferably carbon Those with a few numbers,
X: halogen, CH₃SO₄, C₂H₅SO₄, 1 / 2SO₄, OH, HSO₄, CH₃CO₂Or CH₃-C₆H₄-SO₃Are respectively shown.
[0030]
Examples of such tetra-short-chain alkyl type quaternary ammonium salts include, for example, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydroxide, tetrabutylammonium hydrogensulfate, benzyltrimethylammonium chloride, benzyltrimethyl Examples include ammonium hydroxide, benzyltriethylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium chloride, and trimethylphenylammonium chloride. Examples of the halogen represented by X include a chlorine atom and a bromine atom.
[0031]
(4) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salts.
[R₁  R₂  R₃  R₄  N]⁺・ X⁻
Where R₁  , R₂  And R₃: An alkyl group having 12 to 26 carbon atoms, among which an alkyl group having preferably 14 to 18 carbon atoms;
R₄  : An alkyl group or a benzyl group having 1 to 4 carbon atoms, among which a group having 1 to 2 carbon atoms or a hydroxyalkyl group or a polyoxyalkylene group having 2 to 4 carbon atoms, and particularly preferably a carbon group Those having a number of 2 to 3, X: halogen, CH₃SO₄, C₂H₅SO₄, 1 / 2SO₄, OH, HSO₄, CH₃CO₂Or CH₃-C₆H₄-SO₃Are respectively shown.
[0032]
Examples of such a tri-long-chain alkyl mono-short-chain alkyl type quaternary ammonium salt include trilaurylmethylammonium chloride, tristearylmethylammonium chloride, trioleylmethylammonium chloride, and tricoconut alkylmethylammonium chloride. Examples of the halogen represented by X include a chlorine atom and a bromine atom.
These cationic surfactants may be used alone or as a mixture of several kinds.
[0033]
(Amphoteric surfactant)
Examples of the amphoteric surfactant contained in the granular detergent composition include the following.
(1) Betaines
For example, amidopropyl betaine laurate, amidoethyl betaine stearate, carbobetaine or sulfobetaine and the like.
(2) imidazoline derivatives
For example, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine or N-coconut fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium.
(3) Phosphate type
For example, lecithin (phosphatidyl) choline and the like can be mentioned.
[0034]
These amphoteric surfactants may be used alone or in combination of two or more. These anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants may be used alone or in combination of two or more. In addition, this invention is not limited to the kind of said surfactant.
[0035]
(Inorganic builder)
Examples of the inorganic builder contained in the granular detergent composition include the following.
For example, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate or sodium sesquicarbonate; alkali metal sulfites such as sodium sulfite or potassium sulfite; sodium silicate; crystalline layered sodium silicate or amorphous layered sodium silicate; Alkali metal silicate, sulfate such as sodium sulfate or potassium sulfate, alkali metal chloride such as sodium chloride or potassium chloride or orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate or phytic acid And phosphates such as salts.
[0036]
others,
1) General formula: x₁(M₂O) · Al₂O₂・ Y₁(SiO₂) ・ W₁(H₂O) (wherein, M: an alkali metal atom such as sodium or potassium,
x₁, Y₁And w₁: Indicates the number of moles of each component, and generally, x₁Is a number from 0.7 to 1.5, y₁Is a number from 0.8 to 6, w₁Indicates an arbitrary positive number. ) Crystalline aluminosilicate represented by
2) General formula: x₂(M₂O) · Al₂O₃・ Y₂(SiO₂) ・ W₂(H₂O) (wherein, M: an alkali metal atom such as sodium or potassium,
x₂, Y₂And w₂: Indicates the number of moles of each component, and generally, x₂Is a number from 0.7 to 1.2, y₂Is a number from 1.6 to 2.8, w₂Represents 0 or any positive number. ) Amorphous aluminosilicate represented by
3) General formula: x₃(M₂O) · Al₂O₃・ Y₃(SiO₂) .Z₃(P₂0₅) ・ W₃(H₂O)
(Wherein, M: an alkali metal atom such as sodium or potassium,
x₃, Y₃, Z₃And w₃: Indicates the number of moles of each component, and generally, x₃Is a number from 0.2 to 1.1, y₃Is a number from 0.2 to 4.0, z₃Is the number from 0.001 to 0.8, w₃Represents 0 or any positive number. Amorphous aluminosilicate represented by)
And the like.
[0037]
Among these inorganic builders, sodium carbonate, potassium carbonate, sodium silicate and sodium aluminosilicate are preferred. Among them, as the aluminosilicate, either crystalline or amorphous (amorphous) can be used, but crystalline aluminosilicate is more preferable from the viewpoint of cation exchange ability. Examples of such a crystalline aluminosilicate include A-type, X-type, and P-type zeolites, and the average primary particle diameter is preferably 0.1 to 10 μm. Further, the content of the crystalline aluminosilicate is preferably 0.1 to 40% by mass of the detergent composition, more preferably 1 to 30% by mass.
[0038]
Among the other inorganic builders, as the alkali metal silicate, either crystalline or amorphous one can be used, but crystalline one is preferable from the viewpoint of having cation exchange ability. Further, in the alkali metal silicate, SiO 2₂/ M₂The upper limit of the ratio of O (where M represents an alkali metal) is preferably 2.6 or less, more preferably 2.4 or less, and 2.2 or less from the viewpoint of alkalinity. More preferably, Further, from the viewpoint of storage stability, the lower limit is preferably 0.5 or more, more preferably 1.0 or more, further preferably 1.5 or more, and more preferably 1.7 or more. Is particularly preferred.
[0039]
Alternatively, as the amorphous alkali metal silicate, for example, JIS No. 1 or No. 2 sodium silicate, or Britesil C20, Britesil H20, Britesil C24 or Britesil H24 (granules of dried water glass) (both are registered trademarks, The PQ Corporation). Another example is NABION 15 (registered trademark, manufactured by Rhodia), which is a complex of sodium carbonate and an amorphous alkali metal salt.
[0040]
Such an alkali metal silicate has excellent alkali ability by crystallization and cation exchange ability comparable to 4A type zeolite. Also, from the viewpoint of low-temperature dispersibility, it is very preferable as a base. Here, such a crystalline alkali metal silicate is represented by the following formula (I) and / or formula (II).
[0041]
x (M₂O) ・ y (SiO₂) .Z (Me_mO_n) ・ W (H₂O) (I)
Here, M: an element of Group Ia of the periodic table (preferably K and / or Na),
Me: at least one element (preferably Mg and / or Ca) selected from the group IIa element, group IIb element, group IIIa element, group IVa element or group VIII element of the periodic table;
x, y, z, w, n: positive numbers, y / x = 0.5 to 2.6, z / x = 0.001 to 1.0, w = 0 to 20, n / m = Each number represents 0.5 to 2.0.
[0042]
M₂Ox '(SiO₂) · Y '(H₂O) (II)
Here, M: an alkali metal element (preferably K and / or Na),
x ', y': Positive numbers, each of which represents x '= 1.5 to 2.6 and y' = 0 to 20 (preferably 0).
[0043]
It is preferred that one or more crystalline alkali metal silicates represented by the formula (I) and / or the formula (II) are contained in the detergent composition. The content is preferably 0.5 to 40% by mass, more preferably 1 to 25% by mass, further preferably 3 to 20% by mass, particularly preferably 5 to 15% by mass. Among them, the amount of the crystalline alkali metal silicate contained in the salt is preferably at least 20% by mass, more preferably at least 30% by mass, further preferably at least 40% by mass. preferable. These crystalline alkali metal silicates are available, for example, from Clariant Japan, under the trade name “Na-SKS-6” (δ-Na₂O.2SiO₂) Can be obtained in powder and / or granular form.
[0044]
Among the other inorganic builders mentioned above, potassium salts such as potassium carbonate or potassium sulfate, and metal chlorides such as potassium chloride or sodium chloride are also provided as those having the effect of improving solubility. Of these, alkali metal chlorides such as potassium carbonate, potassium chloride and sodium chloride are preferred from the viewpoint of the balance between the effect of improving solubility and the cost.
[0045]
The content of such potassium carbonate is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, and more preferably 5 to 10% by mass in the detergent particles from the viewpoint of the solubility improving effect. More preferably, Further, the content of the alkali metal chloride is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and more preferably 3 to 7% by mass in the detergent particles from the viewpoint of the solubility improving effect. % Is more preferable.
[0046]
(Organic builder)
Examples of the organic builder contained in the granular detergent composition include the following.
For example, aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, iminodisuccinate and the like, serine diacetate, hydroxyiminodisuccinate Hydroxyaminocarboxylates such as salts, hydroxyethylethylenediamine triacetate, and dihydroxyethylglycine; hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, and gluconate; pyromellitic acid; Cyclocarboxylates such as polycarboxylates and cyclopentanetetracarboxylates; ether carboxylate salts such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; Polyacetal carboxylate such as sulfonic acid, acrylic acid-allyl alcohol copolymer, acrylic acid-maleic acid copolymer, polyglyoxylic acid, hydroxyacrylic acid polymer, acrylic acid polymer such as polysaccharide-acrylic acid copolymer, etc. Copolymers and copolymers, polymers or copolymers of maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid, etc .; starches, celluloses, amylose, pectin, etc. Examples include polysaccharides such as saccharide oxides and carboxymethyl cellulose, and non-dissociated polymer compounds such as polyethylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone.
[0047]
Among these organic builders, citrates, aminocarboxylates, polyacrylates and acrylic acid-maleic acid copolymers are preferred. Among them, hydroxyiminodisuccinate, a salt of an acrylic acid-maleic acid copolymer having a molecular weight of 1,000 to 80,000, and a polyacrylate are more preferred. Further, a polyacetal carboxylate such as polyglyoxylic acid having a molecular weight of 800 to 1,000,000 described in JP-A-54-52196 is also preferable, and the polyacetal carboxylate having a molecular weight of 5,000 to 200,000 is more preferable. preferable.
[0048]
Such an organic builder is highly effective when used in combination with an aluminosilicate such as zeolite from the viewpoint of detergency. The content of the organic builder in the detergent composition is preferably 0.5 to 12% by mass, more preferably 1 to 10% by mass, still more preferably 1 to 7% by mass. It is particularly preferred that the content be 5 to 5% by mass.
[0049]
The inorganic and organic builders may be used alone or in combination of two or more. The amount of the inorganic and organic builders in the detergent composition is preferably from 10 to 80% by mass, and more preferably from 20 to 70% by mass, in order to provide sufficient detergency.
[0050]
(Oil absorbing carrier)
Examples of the oil-absorbing carrier contained in the granular detergent composition include the following.
For example, a substance having an oil absorption of 80 mL / 100 g or more as expressed by the JIS-K5101 test method is preferable, and a substance having an oil absorption of 150 to 600 mL / 100 g is more preferable.
[0051]
As such an oil-absorbing carrier, for example, as a silicate compound, Tokusil N [manufactured by Tokuyama Corporation, oil absorption amount 280 mL / 100 g], Nipsil NS-K [manufactured by Nippon Silica Co., oil absorption amount 320 mL / 100 g] And amorphous silica such as Silicia # 310 (manufactured by Fuji Silysia Chemical Ltd., oil absorption 340 mL / 100 g) and Sildex H-52 (manufactured by Asahi Glass Co., Ltd., oil absorption 260 mL / 100 g). Spherical porous hydrous amorphous silicic acid, amorphous anhydrous amorphous silicic acid such as Aerosil # 300 (manufactured by Nippon Aerosil Co., Ltd., oil absorption amount 350 mL / 100 g), and Fluolite R [manufactured by Tokuyama Corporation, oil absorption Petal-like hydrated amorphous calcium silicate, such as 600 mL / 100 g], and zonotlite (oil absorption 220 mL / 100 g, manufactured by Ube Chemical Co., Ltd.). And Jo hydrated amorphous calcium silicate, amorphous aluminosilicates [Mizusawa Chemical Co., Ltd., oil absorption 170 mL / 100 g] and, like magnesium silicate [oil absorption of 180 mL / 100 g].
[0052]
Examples of other oil-absorbing carriers include, as carbonate compounds, magnesium carbonate (manufactured by Tokuyama Corporation, oil absorption amount 150 mL / 100 g) and calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., oil absorption amount 110 mL / 100 g). And other compounds such as ultrafine spinel (manufactured by Sumitomo Cement Co., Ltd., oil absorption 600 mL / 100 g), ultrafine cordierite (manufactured by Sumitomo Cement Co., oil absorption 600 mL / 100 g), ultrafine mullite Sumitomo Cement Co., Ltd., oil absorption 560 mL / 100 g], and processed starch Pineflow-S [Matsuya Chemical Co., Ltd., oil absorption 130 mL / 100 g], and the like.
[0053]
These oil absorbing carriers may be used alone or as a mixture. The content of the oil-absorbing carrier in the detergent composition is preferably from 0.1 to 25% by mass, more preferably from 0.5 to 20% by mass, based on the mass of the granular detergent. More preferably, the content is 15% by mass.
[0054]
(Granulation aids such as clay minerals)
The following may be mentioned as granulating aids such as clay minerals contained in the granular detergent composition.
As the clay mineral, for example, those belonging to the smectite group and having a crystal structure of a three-layered dioctahedral structure or a three-layered trioctahedral structure are preferable. As the clay mineral that can be used as the detergent component of the present invention, a substance having an oil absorption of less than 80 mL / 100 g is preferable, and a substance having an oil absorption of 30 to 70 mL / 100 g is more preferable. In addition, a substance having a bulk density of 0.1 g / mL or more is preferable, and a substance having a bulk density of 0.2 to 1.5 g / mL is more preferable.
[0055]
As specific examples of such clay minerals, for example, clay minerals having a dioctahedral type three-layer structure include montmorillonite (oil absorption: 50 mL / 100 g, bulk density: 0.3 g / mL), nontronite (oil absorption: 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) / ML) and the like.
[0056]
On the other hand, clay minerals having a trioctahedral type three-layer structure include saponite (oil absorption: 73 mL / 100 g, bulk density: 0.15 g / mL), hectorite (oil absorption: 72 mL / 100 g, bulk density: 0). 0.7 g / mL), stevensite (oil absorption: 30 mL / 100 g, bulk density 1.2 g / mL), talc (oil absorption: 70 mL / 100 g, bulk density: 0.1 g / mL) and the like.
[0057]
These clay minerals may be used alone or as a mixture. The content of the clay mineral in the detergent composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and more preferably 1 to 10% by mass, based on the mass of the detergent granules. More preferably, it is set to be% by mass.
[0058]
(enzyme)
Examples of the enzyme contained in the granular detergent composition include protease, lipase, cellulase, amylase and the like. These enzymes may be used alone or as a mixture. The content of the enzyme in the detergent composition is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and more preferably 0.2 to 3% by mass, based on the mass of the detergent granules. More preferably, the content is 2% by mass.
[0059]
(bleach)
The bleaching agent contained in the granular detergent composition includes, for example, percarbonate or perborate as the inorganic peroxide among the bleaching agents. Examples of the bleaching agent used in the zeolite-containing detergent include sodium percarbonate coated with an inorganic or organic compound for stabilization. Sodium percarbonate coating agents include boric acid, borates, amorphous silicates, magnesium salts or water-insoluble organic compounds such as paraffins and waxes.
[0060]
The coated sodium percarbonate can be manufactured by a known method. For example, JP-A-59-196399, U.S. Pat. No. 4,526,698 (US Pat. No. 4,526,698 (both sodium percarbonate is coated with borate)), JP-A-4-31498, and JP-A-6-40709. And the methods described in JP-A-7-118003 and the like.
The average particle size of such an inorganic peroxide is preferably from 200 to 1000 μm, more preferably from 300 to 800 μm. In order to satisfy both solubility and stability, the content of particles having an average particle size of 125 μm or less and particles having a particle size of 1000 μm or more in the detergent composition is preferably 10% by mass or less.
The content of the inorganic peroxide in the detergent composition is not particularly limited, but is preferably 1% by mass or more, more preferably 1 to 10% by mass, and 2 to 5% by mass. More preferably, it is set to be% by mass. If the content is too small, the concentration of the bleaching agent when dissolved in water becomes too low, and a sufficient bleaching effect cannot be obtained.
[0061]
(Bleaching activator)
The bleach activator contained in the granular detergent composition refers to a compound which is an organic peracid precursor and generates an organic peracid by a peroxide such as hydrogen peroxide. Examples of such a bleaching activator include the following.
[0062]
For example, tetraacetylethylenediamine, pentaacetylglucose, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate Octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene, decanoyloxybenzene, undecanoyloxybenzene , Dodecanoyloxybenzene and the like. Among them, preferred bleaching activators include decanoyloxybenzoic acid, sodium dodecanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, and the like. Among them, from the viewpoint of the bleaching effect, 4-decanoyloxybenzoic acid or sodium 4-nonanoyloxybenzenesulfonate is more preferable.
[0063]
The content of the bleach activator in the present invention is not particularly limited. Among them, the content of the bleach activator in the bleach composition is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass. Further, the content of the bleach activator in the bleaching detergent composition is preferably 0.01 to 2% by mass, more preferably 0.01 to 1% by mass. If the content is less than the above range, the bleaching effect may not be sufficiently obtained, and if the content exceeds the above range, the bleaching effect may not be further enhanced. These bleach activators may be used alone or in combination of two or more.
Further, it is known that the organic peracid generated from the bleaching activator has a bactericidal activity in a washing system and also has an effect of reducing the number of viable microorganisms remaining on clothes. As the bleaching activator, a substance that generates an organic peracid having 8 to 12 carbon atoms is preferable from the viewpoint of bactericidal activity. Sodium nonanoyloxybenzenesulfonate is more preferred.
[0064]
(Bleaching activation catalyst)
The bleaching activation catalyst contained in the granular detergent composition is copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, a transition metal atom such as molybdenum, and a ligand. Refers to a substance that forms a complex via a nitrogen atom, an oxygen atom, or the like. As such a transition metal, cobalt, manganese, or the like is preferable, and among them, manganese is more preferable.
In such a complex, there is any counter ion that balances the charge stoichiometrically generated by the combination of the transition metal atom and the ligand. Preferred counter ions include chloride ions and ammonium ions.
[0065]
As preferred ligands in the present invention, JP-A-2000-144188, JP-A-2000-54256, JP-A-2000-34497, JP-T-2000-508011, JP-T-2000-500518, JP-A-11-57488, JP-A-11-106790, JP-A-11-171893, JP-A-11-342341, JP-T-11-507689, JP-T-11-515049, JP-T-11-507923, JP-A-9-194886, JP-A-8-231987, JP-A-8-0676787, JP-T-8-503247, JP-B-7-065074, JP-B-7-068558, JP-A-5-17485, and WO94 / 11479. Lett (WO94 / 11479), WO93 / 15175 pamphlet (WO93 / 15175), JP-T-2002-530481, JP-T-2002-538268, JP-T-2000-515194, and JP-T-2000-515194. Ligands disclosed in JP-A-2002-294290 can be exemplified.
[0066]
Specific ligands include a carboxylate-containing amine, 1,4,7-trimethyl-1,4,7-triazacyclononane or a compound similar thereto, porphine, porphyrin, phthalocyanine and a skeleton thereof. Water-soluble or water-dispersible derivative, 2,2'-dipyridyl derivative, 1,10-phenanthroline derivative, amine, tris (salicylideneiminoethyl) amine, N, N'-ethylenebis (4-hydroxysalicylideneiminate) ), 13,14-Dichloro-6,6-diethyl-3,4,8,9-tetrahydro-3,3,9,9-tetramethyl-1H-1,4,8,11-benzotetraazacyclotride Syn, 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6,6,2] hexadecane, 5,12-die Le -1,5,8,12- tetraaza - bicyclo [6,6,2] like hexadecane and the like.
[0067]
Specific examples of the bleach-activating catalyst include carboxylate-containing cobalt amine and tris-μ-oxo-bis [(1,4,7-trimethyl-1,4,7-triazacyclononane) manganese (IV). Pentafluorophosphate, porphine or porphine derivative manganese complex, porphyrin or porphyrin derivative manganese complex, phthalocyanine or phthalocyanine derivative manganese complex, 2,2′-dipyridyl derivative manganese complex, 1,10-phenanthroline derivative manganese complex, cobalt amine, (Tris (salicylideneiminoethyl) amine) -manganese complex, (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex, 5,12-dimethyl-1,5,8,12 -Tetraazabicyclo [6,6 2] hexadecanemanganese (II) chloride, [13,14-dichloro-6,6-diethyl-3,4,8,9-tetrahydro-3,3,9,9-tetramethyl-1H-1,4,8 , 11-benzotetraazacyclotridecin] -iron complex and the like.
[0068]
Among them, a more preferred bleach activating catalyst is tris-μ-oxo-bis [(1,4,7-trimethyl-1,4,7-triazacyclononane) manganese (IV)] pentafluorophosphate Salt, (tris (salicylideneiminoethyl) amine) -manganese complex, (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex and the like. A more preferred bleach activating catalyst is (tris (salicylideneiminoethyl) amine) -manganese complex.
[0069]
The molar ratio of the transition metal atom to the ligand in these bleach activation catalysts is preferably from 1: 1 to 1: 4. If the proportion of the ligand is smaller than this ratio, hydrogen peroxide may be decomposed by the transition metal atoms that do not form a complex, resulting in a decrease in the bleaching effect. Even if the amount is too large, the bleaching effect does not increase any more, which may be uneconomical.
The content of the bleach activating catalyst is not particularly limited, but is preferably 0.001 to 1% by mass, more preferably 0.01 to 1% by mass in the bleaching detergent composition. More preferred. If the content of the bleaching activation catalyst is less than the above range, the bleaching effect may not be sufficiently obtained, and if the content exceeds the above range, the bleaching effect may not be further enhanced. These bleach-activating catalysts may be used alone or in combination of two or more.
[0070]
(Other components)
In addition, the detergent particles used in the present invention may contain, in addition to the surfactant compound and the builder, various additives for improving performance and functions.
In particular,
-Fluorescent agent: bis (triazinylamino) stilbene disulfonic acid derivative, bis (sulfostyryl) biphenyl salt [Tinopal CBS-X], etc.
-Antistatic agents: cationic surfactants such as dialkyl-type quaternary ammonium salts.
-Anti-redeposition agents: cellulose derivatives such as carboxymethyl cellulose, polyethylene glycol, polyvinyl alcohol, polypyrrolidone, etc.
Soil release agent: a copolymer or terpolymer of terephthalic acid and ethylene glycol and / or propylene glycol units.
-Bulking agent: sodium sulfate, potassium sulfate or sodium hydrochloride.
-Reducing agent: sodium sulfite or potassium sulfite.
-Foam inhibitors: silicone, silica and / or silicone mixtures and the like.
-Perfumes, dyes, pigments and the like.
[0071]
The impurity component in the raw material may be contained as long as it does not adversely affect the performance and the like. For example, fatty acid methyl ester contained in α-sulfofatty acid methyl ester salt, sodium methyl sulfate, sodium methanesulfonate, α-sulfofatty acid disalt, acrylic acid, maleic acid monomer or salt thereof, and higher alcohol Higher alcohols or polyethylene glycols contained in the ethylene oxide adduct are exemplified.
[0072]
<Container>
Next, the container of the present invention will be described. The container of the present invention is constituted by a box body having an opening on the upper surface, a sealing material for sealing the opening, and an openable and closable lid for covering the opening from outside the sealing material. You. The lid is hingedly connected to the box body and can be opened and closed freely. This hinge connection is made by a hinge piece formed on the box body or a hinge plate formed on the lid. Since the box body and the lid are hingedly connected, a return in the closing direction occurs due to the mass of the lid itself, and the adhesion of the lid to the box body is improved. Therefore, it is possible to prevent intrusion of moisture from the outside of the container to the inside of the container.
A tongue-shaped knob is protruded downward from the lid, and the lid can be freely opened and closed by grasping the knob and pulling it up or down. By providing an upwardly projecting engaging piece at the upper position of the knob piece and providing an engaging hole in the box main body, the engaging piece can be inserted into the engaging hole in a state of hanging. By adopting the kohaze hanging structure, the adhesion of the lid to the box body is further improved.
Hereinafter, the configuration of the container will be described in more detail.
[0073]
(Container A)
1 and 2 show a first embodiment of the container of the present invention. FIG. 1 is an exploded perspective view of the container A, and FIG. 2 is an enlarged sectional view of a hinge mechanism portion of the container A. As shown in FIG. 1, the container A has a box body 1 having an opening 2 on an upper surface, a sealing material for sealing the opening 2, and an openable and closable covering the opening 2 from outside the sealing material. And a lid 3.
[0074]
The box main body 1 has a front plate 1A, a back plate 1B, two left and right side plates 1C, 1C, and a bottom plate 9, and has an opening on the upper surface as shown in FIG. It is a box-shaped container.
[0075]
The upper opening 2 is provided with a front flap 4A, a rear flap 4B, and two left and right side flaps 4C, 4C. By folding these four flaps 4A to 4C inward and bonding them to the inner wall surface of the box body 1, the edge of the upper surface opening 2 is strengthened, and the front flap 4A allows the upper central position of the front plate 1A to be positioned. A gap is formed on the back side of the engaging hole 5 formed in the hole for accommodating the engaging piece 12.
[0076]
The engagement hole 5 and the gap on the back surface thereof are used to lock the lid 3 in the closed position by inserting an engagement piece 12 of the lid 3 to be described later in a closed state. In the state where it is set, it is formed at a position facing the engagement piece 12. The upper edge 5A of the engagement hole 5 is formed in a downwardly convex arc shape, and the engagement piece 12 inserted into and removed from the engagement hole 5 is guided along this arc, It is designed so that the engagement piece 12 can be more smoothly inserted into and removed from the engagement hole 5.
[0077]
The four flaps 4A to 4C are folded inward and adhered to the inner wall surface of the box body 1. Here, the hatched portion 6 of the front flap 4A is provided with a swelled portion that becomes convex inward of the box body 1 when the front flap 4A is bent inward of the box body 1 by embossing. I have. When bonding the front flap 4A to the front plate 1A, an adhesive is applied while avoiding the portion 6. Thereby, a gap is formed on the back surface of the engagement hole 5.
[0078]
Further, the front flap 4A is folded back by the normal fold line 7 having no cut in the portion 6 at the time of the above-mentioned back bonding, and the other portions, the back flap 4B, and the two left and right side flaps 4C, 4C are: Each flap is adhered to the inner wall surface of the box body 1 by being folded back by a half-cut line (half cut) 8 cut from the front side to half the thickness of the cardboard. This is because the portion 6 has a bulge by being turned back and a gap is easily formed on the back surface of the engagement hole 5, and the other portion is sharply bent along the front half cut line 8 by being sharply bent. This is for forming the folded edge.
[0079]
On the other hand, the lid portion 3 is formed of a top plate 3A, a front plate 3B, two left and right side plates 3C, and a flat rear plate 3D on the rear side, and a box-shaped lid portion surrounding four sides of the top plate 3A with side walls. It has been. A hinge piece 15 is cut by a cutting line 16 at an upper position of the back plate 1B of the box body 1 facing the rear plate 3D, and can be opened and closed using the folding lines 17 at the lower right and left as pivot points. A protruding piece 18 is provided at a middle position between the left and right fold lines 17, 17, and is cut by a cutting line 19 so as to protrude below the fold lines 17, 17. The hinge 3 is attached to the inner wall surface of the rear plate 3D of the lid 3 so that the lid 3 is rotatably covered on the upper opening 2 of the box body 1.
[0080]
Further, a tongue-shaped knob piece 11 is protruded downward at the center of the lower edge of the front plate 3B, and at the center position on a horizontal line connecting the left and right upper ends of the knob piece 11, An upwardly convex engaging piece 12 is formed by a cutting line 13. Further, between the left and right lower ends of the cutting line 13 and the left and right upper ends of the knob pieces 11, horizontal fold lines 14 and 14 are engraved, and the entire knob pieces 11 and the engagement pieces 12 are formed. Are rotatable inward and outward of the front plate 3B about the left and right fold lines 14, 14. The width of the engagement piece 12 is set smaller than the width of the engagement hole 5 so that the engagement piece 12 can enter the engagement hole 5 of the box body 1 when the lid 3 is locked. By inserting the engagement piece 12 into the engagement hole 5 in a state of a hook, the adhesion of the lid 3 to the box body 1 is improved.
[0081]
Immediately after purchase, the lid 3 is in an unopened state, and is attached to the box main body 1 so as to be unable to open and close by a method such as tack seal or bonding while being covered with the upper opening 2 of the box main body 1. . Further, a sealing material is bonded and sealed to the box body 1 with an adhesive or the like in the upper opening 2, and a granular detergent is sealed inside the box body by the sealing material. At the first use, the lid 3 can be opened and closed by peeling or tearing the tack seal. Then, by opening the lid 3 and stripping off the sealing material, it becomes possible to take out contents such as granular detergent.
[0082]
When the lid 3 is opened, the hinge pieces 15 rotate rearward with the left and right folding ruled lines 17 and 17 as pivots, and the lid 3 is opened in a state as shown in FIG. At this time, the protruding piece 18 protruding downward rotates toward the front of the box main body 1, stops hitting the rear flap 4 </ b> B of the box main body 1, and can keep the lid 3 open.
[0083]
Next, when the contents such as the detergent are taken out and the lid 3 is pressed from above and closed, the protruding piece 18 rotates from the back flap 4B toward the rear of the box body 1, and the folding lines 17, 17 The lid portion 3 is pushed back in the lid closing direction by the return repulsion force. Therefore, since the lid 3 is constantly urged in the lid closing direction by the repulsive force, the lid closing operation after taking out the contents such as the powdery detergent can be performed more smoothly.
[0084]
As the container of the present invention, a composite material container in which a paper sheet and a resin are integrally formed, in which the bottom plate portion and the periphery of the opening of the container are made of resin, or a bottom plate, a lower portion of the side wall, and an upper portion extending from the lower portion of the side wall A plastic molded body integrally formed with at least two standing pieces, and a paper sheet body which is joined to the outer peripheral surface of the lower part of the side wall and the standing side part and constitutes most of the side wall part of the container. And a paper container made entirely of paper. Among them, paper containers are preferred from the viewpoint of weight reduction of containers and ease of disposal. Further, the paper sheet or paper sheet of the paper container used as a composite material may be made of only a paper material, or may be a material obtained by laminating a resin film or wax on a paper support, A material in which a paper material such as kraft paper is further laminated on the resin film layer may be used.
[0085]
(Container B)
FIG. 3 shows a second embodiment of the container of the present invention. FIG. 3 is an exploded perspective view of the container B. The same or equivalent parts as those of the first embodiment are denoted by the same reference numerals, detailed description thereof will be omitted, and only different parts will be described.
[0086]
In the case of the second embodiment, a hinge plate 20 is provided on the rear surface of the lid 3 at the center of the lower edge of the rear plate 3E via a fold line 27 so as to form a lid. I have. The inner surface of the hinge plate 20 is adhered to a joining portion 28 indicated by hatching on the upper outer surface of the back plate 1B of the box body 1, and the folding line 27 at the upper end of the hinge plate 20 is used as a rotation fulcrum. Is configured to be freely opened and closed. The hinge plate 20 may be bent at the fold line 27 and the outer surface may be attached to the upper outer surface of the back plate 1B.
[0087]
(Container C)
FIG. 4 shows a third embodiment of the container of the present invention. FIG. 4 is an exploded perspective view of the container C. The same or equivalent parts as those of the first embodiment are denoted by the same reference numerals, detailed description thereof will be omitted, and only different parts will be described.
[0088]
In the case of the third embodiment, a tongue-like knob piece 31 is provided at the center of the lower edge of the front plate 3B so as to protrude downward from the front part of the lid 3, and grasps the knob piece 31. The lid 3 can be freely opened and closed by pulling up or pushing down.
[0089]
(Container D)
FIG. 5 shows a fourth embodiment of the container of the present invention. FIG. 5 is an exploded perspective view of the container D. The same or equivalent parts as those of the second embodiment are denoted by the same reference numerals, detailed description thereof will be omitted, and only different parts will be described.
[0090]
In the case of the fourth embodiment, a tongue-shaped knob 31 is projected downward at the center of the lower edge of the front plate 3B on the front surface of the lid 3, and the knob 31 is gripped. The lid 3 can be freely opened and closed by pulling up or pushing down.
[0091]
【Example】
Hereinafter, examples of the present invention will be described.
<Production of detergents "A-1" to "A-5">
Detergents "A-1" to "A-5" were produced. These compositions are shown in Table 1. Of these compositions, sodium α-sulfofatty acid methyl ester (α-SF), a nonionic surfactant, 2.0 mass% of A-type zeolite for addition at the time of kneading, and 3.2 mass% of a grinding aid The remaining components excluding the A-type zeolite and 1.5% by mass of the A-type zeolite for surface coating, enzymes, pigments, and fragrances were dissolved or dispersed in water to prepare a slurry having a water content of 38% by mass. Thereafter, this slurry was spray-dried using a countercurrent spray-drying tower under the condition of a hot air temperature of 280 ° C. to obtain spray-dried particles having a water content of 5% by mass.
On the other hand, based on the production method of Example 4 of Japanese Patent Application No. 2002-278304, a mixed concentrate of sodium α-sulfofatty acid methyl ester and a nonionic surfactant was obtained.
The above-described spray-dried particles, the mixed concentrate, 2.0% by mass of zeolite A, 0.5% by mass of the nonionic surfactant excluding the nonionic surfactant for spray addition, and water are continuously kneaded ( (KRC-S4 type, manufactured by Kurimoto Ironworks Co., Ltd.) and kneaded under conditions of a kneading capacity of 120 kg / h and a temperature of 60 ° C. to obtain an amorphous solid detergent. The amorphous solid detergent is extruded using a pelleter double (EXDFJS-100, manufactured by Fuji Paudal Co., Ltd.) equipped with a die having a hole diameter of 10 mm, and cut with a cutter (cutter peripheral speed is 5 m / s). And a pelleted solid detergent having a length of about 5 to 30 mm was obtained.
Next, 3.2% by mass of a particulate A-type zeolite (average particle size: 180 μm) as a grinding aid was added to the obtained solid detergent, and arranged in three stages in series in the presence of cold air (10 ° C., 15 m / s). (Screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12mm / 6mm / 3mm, rotation speed: 1st stage / 2) using a Fitz mill (manufactured by Hosokawa Micron Corporation, DKA-3). (4700 rpm for both the third and third stages).
Finally, filling is performed with a horizontal cylindrical tumbling mixer (a cylinder having a diameter of 585 mm, a cylinder length of 490 mm, a drum having a clearance of 20 mm from the inner wall surface and a height of 45 mm on the drum inner wall surface of the container 131.7 L). Surface modification by rolling for 1 minute while spraying 0.5% by mass of nonionic surfactant and perfume with 1.5% by mass of fine powder type A zeolite under conditions of 30%, rotation speed of 22 rpm and 25 ° C. Thus, detergent particles were obtained. Other necessary components (percarbonate, bleach activator granules, bleach activator catalyst granules, enzymes, etc.) were arbitrarily added to the obtained detergent particles.
In addition, in order to color a part of the obtained detergent particles, the surface of the detergent particles is transferred at a speed of 0.5 m / s by a belt conveyor (detergent particle layer height on the belt conveyor is 30 mm, layer width is 300 mm). Was sprayed with a 20% aqueous solution of a dye to finally obtain detergents "A-1" to "A-5" (average particle size: 550 μm, bulk density: 0.84 g / mL).
[0092]
<Production of detergents "B-1" and "B-2">
Detergents "B-1" and "B-2" were produced. These compositions are shown in Table 1. Among these compositions, sodium α-sulfofatty acid methyl ester (α-SF), a nonionic surfactant, 7.0 mass% of A-type zeolite for kneading addition, and 3.2 mass% of a pulverization aid The remaining components excluding the A-type zeolite and 1.5% by mass of the A-type zeolite for surface coating, enzymes, pigments, and fragrances were dissolved or dispersed in water to prepare a slurry having a water content of 38% by mass. Thereafter, this slurry was spray-dried using a countercurrent spray-drying tower under the condition of a hot air temperature of 280 ° C. to obtain spray-dried particles having a water content of 5% by mass.
On the other hand, based on the production method of Example 4 of Japanese Patent Application No. 2002-278304, a mixed concentrate of sodium α-sulfofatty acid methyl ester and a nonionic surfactant was obtained.
The above-mentioned dry particles, the mixed concentrate, 7.0 mass% of zeolite A, 0.5 mass% of the remaining nonionic surfactant except for the nonionic surfactant for spray addition and water were continuously kneaded ( (KRC-S4 type, manufactured by Kurimoto Ironworks Co., Ltd.) and kneaded under conditions of a kneading capacity of 120 kg / h and a temperature of 60 ° C. to obtain an amorphous solid detergent. The amorphous solid detergent is extruded using a pelleter double (EXDFJS-100, manufactured by Fuji Paudal Co., Ltd.) equipped with a die having a hole diameter of 10 mm, and cut with a cutter (cutter peripheral speed is 5 m / s). A pelleted solid detergent having a length of about 5 to 30 mm was obtained.
Next, 3.2% by mass of a particulate A-type zeolite (average particle size: 180 μm) as a grinding aid was added to the obtained solid detergent, and arranged in three stages in series in the presence of cold air (10 ° C., 15 m / s). (Screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12mm / 6mm / 3mm, rotation speed: 1st stage / 2) using a Fitz mill (manufactured by Hosokawa Micron Corporation, DKA-3). (4700 rpm for both the third and third stages).
Finally, filling is performed with a horizontal cylindrical tumbling mixer (a cylinder having a diameter of 585 mm, a cylinder length of 490 mm, a drum having a clearance of 20 mm from the inner wall surface and a height of 45 mm on the drum inner wall surface of the container 131.7 L). Surface modification by rolling for 1 minute while spraying 0.5% by mass of nonionic surfactant and perfume with 1.5% by mass of fine powder type A zeolite under conditions of 30%, rotation speed of 22 rpm and 25 ° C. Thus, detergent particles were obtained. Other necessary components (percarbonate, bleach activator granules, bleach activator catalyst granules, enzymes, etc.) were arbitrarily added to the obtained detergent particles.
Further, in order to color a part of the obtained detergent particles, a 20% aqueous solution of a pigment is sprayed in the same manner as in the production of the detergents “A-1” to “A-5”, and the detergent “B-1” And "B-2" (average particle size: 550 μm, bulk density: 0.86 g / mL).
[0093]
[Table 1]

[0094]
<Production of detergents "C-1" and "C-2">
Detergents "C-1" and "C-2" were produced. These compositions are shown in Table 2. Of these compositions, a nonionic surfactant, 2.0% by mass of A-type zeolite for addition at the time of kneading, 3.2% by mass of A-type zeolite for a grinding aid, 1.5% by mass of a surface-coating zeolite Was dissolved or dispersed in water to prepare a slurry having a water content of 38% by mass. Thereafter, the chiller was spray-dried using a counter-current spray-drying tower at a hot air temperature of 300 ° C. to obtain spray-dried particles having a water content of 3% by mass.
Along with the dried particles, 2.0 mass% of zeolite A, 0.5 mass% of the remaining nonionic surfactant excluding the nonionic surfactant for spray addition and water were continuously kneaded (Kurimoto Iron Works Co., Ltd.). (KRC-S4), and kneaded under conditions of a kneading capacity of 120 kg / h and a temperature of 60 ° C. to obtain an amorphous solid detergent. The amorphous solid detergent is extruded using a pelleter double (EXDFJS-100, manufactured by Fuji Paudal Co., Ltd.) equipped with a die having a hole diameter of 10 mm, and cut with a cutter (cutter peripheral speed is 5 m / s). A pelleted solid detergent having a length of about 5 to 30 mm was obtained.
Next, 3.2% by mass of a particulate A-type zeolite (average particle size: 180 μm) as a grinding aid was added to the obtained solid detergent, and arranged in three stages in series in the presence of cold air (10 ° C., 15 m / s). (Screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12mm / 6mm / 3mm, rotation speed: 1st stage / 2) using a Fitz mill (manufactured by Hosokawa Micron Corporation, DKA-3). (4700 rpm for both the third and third stages).
Finally, filling is performed with a horizontal cylindrical tumbling mixer (a cylinder having a diameter of 585 mm, a cylinder length of 490 mm, a drum having a clearance of 20 mm from the inner wall surface and a height of 45 mm on the drum inner wall surface of the container 131.7 L). Surface modification by rolling for 1 minute while spraying 0.5% by mass of nonionic surfactant and perfume with 1.5% by mass of fine powder type A zeolite under conditions of 30%, rotation speed of 22 rpm and 25 ° C. Thus, detergent particles were obtained. Other necessary components (percarbonate, bleach activator granules, bleach activator catalyst granules, enzymes, etc.) were arbitrarily added to the obtained detergent particles.
Further, in order to color a part of the obtained detergent particles, a 20% aqueous solution of a pigment is sprayed in the same manner as in the production of the detergents "A-1" to "A-5", and the detergent "C-1" And "C-2" (average particle size: 540 μm, bulk density: 0.84 g / mL).
[0095]
<Production of detergents "D-1" and "D-2">
Detergents "D-1" and "D-2" were produced. These compositions are shown in Table 2. Detergent particle groups "D-1" and "D-2" were produced by the following procedure.
First, water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 50 ° C. Sodium sulfate and a fluorescent whitening agent were added thereto, and the mixture was stirred for 10 minutes. Subsequently, after adding sodium carbonate, the acrylic acid-based polymer was added, and the mixture was further stirred for 10 minutes, and then sodium chloride and a part of the powder A-type zeolite were added. The mixture was further stirred for 30 minutes to prepare a slurry for spray drying.
The temperature of the obtained slurry for spray drying was 50 ° C. This slurry is spray-dried by a counter-current spray-drying apparatus equipped with a pressure spray nozzle, and has a volatile content (105 ° C., weight loss for 2 hours) of 3% by mass, a bulk density of 500 g / L and an average particle size of 250 μm. To obtain spray-dried particles.
Separately, a nonionic surfactant, polyethylene glycol, soap, and an anionic surfactant (eg, LAS-Na) are mixed at a temperature of 80 ° C. to form a surfactant composition having a water content of 10% by mass. Was prepared. LAS-Na was used in the form of a solution neutralized with an aqueous sodium hydroxide solution.
Then, the spray-dried particles obtained above are introduced into a Loedige mixer (M20 type, manufactured by Matsubo Corporation) equipped with a plow-shaped shovel and having a clearance between the shovel and the wall surface of 5 mm (filling rate: 50%). Then, stirring of the main shaft (150 rpm) and the chopper (4000 rpm) was started while flowing hot water at 80 ° C. through the jacket at a flow rate of 10 L / min. The above-prepared surfactant composition was added thereto over 2 minutes, and then stirred for 5 minutes. Then, the layered silicate (SKS-6, average particle size of 5 μm) and a part of the powder type A zeolite (10 % By mass) and stirred for 2 minutes to obtain detergent particles.
The obtained detergent particles and a part (2% by mass) of the powder type A zeolite are mixed in a V blender, and other necessary components (percarbonate, bleaching activator granulated product, bleaching activated catalyst granulated product) , Enzymes, etc.) and sprayed with perfume. Further, in order to color a part of the detergent particles, a 20% aqueous solution of a pigment is sprayed in the same manner as in the production of the detergents “A-1” to “A-5”, and the detergents “D-1” and “D-5” are sprayed. -2 "(average particle size: 300 m, bulk density: 0.75 g / mL).
[0096]
<Production of detergent "E-1">
Detergent "E-1" was produced. The composition is shown in Table 2. Of these compositions, the remaining components excluding the nonionic surfactant, 5.0% by mass of A-type zeolite for surface coating, layered silicates, enzymes, pigments, and fragrances are dissolved or dispersed in water to obtain water. A slurry having 38% by mass was prepared. Thereafter, the chiller was spray-dried using a counter-current spray-drying tower at a hot air temperature of 300 ° C. to obtain spray-dried particles having a water content of 3% by mass.
The spray-dried particles are charged (filling rate: 50%) into a Loedige mixer (M20, manufactured by Matsubo Co., Ltd.) equipped with a plow-blade excavator and having a clearance between the excavator and the wall surface of 5 mm, and the main shaft is rotated at 200 rpm and the chopper is rotated at 200 rpm. Was started. Thirty seconds after the start of stirring, a nonionic surfactant and water (temperature: 60 ° C.) were added over 2 minutes, and stirring granulation was continued at a jacket temperature of 30 ° C. until the average particle size became 400 μm.
Finally, layered silicate (SKS-6, average particle size 5 μm) and 5.0% by mass of fine powder type A zeolite were added, stirred for 1 minute to modify the surface, and sprayed with fragrance to obtain detergent particles. Other necessary components (percarbonates, bleach activator granules, bleach activator catalyst granules, enzymes, etc.) were arbitrarily added to the obtained detergent particles.
In order to color a part of the obtained detergent particles, the detergent particles are transferred on a belt conveyor at a speed of 0.5 m / s (detergent particle layer height on the belt conveyor is 30 mm, layer width is 300 mm), and a blue color is formed on the surface. The dye solution was sprayed to obtain a detergent “E-1” (average particle size: 400 μm, bulk density: 0.78 g / mL).
[0097]
<Manufacture of detergent "F-1">
Detergent "F-1" was produced. The composition is shown in Table 2. Equip with a plow-blade shovel of all the remaining raw materials (temperature: 25 ° C) excluding the nonionic surfactant, 5.0 mass% P-type zeolite used for surface coating, pigments, enzymes, and fragrances. The extruder was charged into a Reedige mixer (M20 type, manufactured by Matsubo Co., Ltd., type M20) having a clearance between the excavator and the wall surface of 5 mm (filling ratio: 50%), and stirring of the main shaft at 200 rpm and the chopper at 200 rpm was started.
Thirty seconds after the start of stirring, a nonionic surfactant and water (temperature: 60 ° C.) were added over 2 minutes, and stirring granulation was continued at a jacket temperature of 30 ° C. until the average particle size became 400 μm. Finally, 5.0% by mass of P-type zeolite was added, and the mixture was stirred for 30 seconds to modify the surface and spray a fragrance to obtain detergent particles. Other necessary components (enzymes, etc.) were optionally added to the detergent particles.
In addition, in order to color a part of the obtained detergent particles, a 20% aqueous solution of a pigment is sprayed in the same manner as in the production of the detergents "A-1" to "A-5", and the detergent "F-1" (Average particle size: 400 μm, bulk density: 0.80 g / mL) was obtained.
[0098]
[Table 2]

[0099]
Here, components indicated by abbreviations in Tables 1 and 2 will be described.
-Α-SF-Na: sodium salt of α-sulfofatty acid methyl ester having 14: 18 carbon atoms and 18 carbon atoms (manufactured by Lion Corporation)
LAS-K: 48% hydroxylated linear alkyl (C10-14) benzene sulfonic acid (LAIPON LH-200 (LAS-H pure content: 96%) manufactured by Lion Corporation) at the time of producing the surfactant composition Neutralize with aqueous potassium solution. The blending amounts in Tables 1 and 2 indicate mass% as LAS-K.
-LAS-Na: 48% hydroxylation of linear alkyl (10-14 carbon atoms) benzenesulfonic acid (LAIPON LH-200 (LAS-H pure content: 96%) manufactured by Lion Corporation) during the production of a surfactant composition Neutralize with aqueous sodium solution. The blending amounts in Tables 1 and 2 indicate mass% as LAS-Na.
AOS-K: potassium α-olefin sulfonate having an alkyl group having 14 to 18 carbon atoms (manufactured by Lion Corporation)
AOS-Na: α-olefin sulfonate potassium having an alkyl group having 14 to 18 carbon atoms (manufactured by Lion Corporation)
AS-Na: sodium alkyl sulfate having an alkyl group having 10 to 18 carbon atoms (Sandet LNM manufactured by Sanyo Chemical Industries, Ltd.)
Soap: Sodium fatty acid having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C, fatty acid composition: C₁₂: 11.7%, C₁₄: 0.4%, C₁₆: 29.2%, C₁₈₀(Stearin): 0.7%, C₁₈₁(Olein): 56.8%, C₁₈₂(Linol): 1.2%, molecular weight: 289)
-Nonionic surfactant A: ECOROL26 (manufactured by Ecogreen) 15 mol ethylene oxide adduct (manufactured by Lion Corporation)
-Nonionic surfactant B: 7 mole ethylene oxide adduct of ECOROL26 (manufactured by Ecogreen) (manufactured by Lion Corporation)
PEG6000: polyethylene glycol (manufactured by Lion Corporation, PEG # 6000M)
・ Fluorescent Brightener A: Tinopearl CBS-X (Ciba Specialty Chemicals)
-Fluorescent whitening agent B: Tinopearl AMS-GX (Ciba Specialty Chemicals)
・ Sodium silicate: JIS No. 1 sodium silicate (manufactured by Nippon Chemical Co., Ltd.)
・ Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Shikoku Chemical Industry Co., Ltd.)
・ Sodium chloride: Nissei no Yaki salt C (manufactured by Japan Salt Co., Ltd.)
・ Potassium carbonate: Potassium carbonate (made by Asahi Glass Co., Ltd.)
・ Zeolite A: A type zeolite (manufactured by Mizusawa Chemical Co., Ltd.)
-Zeolite B: P-type zeolite (Doucil A24, manufactured by INEOS Silicas)
-Layered silicate: crystalline layered sodium silicate (manufactured by Clariant Tokuyama, SKS-6)
Acrylic acid polymer A: sodium salt of acrylic acid / maleic acid copolymer, trade name Sokalan CP7 (BASF)
Acrylic acid polymer B: sodium polyacrylate, trade name Sokalan PA30 (BASF)
・ Montmorillonite: Montmorillonite (Round Rosil made by SUD CHEMIE)
・ White carbon: fine powder of silica (Tokusil N, manufactured by Tokuyama Corporation)
-Percarbonate A: coated sodium percarbonate (manufactured by Mitsubishi Gas Chemical Co., Ltd., SPC-D), sodium percarbonate content about 85% by mass, average particle size 760 µm
-Bleaching activator granules A: Bleaching activator granules A shown in Japanese Patent Application No. 2002-378409, Tables 1 and 2.
-Bleaching activator granules B: Bleaching activator granules B shown in Japanese Patent Application No. 2002-378409, Tables 1 and 2.
-Bleaching activator granules C: Bleaching activator granules C shown in Japanese Patent Application No. 2002-378409, Tables 1 and 2.
-Bleached activated catalyst granules A: Granulated material 4 shown in Japanese Patent Application No. 2002-250734, Table 9
Enzyme A: a mixture of Evalase 8T (Novozymes) / LIPEX50T (Novozymes) / Termamyl 60T (Novozymes) / Cellzyme 0.7T (Novozymes) = 5/2/2/2 (mass ratio)
Enzyme B: a mixture of cannase 12T (Novozymes) / LIPEX50T (Novozymes) / Termamyl 60T (Novozymes) / Cellzyme 0.7T (Novozymes) = 5/2/2/2 (mass ratio)
-Fragrance A: Fragrance composition A shown in JP-A-2002-146399, Tables 11 to 18
-Fragrance B: Fragrance composition B shown in JP-A-2002-146399, Tables 11 to 18
-Fragrance C: Fragrance composition C shown in JP-A-2002-146399, Tables 11 to 18
-Fragrance D: Fragrance composition D shown in JP-A-2002-146399, and Tables 11 to 18
-Dye A: Ultramarine (Ultramarine Blue)
Dye B: Pigment Green 7 (manufactured by Dainichi Seika Kogyo)
・ Sodium carbonate: Heavy sodium carbonate (Soda ash, manufactured by Asahi Glass Co., Ltd.)
[0100]
<Measurement of mass increase of detergent composition>
Next, these detergents were filled in containers A to E, respectively, to obtain products (Examples 1 to 15, Comparative Examples 1 and 2). After these lids were once opened and the sealing material such as the inner seal was opened and removed, the lids were closed again. Then, a 24-hour leaving step of leaving the substrate at a temperature of 45 ° C. and a humidity of 85% for 16 hours in an environment of 85% humidity and a temperature of 25 ° C. for 8 hours was continued for 14 days. Thereafter, the mass of the detergent composition was measured, and the increase in mass relative to the mass of the detergent composition before opening the sealing material was determined. The results are shown in Tables 3 and 4.
here,
-Container A: Container shown in Fig. 1 (with a hook-and-loop engaging part-with a hinge piece on the box body)
-Container B: Container shown in Fig. 3 (with a goby hook engaging portion-hinge plate on lid)
-Container C: Container shown in Fig. 4 (No engaging part for goby hook-Hinge piece on box body)
-Container D: Container shown in Fig. 5 (without hooked engaging portion-hinge plate on lid)
Container E: Container shown in FIG. 1 of JP-A-09-278030.
Detergent G-1: Detergent of Example 2 described in Table 1 of JP-A-2002-012900
LAS amount: mass% of linear alkylbenzene sulfonate
・ Nonionic amount: mass% of nonionic surfactant
・ Amount of fine powder: Differential amount of 100 μm or less (% by mass)
Respectively.
[0101]
<Solidability test (easy to remove with a spoon)>
1000 g of each of the produced granular detergent compositions was filled in the above-mentioned containers A to E, and the above-mentioned standing process for 24 hours was continued for 14 days. Thereafter, the lid was opened and the resistance to scooping the detergent with a detergent spoon was judged by 10 women in their 20s and 40s, and scored based on the following criteria.
◎: 10 out of 10 respondents answered, "We saved with a spoon without resistance."
：: 6 to 9 out of 10 respondents answered that they could save with a spoon
△: 1 to 5 out of 10 respondents answered, “We saved with a spoon without resistance”
×: 0 out of 10 respondents answered, “We saved without a spoon.”
The results are shown in Tables 3 and 4.
[0102]
<Exudation test>
1000 g of each of the produced detergent compositions was filled in the containers A to E, and the standing process for 24 hours was continued for 14 days. Then, after taking out the detergent composition, the inner wall of the container was visually judged by 10 women in their 20s and 40s, and scored based on the following criteria.
◎: 0 out of 10 people answered "I feel unpleasant"
：: 1 to 5 out of 10 respondents answered "feeling exudation unpleasant"
△: 6 to 9 out of 10 respondents answered that "feeling exudation was uncomfortable"
×: 10 out of 10 people answered "I feel unpleasant"
The results are shown in Tables 3 and 4.
[0103]
<Evaluation of detergency>
1. Adjustment of stained cloth
In order to evaluate the detergency, an artificially soiled cloth was prepared according to the description in Examples of JP-A-2001-64694.
2. Cleaning method
A set of 10 test cloths is sewn to one piece of fleece clothing, and one piece of fleece clothing, 14 cotton long-sleeved shirts, and 7 acrylic jersey long-sleeved shirts (3.5 kg in total) are fully automatic washing machine (MAW-V8QP). , Manufactured by Mitsubishi Electric Corporation). Then, each detergent obtained by continuing the above-mentioned standing process for 24 hours for 14 days was spooned, sprinkled on clothing, and then washed with a normal course by pouring 15 ° C. tap water.
3. Evaluation method
According to the description in the examples of JP-A-2001-64694, the cleaning rate was determined and evaluated according to the following criteria.
◎: 90% or more of cleaning rate
：: 75% or more and less than 90% of cleaning rate
Δ: Cleaning rate of 60% or more and less than 75%
×: less than 60% cleaning rate
The results are shown in Tables 3 and 4.
[0104]
[Table 3]

[0105]
[Table 4]

[0106]
As a result, the detergent whose mass increase of the detergent composition was 5% by mass or less was of good quality. Further, those having a mass increase of 4% by mass or less had a higher cleaning rate, and those having a mass increase of 3% by mass or less had a further higher cleaning rate, and had very good quality.
[0107]
【The invention's effect】
As described above in detail, the detergent product of the present invention, after opening the sealing material, even if the product is left in a high-temperature and high-humidity environment, solidification of the granular detergent composition and exudation of components occur. In addition, the detergency of bulky clothes does not decrease.
[Brief description of the drawings]
FIG. 1 is an exploded perspective view of a container A according to a first embodiment.
FIG. 2 is an enlarged sectional view of a hinge mechanism portion of the container A according to the first embodiment.
FIG. 3 is an exploded perspective view of a container B according to a second embodiment.
FIG. 4 is an exploded perspective view of a container C according to a third embodiment.
FIG. 5 is an exploded perspective view of a container D according to a fourth embodiment.
[Explanation of symbols]
1 box body
1A front panel
1B back plate
2 Top opening
3 Lid
3A top panel
3B front plate
3C side plate
3D, 3E rear plate
4A front flap
4B back flap
5 Engagement hole
5A Upper edge of engagement hole
7 folding line
8 Half cut line
11, 31 knob piece
12 Engagement piece
13 Cutting line
14 Folded lines
15 Hinge piece
16 Cutting line
17, 27 Folded line
18 projection
19 Cutting line
20 hinge plate
28 joint

Claims (4)

A granular detergent composition comprises a box body having an opening on the upper surface, a sealing material for sealing the opening, and an openable and closable lid for covering the opening from the outside of the sealing material. In the stored detergent product, after the sealing material is opened, the lid is closed, and the temperature is 45 ° C. and the humidity is 85% for 16 hours, and the temperature is 25 ° C. and the humidity is 65% in an environment. When the 24-hour standing step of leaving for 24 hours is continued for 14 days, the increase in the mass of the granular detergent composition is 5% by mass or less based on the mass of the granular detergent composition before opening the sealing material. Detergent products The box body has a front plate, a back plate, left and right side plates and a bottom plate, and the lid has a front plate, a rear plate, left and right side plates and a top plate, and a back plate of the box body. At the upper position, a hinge piece is provided which is surrounded by an upward convex cutting line, a crease line formed horizontally at the lower left and right sides of the convex cutting line, and a cutting line communicating between the left and right crease lines. 2. The detergent product according to claim 1, wherein the hinge piece is attached to an inner surface of a rear plate of the lid portion, whereby the lid portion is hingedly connected to the box body with the folding line as a pivot. The box body has a front plate, a rear plate, left and right side plates and a bottom plate, and the lid has a front plate, a rear plate, left and right side plates and a top plate, and a rear plate of the lid. A hinge plate is continuously provided via a crease line, and the hinge plate is attached to the back plate of the box main body, whereby the lid portion is hinged to the box main body with the crease line as a pivot point. The detergent product of claim 1. 4. The detergent product according to claim 2, wherein the container is a paper container.

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