JP3694063B2 - Method for producing high-density granular detergent composition - Google Patents

Description

【００２２】
（式中Y は炭素数１〜３のアルキル基（好ましくはメチル基）又は対イオンである。Z は対イオンである。R は炭素数10〜20のアルキル基又はアルケニル基を表す。）
(9) その他、飽和又は不飽和脂肪酸塩、アルキルまたはアルケニルエーテルカルボン酸塩、アミノ酸型界面活性剤、Ｎ−アシルアミノ酸型界面活性剤、アルキルまたはアルケニルリン酸エステル又はその塩が例示される。
【００２３】
上記の中で特に好ましいアニオン性界面活性剤としては、(1) 、(2) 、(3) 及び(6) である。
【００２４】
アニオン性界面活性剤の配合量は限定されないが、洗浄力や溶解性の面から、最終洗剤組成物中10〜40重量％、好ましくは20〜35重量％配合するのがよい。
【００２５】
また、ビルダーとしては、通常の洗剤用のビルダーとして知られているものを用いることができ、具体的には以下のようなものが使用できる。ビルダーは、最終組成物中に通常10〜60重量％配合される。
【００２６】
（Ｉ）無機ビルダー
1) 炭酸ナトリウム、炭酸カリウム、重炭酸ナトリウム、亜硫酸ナトリウム、セスキ炭酸ナトリウム、JIS 1 号珪酸ナトリウム等のアルカリ金属珪酸塩に代表されるアルカリ性塩。
2) 硫酸ナトリウムなどの中性塩。
3) オルソリン酸塩、ピロリン酸塩、トリポリリン酸塩、メタリン酸塩、ヘキサメタリン酸塩、フィチン酸塩などのリン酸塩（ナトリウム、カリウム等のアルカリ金属塩）。
4) 更に以下の結晶性アルミノ珪酸塩、又は上記のアルカリ金属珪酸塩とは異なる結晶性層状珪酸塩も挙げることができる。
具体的には次式で示される結晶性アルミノ珪酸塩が挙げられる。
x'(M₂O)・Al₂O₃・y'(SiO₂)・w'(H₂O)
（式中、M はナトリウム、カリウム等のアルカリ金属原子、x',y',w'は各成分のモル数を表わし、一般的には、0.7 ≦x'≦1.5 、0.8 ≦y'≦６、w'は任意の定数である。）
これらの中で、特に次の一般式で示されるものが好ましい。
Na₂O・Al₂O₃・ｙSiO₂・ｗH₂O
（式中、ｙは1.8 〜3.0 、ｗは１〜６の数を表わす。）
また、下式
M₂Si_xO_(2x+1)・y(H₂O)
（式中、M はアルカリ金属を表わし、x ，y は1.5 ≦x ≦４、y ≦25、好ましくはy ≦20、更に好ましくはy ＝０である。）
で示される結晶性層状珪酸塩も挙げられる。この化合物は、特開昭60−227895号公報にその製法が記載されており、一般的には無定形のガラス状珪酸ソーダを 200〜1000℃で焼成して結晶性とすることによって得られる。合成方法の詳細は、例えば Phys.Chem.Glasses.7,127-138(1966)、Z.Kristallogr.,129, 39 6-404(1969) 等に記載されている。
また、この結晶性層状珪酸塩は例えばヘキスト社より商品名「Na-SKS-6」（σ−Na₂Si₂O₅) として微粉末状、粉末状、顆粒状のものが入手でき、本発明では粒径が５〜500 μm のものを使用できるが、好ましくは10〜300 μm のものである。
【００２７】
5) 更に、高吸油性で且つ陽イオン交換能の高い吸油性担体として下記一般式(1 ) で表される吸油性非晶質アルミノ珪酸塩が例示される。吸油性担体は液状の非イオン性界面活性剤を使用する粉末洗剤の場合において好ましいビルダーである。
a(M₂O)・Al₂O₃・b(SiO₂)・c(H₂O) (1)
〔式中、M はアルカリ金属原子、a,b,c は各成分のモル数を表し、0.7 ≦a ≦2.0 、 0.8≦b ＜４、c は任意の正数である。〕
特に次の一般式(2)
Na₂O・Al₂O₃・m(SiO₂)・c(H₂O) (2)
〔ここで、m は 1.8〜3.2 、c は１〜６の数を表す。〕
で表されるものが好ましい。
本発明で使用可能な高吸油性且つ高イオン交換能を有する前記非晶質アルミノ珪酸塩の製法は、例えばSiO₂とM₂O (Mはアルカリ金属を意味する) のモル比がSiO₂／M₂O ＝ 1.0〜4.0 であり、H₂OとM₂Oのモル比が H₂O／M₂O ＝12〜200 である珪酸アルカリ金属塩水溶液に、M₂O とAl₂O₃ のモル比が M₂O／Al₂O₃ ＝ 1.0〜2.0 であり、H₂O とM₂O のモル比が H₂O／M₂O ＝ 6.0〜500 である低アルカリアルミン酸アルカリ金属塩水溶液を15〜60℃、好ましくは30〜50℃の温度のもとで強攪拌下に添加する。また、アルミン酸アルカリ金属塩水溶液に珪酸アルカリ金属塩水溶液を添加してもよい。
次いで生成した白色沈澱物スラリーを70〜100℃、好ましくは90〜100℃の温度で10分以上10時間以下、好ましくは５時間以下加熱処理し、その後濾過、洗浄、乾燥することにより有利に得ることができる。この方法によりイオン交換能100 CaCO₃ mg／ｇ以上、吸油能 200ml／100 ｇ以上の非晶質アルミノ珪酸塩吸油性担体を容易に得ることができる（特開昭62−191417号公報、特開昭62− 191419号公報参照）。
【００２８】
これらの無機ビルダーの中では、トリポリリン酸ナトリウム、炭酸ナトリウム、結晶性アルミノ珪酸塩、結晶性層状珪酸塩がより好ましい。特に、結晶性アルミノ珪酸塩（ゼオライト）としては、Ａ型、Ｘ型ゼオライトに代表される一次粒子の平均粒子径が 0.1〜10μm の合成ゼオライトが好適に使用される。ゼオライトは粉末及び／又はゼオライトスラリーを乾燥して得られるゼオライト凝集乾燥粒子として配合される。ゼオライトは、通常、全組成物中に５〜60重量％配合してもよい。
【００２９】
(II)有機ビルダー
有機ビルダーとしては以下の物質が例示される。
1) エタン−1,1 −ジホスホン酸、エタン−1,2 −トリホスホン酸、エタン−１−ヒドロキシ−1,1 −ジホスホン酸及びその誘導体、エタンヒドロキシ−1,1, 2 −トリホスホン酸、エタン−1,2 −ジカルボキシ−1,2 −ジホスホン酸、メタンヒドロキシホスホン酸等のホスホン酸の塩
2) ２−ホスホノブタン−1,2 −ジカルボン酸、１−ホスホノブタン−2,3,4 −トリカルボン酸、α−メチルホスホノコハク酸等のホスホノカルボン酸の塩
3) アスパラギン酸、グルタミン酸等のアミノ酸の塩
4) ニトリロ三酢酸塩、エチレンジアミン四酢酸塩、ジエチレンジアミン五酢酸塩等のアミノポリ酢酸塩
5) ポリアクリル酸、特開昭54−52196 号公報記載のポリグリオキシル酸塩、ポリアコニット酸、ポリイタコン酸、ポリシトラコン酸、ポリフマル酸、ポリマレイン酸、ポリメタコン酸、ポリ−α−ヒドロキシアクリル酸、ポリビニルホスホン酸、スルホン化ポリマレイン酸、無水マレイン酸−ジイソブチレン共重合体、無水マレイン酸−スチレン共重合体、無水マレイン酸−メチルビニルエーテル共重合体、無水マレイン酸−エチレン共重合体、無水マレイン酸−エチレンクロスリンク共重合体、無水マレイン酸−酢酸ビニル共重合体、無水マレイン酸−アクリロニトリル共重合体、無水マレイン酸−アクリル酸エステル共重合体、無水マレイン酸−ブタジエン共重合体、無水マレイン酸−イソプレン共重合体、無水マレイン酸と一酸化炭素から誘導されるポリ−β−ケトカルボン酸、イタコン酸、エチレン共重合体、イタコン酸−アコニット酸共重合体、イタコン酸−マレイン酸共重合体、イタコン酸−アクリル酸共重合体、マロン酸−メチレン共重合体、イタコン酸−フマル酸共重合体、アクリル酸−マレイン酸共重合体、エチレングリコール−エチレンテレフタレート共重合体、ビニルピロリドン−酢酸ビニル共重合体、１−ブテン−2,3,4 −トリカルボン酸−イタコン酸−アクリル酸共重合体、第四アンモニウム基を有するポリエステルポリアルデヒドカルボン酸、エポキシコハク酸のシス−異性体、ポリ〔N,N −ビス（カルボキシメチル）アクリルアミド〕、ポリ（オキシカルボン酸）、デンブンコハク酸あるいはマレイン酸あるいはテレフタル酸エステル、デンプンリン酸エステル、ジカルボキシデンプン、ジカルボキシメチルデンプン、カルボキシルメチルセルロース、コハク酸エステル等の高分子電解質
6) ポリエチレングリコール、ポリビニルアルコール、ポリビニルピロリドン、カルボキシメチルセルロース、冷水可溶性ウレタン化ポリビニルアルコール等の非解離高分子
7) ジグリコール酸、オキシジコハク酸、カルボキシメチルオキシコハク酸、シクロペンタン−1,2,3,4 −テトラカルボン酸、テトラヒドロフラン−1,2,3,4 −テトラカルボン酸、テトラヒドロフラン−2,2,5,5 −テトラカルボン酸、クエン酸、乳酸、酒石酸、ショ糖、ラクトース、ラフィノース等のカルボキシメチル化物、ペンタエリスリトールのカルボキシメチル化物、グルコン酸のカルボキシメチル化物、多価アルコールあるいは糖類と無水マレイン酸あるいは無水コハク酸との縮合物、オキシカルボン酸と無水マレイン酸あるいは無水コハク酸との縮合物、メリット酸で代表されるベンゼンポリカルボン酸、エタン− 1,1,2,2 −テトラカルボン酸、エテン−1,1,2,2 −テトラカルボン酸、ブタン−1,2,3,4 −テトラカルボン酸、プロパン−1,2,3 −トリカルボン酸、ブタン−1,4 −ジカルボン酸、シュウ酸、スルホコハク酸、デカン−1,10−ジカルボン酸、スルホトリカルバリル酸、スルホイタコン酸、リンゴ酸、オキシジコハク酸、グルコン酸、CMOS、ビルダーM 等の有機酸塩。
【００３０】
これらの有機ビルダーの中では、クエン酸塩、ポリアクリル酸塩、ポリグリオキシル酸塩、アクリル酸−マレイン酸共重合体、ポリエチレングリコールがより好ましい。
【００３１】
なお本発明においては、最終的な高密度洗剤組成物に下記成分を配合することができ、各成分の性質によって噴霧乾燥生成物中に予め添加しても、造粒中に添加しても、或いは造粒後にアフターブレンドしてもよい。
【００３２】
(1) その他の界面活性剤
本発明で規定する以外の非イオン性界面活性剤、ベタイン型両性界面活性剤、スルホン酸型両性界面活性剤、リン酸エステル系界面活性剤、又はカチオン性界面活性剤（アミン類も含む）等
(2) 漂白剤
過炭酸ナトリウム、過ホウ酸ナトリウム（１水塩が好ましい）、又は硫酸ナトリウム過酸化水素付加体等が挙げられ、特に過炭酸ナトリウムが好ましい。
(3) 漂白活性化剤
テトラアセチルエチレンジアミン、アセトキシベンゼンスルホン酸塩、特開昭59−22999 号公報、特開昭63−258447号公報、もしくは特開平６−316700号公報記載の有機過酸前駆体、または遷移金属を金属イオン封鎖剤で安定化させた金属触媒等
(4) 酵素（本来的に酵素作用を洗浄工程中になす酵素である。）
酵素の反応性から分類すると、ヒドロラーゼ類、ヒドラーゼ類、オキシドレダクターゼ類、デスモラーゼ類、トランスフェラーゼ類及びイソメラーゼ類が挙げられるが、本発明にはいずれも適用できる。特に好ましいのはヒドロラーゼ類であり、プロテアーゼ、エステラーゼ、リパーゼ、カルボヒドラーゼ、ヌクレアーゼ、セルラーゼ及びアミラーゼが含まれる。
プロテアーゼの具体例は、ペプシン、トリプシン、キモトリプシン、コラーゲナーゼ、ケラチナーゼ、エラスターゼ、スプチリシン、BPN 、パパイン、プロメリン、カルボキシペプチターゼＡ及びＢ、アミノペプチターゼ、アスパーギロペプチターゼＡ及びＢであり、市販品として、サビナーゼ、アルカラーゼ（ノボインダストリー社）、API 21（昭和電工 (株) ）、マクサカル（ギストブロケイデス社）、特開平５−43892 号公報記載のプロテアーゼK-14もしくは K-16がある。
エステラーゼの具体例は、ガストリックリパーゼ、パンクレアチックリパーゼ、植物リパーゼ類、ホスホリパーゼ類、コリンエステラーゼ類及びホスホターゼ類がある。
例えばリパーゼとしては、リポラーゼ（ノボインダストリー社）等の市販のリパーゼを用いることができる。
カルボヒドラーゼの具体例としては、セルラーゼ、マルターゼ、サッカラーゼ、アミラーゼ、ペクチナーゼ、リゾチーム、α−グリコシダーゼ及びβ−グリコシダーゼが挙げられる。
また、セルラーゼとしては、例えば市販のセルザイム（ノボインダストリー社）、特開昭63−264699号公報の請求項４記載のセルラーゼが使用でき、アミラーゼとしては、例えば市販のターマミル（ノボインダストリー社）等が使用できる。
【００３３】
(5) 酵素安定剤
還元剤（亜硫酸ナトリウム、亜硫酸水素ナトリウム）、カルシウム塩、マグネシウム塩、ポリオール、ホウ素化合物など
(6) 青味付剤
各種の青味付剤も必要に応じて配合できる。例えば次の式 (ｉ) 及び式(ii)の構造のものが奨用される。
【００３４】
【化２】

【００３５】
（式中、D₁は青色乃至紫色のモノアゾ、ジスアゾ又はアントラキノン系色素残基を表わし、X₁及びY₁は水酸基；アミノ基、水酸基、スルホン酸基、カルボン酸基又はアルコキシ基で置換されていることもある脂肪族アミノ基；ハロゲン原子、水酸基、スルホン酸基、カルボン酸基、低級アルキル基又は低級アルコキシ基で置換されていることもある芳香族アミノ基又は環状脂肪族アミノ基を表わし、R は水素原子又は低級アルキル基を表わす。ただし、R が水素原子を表わす場合であって、▲１▼X₁及びY₁が同時に水酸基又はアルカノールアミノ基を表わす場合、並びに▲２▼X₁及びY₁のいずれか一方が水酸基であり、他方がアルカノールアミノ基である場合を除く。ｎは２以上の整数を表わす。）
【００３６】
【化３】

【００３７】
（式中、D₂は青色乃至紫色のアゾ又はアントラキノン系色素残基を表わし、R は水素原子又は低級アルキル基を表わし、X₂及びY₂は同一又は相異なるアルカノールアミノ基又は水酸基を表わす。）
(7) ケーキング防止剤
ケーキング防止剤としては、パラトルエンスルホン酸塩、キシレンスルホン酸塩、酢酸塩、スルホコハク酸塩、タルク、微粉末シリカ、粘土、酸化マグネシウム等が挙げられる。なお、微粉末シリカ等で多孔質のものは、非イオン性界面活性剤の担体として使用できる。また、粘土（スメクタイト状粘土）は、柔軟化剤としても効果的である。
【００３８】
(8) 酸化防止剤
酸化防止剤としては、第３ブチルヒドロキシトルエン、4,4'−ブチリデンビス−（６−第３ブチル−３−メチルフェノール）、2,2'−ブチリデンビス−（６−第３ブチル−４−メチルフェノール）、モノスチレン化クレゾール、ジスチレン化クレゾール、モノスチレン化フェノール、ジスチレン化フェノール、 1,1'−ビス−（４−ヒドロキシフェニル）シクロヘキサン等が挙げられる。
【００３９】
(9) 蛍光染料
蛍光染料として、4,4'−ビス−（２−スルホスチリル）−ビフェニル塩、4, 4'−ビス−（４−クロロ−３−スルホスチリル）−ビフェニル塩、２−（スチリルフェニル）ナフトチアゾール誘導体、4,4'−ビス（トリアゾール−２−イル）スチルベン誘導体、ビス（トリアジニルアミノ）スチルベンジスルホン酸誘導体の１種又は２種以上を、組成物中に０〜１重量％含有することができる。
(10)光活性化漂白剤
スルホン化アルミニウムフタロシアニン、スルホン化亜鉛フタロシアニンの１種又は２種を組成物中に０〜0.2 重量％含有することができる。
(11)香料
香料としては、従来洗剤に配合される香料、例えば特開昭63−101496号公報記載の香料を使用することができる。
(12)消泡剤
消泡剤としては、例えばシリコーン／シリカ系のものが挙げられ、特開平３−186307号公報記載の方法を用いて製造した消泡剤造粒物を用いてもよい。
【００４０】
上記した本発明の製造方法により製造された粒状洗剤組成物の嵩密度は0.65ｇ／cm³以上、好ましくは0.65〜0.85ｇ／cm³、更に好ましくは0.70〜0.82ｇ／cm³ である。
【００４１】
【発明の効果】
本発明によって製造された高密度粒状洗剤組成物は、造粒時に水和塩が均一に水和して粒子中に存在するため、洗剤粒子の結合や塊状化が回避され、溶解性が向上する。特に、本発明により得られた高密度洗剤組成物は、低温の洗濯水を用いた場合でも優れた溶解性を示し、且つ十分な洗浄力も発揮する。
【００４２】
【実施例】
以下実施例にて本発明を説明するが、本発明はこれらの実施例に限定されるものではない。
【００４３】
実施例１〜10及び比較例１〜６
(1) 噴霧乾燥生成物の調製
表１に示す成分を水と混合して固形分が50重量％の洗剤スラリーを調整した（温度65℃）。この洗剤スラリーを向流式噴霧乾燥装置で噴霧乾燥して噴霧乾燥生成物ａ〜ｅを得た。得られた噴霧乾燥生成物の水分（105 ℃、２時間の減量）は何れも５％であった。
【００４４】
【表１】

【００４５】
（注）表１中の記号は以下の意味である。
・LAS-Na；直鎖アルキル(C₁₀〜C₁₄)ベンゼンスルホン酸ナトリウム
・AS-Na ；アルキル(C₁₂〜C₁₆)硫酸ナトリウム
・AOS-Na；アルファオレフィン(C₁₄〜C₁₈)スルホン酸ナトリウム
・α-SFE-Na ；α−スルホ脂肪酸(C₁₄〜C₁₈)メチルエステルナトリウム
・ノニオン活性剤；ポリオキシエチレンアルキルエーテル（アルキル基の炭素12〜14の第１級アルコールにエチレンオキシドを平均10モル付加）
・AA／MAコポリマー；アクリル酸／マレイン酸共重合体ナトリウム塩（モノマー比３：７、Mw≒70000 、中和度80％）、商品名「Sokalan CP-5」（BASF社製)
・チノパール CBS-X；蛍光染料、ジスチリルビフェニル誘導体（チバガイギー社製）
・チノパール DMS-X；蛍光染料、ビス−（トリアジニルアミノ）−スチルベン−ジスルホン酸誘導体（チバガイギー社製）
(2) 高密度洗剤組成物の調製
上記で得られた噴霧乾燥生成物ａ〜ｅと表２或いは表３に示す成分をレディゲミキサー（松坂貿易 (株) 、実施例１〜４及び比較例１〜２に使用）もしくはハイスピードミキサー（深江工業 (株) 、実施例５〜10及び比較例３〜６に使用）を用いて攪拌造粒した。ここで、非イオン性界面活性剤は所望の量を滴下して噴霧乾燥生成物に添加した。また、造粒終了１分前に平均粒径2.7 μｍの粉末ゼオライト（４Ａ型、トヨビルダー、東ソー (株) 製）を５重量部追加添加して流動性を改善した。得られた粉末洗剤組成物の嵩密度は0.70〜0.82ｇ／cm³ であった。
【００４６】
次に、この粉末洗剤組成物を1.4 mmの目開きのふるいでふるい分けし、ふるい上の残留物は粉砕機で粉砕した後にふるい通過物とブレンドした。このふるい分け終了品に対して粉末ゼオライト（４Ａ型、トヨビルダー、東ソー (株) 製）３重量部、酵素（API-21H 、昭和電工 (株) 製）１重量部をブレンドして最終粉末洗剤組成物を得た。なお、最終粉末洗剤組成物の平均粒径は300 〜400 μｍであった。この粉末洗剤組成物の洗浄力と溶解性の評価を以下の方法により行なった。
【００４７】
(3) 溶解性の評価
松下電器産業 (株) 製全自動洗濯機 4.2kg「愛妻号 NA-F42y1 」を用い、洗濯槽底部一端に洗剤33ｇをまとめて置き、その上に衣料（木綿肌着60重量％とポリエステル／綿混のワイシャツ40重量％）を３kg投入し、５℃の水道水を毎分10リットルの流速で洗剤に直接水があたらないように40リットルになるまで４分間かけて注水する。その後手洗い水流の設定で攪拌を３分間行い、排水して洗濯槽に残留する洗剤を目視判定する。その結果を表２及び表３に示す。なお、判定基準は以下の通りである。
◎；残留洗剤なし
○；僅かに小粒状の残留洗剤あり
△；多数の小粒状残留洗剤又は僅かに塊状残留洗剤あり
×；塊状の残留洗剤がかなり残る
【００４８】
【表２】

【００４９】
【表３】

【００５０】
実施例11〜13及び比較例７〜９
実施例１，３，５で得られた粉末洗剤組成物と、非イオン性界面活性剤としてエチレンオキサイド平均付加モル数が15のポリオキシエチレンアルキル(C₁₂) エーテルを用いた場合の溶解性及び洗浄力を評価した。ここで、洗浄力の評価は以下の方法により行なった。その結果を表４に示す。なお、各比較例の粉末洗剤組成物は何れも対応する実施例と同様のミキサーを用いて攪拌造粒した。
【００５１】
(4) 洗浄力の評価
洗剤水溶液１リットルに、下記組成の汚垢が塗布された10×10cmの人工汚染布12枚を入れ、浴比が１／60になるように同一サイズの汚染していない布を更に加えターゴトメーターにて100 r.p.m.で次の条件で洗浄した。
（汚垢の組成）
綿実油 60重量％
コレステロール 10重量％
オレイン酸 10重量％
パルミチン酸 10重量％
液体及び固体パラフィン 10重量％
（洗浄条件）
洗浄時間；10分
洗剤濃度；0.067 重量％
水温；20℃
水の硬度；４°DH
すすぎ；水道水にて５分間
洗浄力は汚染（インジケーターとしてカーボンブラックを常用により混入）前の原布及び洗浄前後の汚染布の反射率を測色計にて測定し、次式によって洗浄率（％）を求めた。その結果を表４に示すが、表４には汚染布12枚についての洗浄率の平均値を示す。
【００５２】
【数１】

【００５３】
【表４】

[0001]
[Industrial application fields]
The present invention relates to a method for producing a high-density granular detergent composition having good dispersion solubility in washing water.
[0002]
[Prior art]
Conventionally, low-density products obtained by a spray drying method have been mainly used as powder detergents, but in recent years, more compact high-density detergents have been put on the market for convenience of transporting, carrying and placing detergents. For example, Japanese Patent Laid-Open No. 48-61511 discloses a surfactant containing 30% or more and a bulk density of 0.5 g / cm. ^Three A granulated detergent composition having a particle diameter in the range of 0.5 to 5 mm is disclosed. Japanese Patent Laid-Open No. 48-61511 discloses a bulk density of 0.55 g / cm in which a specific amount of a surfactant 30% to 70% and various detergent builders are dry-blended. ^Three The above detergents are disclosed. Further, JP-A-58-132093 discloses a granular detergent composition having improved solubility, which contains an anionic surfactant and an anionic polymer which are intimately mixed. This publication was prepared by adding a water-soluble neutral or alkaline salt and mixtures thereof by preparing an intimate mixture of a specific water-soluble anionic polymer in advance with a non-soap anionic active agent. High density (eg 0.67 g / cm) obtained by blending the spray-dried granular mixture with other detergent ingredients ^Three Degree) granular detergent.
[0003]
However, such a high-density powder detergent generally does not have satisfactory dispersibility and solubility, and even in the example described in the above-mentioned Japanese Patent Application Laid-Open No. 58-132093, cold water that is generally used in the winter season. In the condition where the detergent particles are left for a certain period of time without receiving a relatively large mechanical force, the dispersion solubility is still insufficient, and the fundamental solution has not been achieved. It was.
[0004]
In addition, there is also a problem of a decrease in solubility due to an aspect when a fully automatic washing machine is used in a general household. That is, when using a fully automatic washing machine in a general household, first a predetermined amount of high-density detergent is put into the washing machine and then water is poured, but during the water filling, the stirring of the washing machine is stopped, The detergent particles exist in a localized state without being dispersed, and are slowly infiltrated with water, together with the formation of a paste-like phase containing a very high concentration of detergent components and water on the particle surface. Unification occurs. As a result, the entire localized detergent particles are covered with a hydrated, highly viscous paste-like phase that cannot be dispersed by the mechanical force of just the wash cycle that begins after water injection and remains undissolved during normal washing times. May occur. The formation of a pasty phase is more remarkable as the temperature of tap water is lower, and is particularly likely to occur when the surfactant component of the composition is mainly an anionic surfactant.
[0005]
[Problems to be solved by the invention]
In order to solve the problem of solubility and dispersibility of high-density detergents, the present applicants have previously focused on crystalline inorganic salts present in detergent particles as a cause of solubility reduction, and means for improving solubility It was proposed to limit the amount of crystalline inorganic salt such as soda ash added to the detergent dough and dry blend the inorganic salt (Japanese Patent Laid-Open No. 62-167399). However, this method needs to manage the particle size and bulk density of the detergent dough and the crystalline particles in order to prevent classification between particles, and additionally requires a step of dry blending the crystalline particles with the detergent particles. Compared with the conventional method, it was disadvantageous on the manufacturing apparatus.
[0006]
On the other hand, Japanese Patent Application Laid-Open No. 5-271700 and Japanese Patent Application Laid-Open No. 6-2000 propose the addition of potassium carbonate to the detergent slurry in order to suppress the dry mixing amount of the crystalline inorganic salt. Is expensive, and is not necessarily desirable in practice.
[0007]
Thus, it is difficult to say that the solubility and dispersibility problems of powder or granular high-density detergents have been sufficiently solved, and high-density detergents that have improved these problems without reducing the cleaning power It is desired.
[0008]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the present inventors stir and granulate a spray-dried product containing at least one anionic surfactant and at least one builder to form a high-density granular detergent composition. In the production of a product, it is an ethylene oxide adduct of a primary or secondary alcohol having 10 to 16 carbon atoms, wherein the average added mole number of ethylene oxide is in a specific range and the water content is 5 to 20% by weight. It has been found that the solubility of the resulting high-density granular detergent composition is improved by adding an ionic surfactant during the stirring granulation, and the present invention has been completed.
[0009]
That is, the present invention stirs and granulates a spray-dried product containing at least one anionic surfactant and at least one builder to give a bulk density of 0.65 g / cm. ^Three In producing the above high-density granular detergent composition, it is an ethylene oxide adduct of a primary or secondary alcohol having 10 to 16 carbon atoms, the average number of moles of ethylene oxide added is 4 to 12, and the water content is The present invention provides a method for producing a high-density granular detergent composition, wherein 5 to 20% by weight of a water-containing nonionic surfactant is added during the stirring granulation.
[0010]
The production method of the present invention is to add a nonionic surfactant having a limited ethylene oxide average addition mole number and water content when stirring and granulating a spray-dried product containing an anionic surfactant and a builder. It is characterized by.
[0011]
By using a nonionic surfactant containing an ethylene oxide average addition mole number and water in such a specific range, the water contained in the nonionic surfactant gradually becomes water in the spray-dried product. Uniform hydration is achieved by combining with a salt. By uniformly hydrating, detergent particles are bonded and agglomerated by hydration of the hydrated salt in low-temperature water, and when the detergent mixed with water is pasted, delay of dissolution due to hardening of the paste, Residue is avoided. On the other hand, when only the water is added when the spray-dried product is stirred and granulated, hydration with the hydrated salt occurs as soon as the water comes into contact with the spray-dried product. It becomes inhomogeneous and many unhydrated parts are localized, resulting in poor solubility in low-temperature water.
[0012]
As described above, the nonionic surfactant used in the present invention has a water content of 5 to 20% by weight, preferably 5 to 10% by weight. If the water content of the nonionic surfactant is less than 5% by weight, sufficient hydration of the hydrated salt cannot be achieved. On the other hand, if the water content exceeds 20% by weight, the water contained in the granulated product becomes too much and the physical properties of the granulated product are deteriorated, so that a detergent of good quality cannot be obtained.
[0013]
The nonionic surfactant used in the present invention is an ethylene oxide adduct of a primary or secondary alcohol having 10 to 16 carbon atoms, and the average added mole number of ethylene oxide is preferably 4 to 12, preferably Is 5-10. If the carbon number of the alcohol used as the raw material for the nonionic surfactant is outside the above range, the detergency is poor. Moreover, the thing whose average added mole number of ethylene oxide remove | deviates from the said range is inferior to a detergency, and mixability with water will worsen that an average added mole number is less than four. In view of the solubility of the final detergent, the most preferable embodiment of the nonionic surfactant is a polyoxyethylene alkyl ether obtained by adding an average of 5 to 10 moles of ethylene oxide to a primary alcohol having an alkyl chain length of 12 to 14. It is to be used as an aqueous solution whose amount is 5 to 10%.
[0014]
The spray-dried product containing at least one anionic surfactant and at least one builder used in the present invention is prepared by a known method for producing this kind of spray-dried dough, such as a countercurrent spray dryer. It is prepared by the method used.
[0015]
The average particle size of the spray-dried product is preferably about 300 to 1000 μm, and the water content of the spray-dried product is preferably about 1 to 12% by weight (weight loss at 105 ° C. for 2 hours).
[0016]
Subsequently, the spray-dried product is subjected to a step of granulating with stirring to increase the bulk density. The method of stirring and granulating and the method of increasing the bulk density can also be performed according to known methods. For stirring granulation of spray-dried products, so-called vertical mixers such as high-speed mixers (stirring rolling granulators), Henschel mixers (high-speed stirring granulators), and so-called Redige mixers are used. Any of the horizontal mixers can be used. In order to increase the bulk density of the spray-dried product, for example, as described in JP-A-61-69897, JP-A-61-69900, JP-A-2-232299, and JP-A-2-232300. A method or the like is used.
[0017]
In the present invention, the specific water-containing nonionic surfactant described above is added to the spray-dried product in this spray-drying stirring granulation step. The method for adding the water-containing nonionic surfactant is not limited, and it may be a method of dripping or spraying the spray-dried product. The nonionic surfactant is preferably added in an amount of 1 to 10% by weight, preferably 1 to 5% by weight in the final composition, excluding moisture. When the addition amount of the nonionic surfactant increases, the powder physical properties tend to decrease.
[0018]
Moreover, after stirring granulation, in order to improve fluidity | liquidity and non-caking property, an appropriate fine powder can be added to granulated particle as a surface coating agent, and the surface of granulated particle can also be coat | covered. Examples of the surface coating agent include aluminosilicate, silicon dioxide, and amorphous silica derivatives. Among these, those having an average primary particle size of 10 μm or less are preferable. The surface coating agent is added in an amount of 0.5 to 30 parts by weight, preferably 1 to 25 parts by weight, based on 100 parts by weight of the granulated particles.
[0019]
The spray-dried product used in the production method of the present invention contains at least one anionic surfactant and at least one builder.
[0020]
Examples of the anionic surfactant include the following.
(1) Linear or branched (preferably linear) alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16
(2) having a linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 20, ethylene oxide, or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1, or ethylene oxide / butylene oxide 0.1 /9.9 to 9.9 / 0.1 is an average of 1 to 8 moles of alkyl or alkenyl ether sulfate added, preferably ethylene oxide is averaged to a linear or branched alkyl group having a primary carbon number of 12 to 18 Alkyl ether sulfate added 1-3
(3) Alkyl or alkenyl sulfate having an alkyl group or alkenyl group having an average carbon number of 10 to 20
(4) Olefin sulfonates with an average of 10-20 carbon atoms in one molecule
(5) Alkane sulfonates with an average 10-20 carbon atoms in one molecule
(6) Saturated or unsaturated fatty acid salts having an average of 10 to 24 carbon atoms in one molecule
(7) having an average of 10 to 20 alkyl or alkenyl groups, ethylene oxide, or propylene oxide / ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1, or ethylene oxide / butylene oxide = 0.1 / 9.9 to 9.9 / Alkyl or alkenyl ether carboxylate in which 0.1 is added in an average of 0.5 to 8 mol per molecule
(8) α-sulfo fatty acid salt or ester represented by the following formula
[0021]
[Chemical 1]

[0022]
(In the formula, Y represents an alkyl group having 1 to 3 carbon atoms (preferably a methyl group) or a counter ion. Z represents a counter ion. R represents an alkyl group or an alkenyl group having 10 to 20 carbon atoms.)
(9) Other examples include saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof.
[0023]
Among these, particularly preferred anionic surfactants are (1), (2), (3) and (6).
[0024]
The blending amount of the anionic surfactant is not limited, but 10 to 40% by weight, preferably 20 to 35% by weight in the final detergent composition may be blended from the viewpoint of detergency and solubility.
[0025]
Moreover, as a builder, what is known as a builder for normal detergents can be used, and specifically, the following can be used. Builders are usually blended in the final composition at 10-60% by weight.
[0026]
(I) Inorganic builder
1) Alkali salts represented by alkali metal silicates such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, JIS No. 1 sodium silicate.
2) Neutral salts such as sodium sulfate.
3) Phosphate (alkali metal salts such as sodium and potassium) such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate and phytate.
4) Further, the following crystalline aluminosilicates or crystalline layered silicates different from the above alkali metal silicates can also be mentioned.
Specific examples include crystalline aluminosilicates represented by the following formula.
x '(M ₂ O) ・ Al ₂ O _Three ・ Y '(SiO ₂ ) ・ W '(H ₂ O)
(In the formula, M is an alkali metal atom such as sodium or potassium, x ′, y ′, w ′ represents the number of moles of each component, generally 0.7 ≦ x ′ ≦ 1.5, 0.8 ≦ y ′ ≦ 6. , W 'is an arbitrary constant.)
Of these, those represented by the following general formula are particularly preferred.
Na ₂ O ・ Al ₂ O _Three ・ YSiO ₂ ・ WH ₂ O
(In the formula, y represents 1.8 to 3.0 and w represents a number of 1 to 6.)
Also, the following formula
M ₂ Si _x O _{(2x + 1)} ・ Y (H ₂ O)
(In the formula, M represents an alkali metal, and x and y are 1.5 ≦ x ≦ 4, y ≦ 25, preferably y ≦ 20, and more preferably y = 0.)
The crystalline layered silicate shown by these is also mentioned. This compound is described in Japanese Patent Application Laid-Open No. 60-227895, and is generally obtained by baking amorphous glassy sodium silicate at 200 to 1000 ° C. to make it crystalline. Details of the synthesis method are described in, for example, Phys. Chem. Glasses. 7, 127-138 (1966), Z. Kristallogr., 129, 396-404 (1969).
This crystalline layered silicate is, for example, a product name “Na-SKS-6” (σ-Na ₂ Si ₂ O _Five ) Can be obtained in the form of fine powder, powder or granule. In the present invention, those having a particle size of 5 to 500 μm can be used, but those having a particle size of 10 to 300 μm are preferred.
[0027]
5) Further, an oil-absorbing amorphous aluminosilicate represented by the following general formula (1) is exemplified as an oil-absorbing carrier having a high oil-absorbing property and a high cation exchange capacity. Oil-absorbing carriers are the preferred builder in the case of powder detergents using liquid nonionic surfactants.
a (M ₂ O) ・ Al ₂ O _Three ・ B (SiO ₂ ) ・ C (H ₂ O) (1)
[In the formula, M represents an alkali metal atom, a, b, and c represent the number of moles of each component, 0.7 ≦ a ≦ 2.0, 0.8 ≦ b <4, and c is an arbitrary positive number. ]
In particular, the following general formula (2)
Na ₂ O ・ Al ₂ O _Three ・ M (SiO ₂ ) ・ C (H ₂ O) (2)
[Where m represents a number from 1.8 to 3.2 and c represents a number from 1 to 6. ]
The thing represented by these is preferable.
The method for producing the amorphous aluminosilicate having high oil absorption and high ion exchange capacity usable in the present invention is, for example, SiO. ₂ And M ₂ The molar ratio of O (M means alkali metal) is SiO ₂ / M ₂ O = 1.0-4.0 and H ₂ O and M ₂ The molar ratio of O is H ₂ O / M ₂ M is added to an alkali metal silicate aqueous solution with O = 12 to 200. ₂ O and Al ₂ O _Three Molar ratio is M ₂ O / Al ₂ O _Three = 1.0 to 2.0, H ₂ O and M ₂ The molar ratio of O is H ₂ O / M ₂ A low alkali alkali metal aluminate aqueous solution of O = 6.0 to 500 is added under strong stirring at a temperature of 15 to 60 ° C., preferably 30 to 50 ° C. Further, an alkali metal silicate aqueous solution may be added to the alkali metal aluminate aqueous solution.
The resulting white precipitate slurry is then heat-treated at a temperature of 70 to 100 ° C., preferably 90 to 100 ° C. for 10 minutes to 10 hours, preferably 5 hours or less, and then advantageously obtained by filtration, washing and drying. be able to. Ion exchange capacity 100 CaCO by this method _Three An amorphous aluminosilicate oil-absorbing carrier having a mg / g or more and an oil absorption capacity of 200 ml / 100 g or more can be easily obtained (see JP-A-62-191417 and JP-A-62-191419).
[0028]
Among these inorganic builders, sodium tripolyphosphate, sodium carbonate, crystalline aluminosilicate, and crystalline layered silicate are more preferable. In particular, as the crystalline aluminosilicate (zeolite), a synthetic zeolite having an average primary particle diameter of 0.1 to 10 μm represented by A-type and X-type zeolite is preferably used. Zeolite is blended as zeolite agglomerated dry particles obtained by drying powder and / or zeolite slurry. Zeolite may usually be blended in an amount of 5 to 60% by weight in the total composition.
[0029]
(II) Organic Builder
Examples of the organic builder include the following substances.
1) Ethane-1,1-diphosphonic acid, ethane-1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane- Phosphonic acid salts such as 1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid
2) Salts of phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid
3) Salts of amino acids such as aspartic acid and glutamic acid
4) Aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate, diethylenediaminepentaacetate, etc.
5) Polyacrylic acid, polyglyoxylate, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinyl as described in JP-A-54-52196 Phosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride- Ethylene crosslink copolymer, maleic anhydride-vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride- Isoprene copolymer from maleic anhydride and carbon monoxide Derived poly-β-ketocarboxylic acid, itaconic acid, ethylene copolymer, itaconic acid-aconitic acid copolymer, itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, malonic acid-methylene copolymer Polymer, itaconic acid-fumaric acid copolymer, acrylic acid-maleic acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer, 1-butene-2,3,4-tricarboxylic acid Acid-itaconic acid-acrylic acid copolymer, polyester polyaldehyde carboxylic acid having a quaternary ammonium group, cis-isomer of epoxy succinic acid, poly [N, N-bis (carboxymethyl) acrylamide], poly (oxycarboxylic) Acid), denbun succinic acid or maleic acid or terephthalic acid ester, starch phosphate ester Le, dicarboxylate starch, di carboxymethyl starch, carboxymethyl cellulose, a polymer electrolyte such as succinic acid ester
6) Non-dissociating polymers such as polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, cold water soluble urethanized polyvinyl alcohol
7) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-2,2, 5,5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, sucrose, lactose, raffinose and other carboxymethylated products, pentaerythritol carboxymethylated product, gluconic acid carboxymethylated product, polyhydric alcohol or saccharide and maleic anhydride Or a condensate with succinic anhydride, a condensate of oxycarboxylic acid with maleic anhydride or succinic anhydride, benzene polycarboxylic acid represented by merit acid, ethane-1,1,2,2-tetracarboxylic acid, Ethene-1,1,2,2-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, propane-1,2,3-trica Rubonic acid, butane-1,4-dicarboxylic acid, oxalic acid, sulfosuccinic acid, decane-1,10-dicarboxylic acid, sulfotricarballylic acid, sulfoitaconic acid, malic acid, oxydisuccinic acid, gluconic acid, CMOS, Builder M, etc. Organic acid salt.
[0030]
Among these organic builders, citrate, polyacrylate, polyglyoxylate, acrylic acid-maleic acid copolymer, and polyethylene glycol are more preferable.
[0031]
In the present invention, the following components can be blended in the final high-density detergent composition, depending on the properties of each component, whether added in advance to the spray-dried product or during granulation, Alternatively, after blending, after-blending may be performed.
[0032]
(1) Other surfactants
Nonionic surfactants other than those prescribed in the present invention, betaine-type amphoteric surfactants, sulfonic acid-type amphoteric surfactants, phosphate-based surfactants, or cationic surfactants (including amines), etc.
(2) Bleach
Examples include sodium percarbonate, sodium perborate (monohydrate is preferred), sodium sulfate hydrogen peroxide adduct, and the like, and sodium percarbonate is particularly preferred.
(3) Bleach activator
Tetraacetylethylenediamine, acetoxybenzene sulfonate, organic peracid precursor described in JP-A-59-22999, JP-A-63-258447, or JP-A-6-316700, or a transition metal as a metal ion Metal catalysts stabilized with a blocking agent
(4) Enzyme (Enzyme is an enzyme that naturally performs its action during the washing process.)
When classified from the reactivity of the enzyme, hydrolases, hydrases, oxidoreductases, desmolases, transferases and isomerases can be mentioned, but any of them can be applied to the present invention. Particularly preferred are hydrolases, including proteases, esterases, lipases, carbohydrases, nucleases, cellulases and amylases.
Specific examples of proteases are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promeline, carboxypeptidase A and B, aminopeptidase, aspergillopeptidase A and B, commercially available products Examples include sabinase, alcalase (Novo Industry), API 21 (Showa Denko KK), Maxacar (Gist Brocades), and protease K-14 or K-16 described in JP-A-5-43892. .
Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipase, phospholipase, cholinesterase and phosphotase.
For example, as the lipase, a commercially available lipase such as lipolase (Novo Industry) can be used.
Specific examples of carbohydrase include cellulase, maltase, saccharase, amylase, pectinase, lysozyme, α-glycosidase and β-glycosidase.
As cellulase, for example, commercially available cellzyme (Novo Industry), cellulase described in claim 4 of JP-A-63-264699 can be used, and as amylase, for example, commercially available Termamyl (Novo Industry), etc. Can be used.
[0033]
(5) Enzyme stabilizer
Reducing agent (sodium sulfite, sodium hydrogen sulfite), calcium salt, magnesium salt, polyol, boron compound, etc.
(6) Blue tinting agent
Various bluing agents can be blended as necessary. For example, the structures of the following formulas (i) and (ii) are recommended.
[0034]
[Chemical formula 2]

[0035]
(Where D ₁ Represents a blue to purple monoazo, disazo or anthraquinone dye residue, X ₁ And Y ₁ Is a hydroxyl group; an aliphatic amino group which may be substituted with an amino group, a hydroxyl group, a sulfonic acid group, a carboxylic acid group or an alkoxy group; a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxylic acid group, a lower alkyl group or a lower alkoxy group Represents an aromatic amino group or a cycloaliphatic amino group which may be substituted with a group, and R represents a hydrogen atom or a lower alkyl group. Where R 1 represents a hydrogen atom and (1) X ₁ And Y ₁ Simultaneously represent a hydroxyl group or an alkanolamino group, and (2) X ₁ And Y ₁ Except that either one is a hydroxyl group and the other is an alkanolamino group. n represents an integer of 2 or more. )
[0036]
[Chemical 3]

[0037]
(Where D ₂ Represents a blue to purple azo or anthraquinone dye residue, R represents a hydrogen atom or a lower alkyl group, X ₂ And Y ₂ Represent the same or different alkanolamino groups or hydroxyl groups. )
(7) Anti-caking agent
Examples of the anti-caking agent include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, and magnesium oxide. A porous material such as fine powder silica can be used as a carrier for a nonionic surfactant. Clay (smectite clay) is also effective as a softening agent.
[0038]
(8) Antioxidants
Antioxidants include tert-butylhydroxytoluene, 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2′-butylidenebis- (6-tert-butyl-4-methylphenol) ), Monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1′-bis- (4-hydroxyphenyl) cyclohexane and the like.
[0039]
(9) Fluorescent dye
As fluorescent dyes, 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole 1 to 2% by weight of a derivative, 4,4′-bis (triazol-2-yl) stilbene derivative, bis (triazinylamino) stilbene disulfonic acid derivative in the composition Can do.
(10) Photo-activated bleach
One or two kinds of sulfonated aluminum phthalocyanine and sulfonated zinc phthalocyanine can be contained in the composition in an amount of 0 to 0.2% by weight.
(11) Fragrance
As the fragrance, a fragrance conventionally blended with a detergent, for example, a fragrance described in JP-A-63-101496 can be used.
(12) Antifoam agent
Examples of the antifoaming agent include silicone / silica-based ones, and an antifoaming agent granulated product produced using the method described in JP-A-3-186307 may be used.
[0040]
The bulk density of the granular detergent composition produced by the production method of the present invention described above is 0.65 g / cm. ^Three Or more, preferably 0.65-0.85 g / cm ^Three More preferably, 0.70 to 0.82 g / cm ^Three It is.
[0041]
【The invention's effect】
In the high-density granular detergent composition produced according to the present invention, the hydrated salt is uniformly hydrated and present in the particles at the time of granulation, so that the binding and agglomeration of the detergent particles are avoided and the solubility is improved. . In particular, the high-density detergent composition obtained according to the present invention exhibits excellent solubility and exhibits sufficient detergency even when low temperature washing water is used.
[0042]
【Example】
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
[0043]
Examples 1-10 and Comparative Examples 1-6
(1) Preparation of spray-dried product
The ingredients shown in Table 1 were mixed with water to prepare a detergent slurry having a solid content of 50% by weight (temperature 65 ° C.). The detergent slurry was spray dried with a countercurrent spray dryer to obtain spray dried products ae. The resulting spray-dried product had a water content of 5% (105 ° C., reduced for 2 hours).
[0044]
[Table 1]

[0045]
(Note) The symbols in Table 1 have the following meanings.
・ LAS-Na; linear alkyl (C _Ten ~ C ₁₄ ) Sodium benzenesulfonate
AS-Na; alkyl (C ₁₂ ~ C ₁₆ ) Sodium sulfate
・ AOS-Na; Alpha olefin (C ₁₄ ~ C ₁₈ ) Sodium sulfonate
・ Α-SFE-Na; α-sulfo fatty acid (C ₁₄ ~ C ₁₈ ) Methyl ester sodium
Nonionic activator; polyoxyethylene alkyl ether (addition of an average of 10 moles of ethylene oxide to a primary alcohol having 12 to 14 carbon atoms in the alkyl group)
AA / MA copolymer; acrylic acid / maleic acid copolymer sodium salt (monomer ratio 3: 7, Mw≈70000, neutralization degree 80%), trade name “Sokalan CP-5” (manufactured by BASF)
・ Chinopearl CBS-X; fluorescent dye, distyrylbiphenyl derivative (Ciba Geigy)
・ Chinopearl DMS-X; fluorescent dye, bis- (triazinylamino) -stilbene-disulfonic acid derivative (manufactured by Ciba Geigy)
(2) Preparation of high-density detergent composition
The spray-dried products a to e obtained above and the components shown in Table 2 or Table 3 are used as a Redige mixer (used in Matsuzaka Trading Co., Ltd., Examples 1 to 4 and Comparative Examples 1 to 2) or a high speed mixer. (Used in Fukae Kogyo Co., Ltd., Examples 5 to 10 and Comparative Examples 3 to 6), and granulated with stirring. Here, the desired amount of nonionic surfactant was added dropwise to the spray-dried product. One minute before the end of granulation, 5 parts by weight of powdered zeolite (4A type, Toyo Builder, manufactured by Tosoh Corporation) having an average particle diameter of 2.7 μm was added to improve the fluidity. The bulk density of the obtained powder detergent composition is 0.70 to 0.82 g / cm. ^Three Met.
[0046]
The powder detergent composition was then screened with a 1.4 mm sieve and the residue on the sieve was ground with a grinder and blended with the sieve pass through. The final powder detergent composition by blending 3 parts by weight of powdered zeolite (4A type, Toyo Builder, manufactured by Tosoh Corporation) and 1 part by weight of enzyme (API-21H, manufactured by Showa Denko Co., Ltd.) I got a thing. The average particle size of the final powder detergent composition was 300 to 400 μm. The cleaning power and solubility of this powder detergent composition were evaluated by the following methods.
[0047]
(3) Evaluation of solubility
Using Matsushita Electric Industrial Co., Ltd.'s fully automatic washing machine 4.2kg "Aizuma No. NA-F42y1", 33g of detergent is put together on the bottom of the washing tub, and clothing (60% cotton underwear and polyester / cotton blend) is placed on it. 3kg of shirt (40% by weight) is poured in at a flow rate of 10 liters per minute for 4 minutes until it reaches 40 liters so that the detergent is not directly exposed to water. Then, stirring is performed for 3 minutes with the setting of the water flow of hand washing, and the detergent remaining in the washing tub after being drained is visually determined. The results are shown in Tables 2 and 3. The determination criteria are as follows.
◎: No residual detergent
○: Slightly granular residual detergent present
Δ: Many small granular residual detergents or slightly bulk residual detergents
×: Massive residual detergent remains
[0048]
[Table 2]

[0049]
[Table 3]

[0050]
Examples 11-13 and Comparative Examples 7-9
The powder detergent compositions obtained in Examples 1, 3 and 5 and polyoxyethylene alkyl (C) having an average addition mole number of ethylene oxide of 15 as a nonionic surfactant ₁₂ ) The solubility and detergency when using ether were evaluated. Here, the cleaning power was evaluated by the following method. The results are shown in Table 4. In addition, each powder detergent composition of each comparative example was stirred and granulated using the same mixer as the corresponding Example.
[0051]
(4) Detergency evaluation
Add 12 sheets of 10 x 10 cm artificially soiled cloth with the following composition to 1 liter of aqueous detergent solution, and add another unstained cloth of the same size so that the bath ratio is 1/60. Washing was performed with a meter at 100 rpm under the following conditions.
(Soil composition)
Cottonseed oil 60% by weight
Cholesterol 10% by weight
Oleic acid 10% by weight
Palmitic acid 10% by weight
10% by weight of liquid and solid paraffin
(Cleaning conditions)
Cleaning time: 10 minutes
Detergent concentration: 0.067% by weight
Water temperature: 20 ° C
Water hardness: 4 ° DH
Rinse; 5 minutes with tap water
The detergency was measured with a colorimeter to measure the reflectance of the raw cloth before contamination (carbon black was mixed as a normal indicator) and the contaminated cloth before and after washing, and the washing rate (%) was obtained by the following equation. The results are shown in Table 4. Table 4 shows the average value of the cleaning rate for 12 sheets of contaminated cloth.
[0052]
[Expression 1]

[0053]
[Table 4]

Claims (4)

In producing a high-density granular detergent composition having a bulk density of 0.65 g / cm ³ or more by stirring and granulating a spray-dried product containing at least one anionic surfactant and at least one builder, carbon is used. A water-containing nonionic surfactant having an ethylene oxide adduct of several tens to 16 primary or secondary alcohols having an average ethylene oxide addition mole number of 4 to 10 and a water content of 5 to 20% by weight. It adds at the time of the said stirring granulation, The manufacturing method of the high-density granular detergent composition characterized by the above-mentioned.   The method for producing a high-density granular detergent composition according to claim 1, wherein the nonionic surfactant has an average added mole number of ethylene oxide of 5 to 10. The final high-density granular detergent composition is an ethylene oxide adduct of 10 to 40% by weight of an anionic surfactant and a primary or secondary alcohol having 10 to 16 carbon atoms, and the average number of moles of ethylene oxide added is 4 to 4 non-ionic surfactants 1-10% by weight of 10, the production method according to claim 1 or 2 high density granular detergent composition according containing builder 10-60 wt%.   The water-containing nonionic surfactant is an ethylene oxide adduct of a primary alcohol having 12 to 14 carbon atoms, and contains a nonionic surfactant having an ethylene oxide average addition mole number of 5 to 10, The method for producing a high-density granular detergent composition according to any one of claims 1 to 3, which is a hydrous nonionic surfactant having a water content of 5 to 10% by weight.