JP3556806B2 - Detergent composition - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は洗浄剤原液塗布により頑固な油汚れでも良好な洗浄力を有し、つけ置き洗いでも実用的な洗濯が行える液体洗浄剤に関し、更に詳細にはシルク製品、ウ−ル製品、おしゃれ着などわずかな汚れでも洗浄の必要が生じる衣類に対し、つけ置き洗いにより実用的な洗浄力と形態保持機能を有し、特に、水洗いでは汚れ落ちが困難な油性汚れまで、洗浄剤組成物原液を塗布することで非常に高い洗浄力を有し、かつ、従来の洗浄剤組成物よりも優れた風合いを生じるつけ置き洗い専用の洗浄剤組成物に関する。
【０００２】
【従来の技術】
従来のつけ置き洗いとは一般に洗濯機、手洗い（もみ洗い）等で洗濯する前の予洗のことを指したり、酵素を配合し洗浄力を強化した洗剤溶液につけておくこと等を指していた。従って長時間（例えば一晩）つけておかないと十分に汚れが落ちなかった為、シルクやウ−ルの衣料をこのように長時間つけておくと、衣類が縮むという問題が多々生じていた。従って、ここでいうつけ置き洗いとは極めて短時間１０〜３０分でよいため、シルクやウ−ル等デリケ−トな衣類の縮み等の不都合もなく、汚れを落とし、風合いも良く洗濯して仕上げることが出来る利点がある。
家庭における衣類の洗濯は、従来よりアニオン界面活性剤或いはノニオン界面活性剤を主成分とする洗浄剤で洗浄を行った後、繊維の風合い及び帯電防止能を付与するために、カチオン界面活性剤を主成分とする柔軟剤で更に柔軟処理を行っている。しかし、この方法では洗浄及び柔軟性付与という２操作が必要となり煩雑さを伴う。そこで、特公昭４７−４７５０号公報及び特開昭５７−１２６８９６号公報には、上記２液型とは異なり、上記操作を同時に行う１液型の洗浄方法が開示されている。
この１液型組成物は主として、ノニオン界面活性剤或いは半極性界面活性剤を主成分とし、分子内に長鎖の飽和基を有するモノアルキルまたはジアルキル型カチオン界面活性剤を柔軟剤成分として配合しているものである。この系は配合当初においては常温で透明であるが、長期にわたり保存すると不溶化物を析出したり、低温で白濁や沈澱を生じ商品価値を著しく低下させる。その結果、性能面では適度な洗浄力と風合いを保持しながらも、安定性の面で問題があり、産業的実施を困難にしていた。
【０００３】
そこで、特開平４−４２９８号公報及び特開平４−１５３３００号公報、米国４２２２９０５号公報、米国４２５９２１７号公報、米国４２３９６５９号公報などには、ノニオン界面活性剤とカチオン界面活性剤を基本骨格とする中性透明液体洗浄剤が開示されている。これら１液型の洗浄方法で適度な洗浄力を有し、優れた風合いを損なわず、しかも保存安定性に優れた中性透明液体洗浄剤が記載されている。しかし、おしゃれ着、特にシルク製品、ウ−ル製品は通常の洗濯方法（具体的には洗濯機でのマイルドな水流での洗浄方法やもんだり、押したりして手の動作を加えて洗浄する方法）では洗浄後の衣料が収縮したり、型くずれしたりして、衣料の商品価値を著しく低下させる。衣料の収縮や型くずれを防止する洗濯方法として、つけ置き洗浄法が知られているが、上記の洗浄剤では洗浄力が不十分であり、特にしみ汚れ等部分的に目立つ汚れを除去する効果に劣る。また、おしゃれ着、特にシルク製品、ウ−ル製品には、衣料の風合・形態保持機能に優れ、且つ洗浄機能にも優れる洗浄方法及び洗浄剤が求められていた。そこで、特開平７−５４２６４号公報、特開平６−３１３１９３号公報、特開平８−４８９９３号公報、特開平８−４８９９４号公報及び特開平８−４８９９５号公報には、水に易溶性の溶剤を配合することにより、水系での洗濯で落ち難い油汚れが落ちやすくなるとされている。
【０００４】
一方、ドライクリ−ニングもフロン、パ−クロロエチレン、石油等、環境に悪影響を与える溶剤を大量に使用することから最近では大きな環境問題になってきており、水溶性汚れの除去が十分でない点が、最近注目されてきている。しかし、おしゃれ着、特にシルク製品、ウ−ル製品は通常の洗濯方法（具体的には洗濯機でのマイルドな水流での洗浄方法やもんだり、押したりして手の動作を加えて洗浄する方法）が行なえないため、頑固な油汚れを落とすためにはドライクリ−ニングを行なわなければならない。そこで、特開平５−５１５９８公報には、グリコ−ルエ−テル系溶剤を用いる新しいドライクリ−ニング溶剤に関する記載で、環境安全性と水溶性汚れの除去がこれまでより改善された報告がなされている。ところが、水溶性汚れの除去は、水系の洗濯と比較するとまだまだ不十分であり、溶剤中心としたドライクリ−ニングでは、いまだに十分解決されるに至っていない。
こうした、背景からおしゃれ着、特にシルク製品、ウ−ル製品等の通常の洗濯方法が不向きな衣料に関しては、水溶性汚れもしくは頑固な油汚れのどちらかに重点をおいた洗濯方法しかなされていなかった。
【０００５】
そこで、従来のつけおき洗剤と同等以上の洗浄力と風合いを有し、且つ、これまでドライクリ−ニングでしか落とせなかった頑固な油汚れを、手軽に落とす事が出来る、水溶性汚れ及び頑固な油汚れ共に汚れ落ち効果の高い洗浄剤組成物が求められている。
【０００６】
【発明が解決しようとする課題】
本発明は、おしゃれ着、特にシルク製品、ウ−ル製品に対して実用的な洗浄力と形態保持機能を有し、洗浄後の衣料に優れた柔軟性と風合いを付与すると共に、頑固な油汚れ部分に洗浄剤原液を塗布することで落ちが良く、常温及び低温において低粘度で安定なつけ置き洗い専用の洗浄剤組成物を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明は、（Ａ）式（１）：
【０００８】
【化１９】
式中、［Ｒ１ は炭素数１０〜２２の直鎖もしくは分岐アルキル基及びアルケニル基、または炭素数６〜１２のアルキル基をもつアルキルフェニル基を、またｎは５〜１５を表す］で示されるノニオン界面活性剤、
（Ｂ）式（２）：
【００１０】
【化２０】
［式中、Ｒ2 、Ｒ3 、Ｒ4 及びＲ5 は互いに独立で、そのうち２つは炭素数１２〜２４のアルキル基またはアルケニル基、残り２つはメチル基、エチル基、ポリオキシエチレン基またはポリオキシプロピレン基を表し、Ｘはハロゲン原子、ＣＨ3 ＳＯ4 またはＣ2 Ｈ5 ＳＯ4 のいずれかを表す］で示される１種又は２種以上で且つその全体のヨウ素価が４０〜１００であるカチオン性界面活性剤、（Ｃ） 式（４）
【００１４】
【化２２】
式中、［Ｒ7 は炭素数５〜１２の直鎖もしくは分岐のアルキル基、炭素数５〜１２の直鎖もしくは分岐のアルキル基をもつアルキルフェニル基のいずれかを表し、Ｒ8 は炭素数２〜５のアルキレン基、またｍは１〜３を表す］で示される水難溶性溶剤の１種または２種以上、及び（Ｄ） 式（６）：
【００１８】
【化２４】
式中、［Ｒ10は炭素数４以下のの直鎖もしくは分岐アルキル基またはアルケニル基、フェニル基、ベンジル基及び水素のいずれかを表し、Ｒ11は炭素数２〜５の直鎖もしくは分岐のアルキレン基、またｌは１〜３を表す］で示される水易溶性溶剤の１種または２種以上、（Ｅ）アミドベタイン系両性界面活性剤、さらに任意成分として（Ｆ）水に対する溶解度が１０重量％以上の塩を含有する洗浄剤組成物を提供するものである。
【００２０】
【発明の実施の形態】
本発明に用いる式（１）で示すノニオン界面活性剤はエチレンオキシド付加型のノニオン界面活性剤であって、エチレンオキシドの付加モル数が５〜１５で、炭素数１０〜２２のアルキル基またはアルケニル基を有するポリオキシエチレンアルキルまたはアルケニルエーテル、あるいは炭素数が６〜１２のアルキル基を持つポリオキシエチレンアルキルフェニルエーテルである。本発明では、これらの１種又は２種以上を用いることができ、その配合量は組成物全量に対して好ましくは１０〜５０重量％、より好ましくは１５〜４０重量％である。配合量が１０重量％未満では洗浄力が弱いばかりでなく、低温での安定性が低下する。一方、５０重量％超えて配合すると常温での溶解性が悪くゲル状となりがちである。特に好ましくは３０重量以下である。
【００２１】
本発明に用いる式（２）で示されるカチオン界面活性剤はジ長鎖アルキル第４級アンモニウム塩の１種又は２種以上であって、カチオン界面活性剤全体のヨウ素価として４０〜１００である。そのジ長鎖アルキルは、アルキル基またはアルケニル基の何れであってもよく、その炭素数は１２〜２４、好ましくは１６〜２０であり、長鎖アルキルの炭素数が１２未満の場合は洗浄後の布地に充分な柔軟性や風合いが得られず、炭素数が２４を超えると低温で透明に溶解しない。また２つの長鎖アルキルは同一でも異なっていてもよい。
他のアルキルとしてはメチル基、エチル基、また好ましくは付加モル数が１〜５のポリオキシエチレン基またはポリオキシプロピレン基が挙げられ、特に好ましくはメチル基である。Ｘは塩素、臭素またはヨウ素などのハロゲン原子、ＣＨ３ ＳＯ４ 、Ｃ２ Ｈ５ ＳＯ４ のいずれかであり、好ましくは塩素である。
【００２２】
ジ長鎖アルキル第４級アンモニウム塩は、ジオレイルジメチルアンモニウムクロリド、オレイン酸や牛脂脂肪酸由来或いは大豆油脂肪酸由来の混合不飽和アルキル基のジアルキルジメチルアンモニウムクロリドなどが好ましく、特にジオレイルジメチルアンモニウムクロリドが好ましい。又２種以上を組み合わせて用いる場合には上記ジオレイルジメチルアンモニウムクロリド等の不飽和アルキル基を含むものに加え、ジステアリルジメチルアンモニウムクロリド等の飽和アルキル基を含むものを用いてもよい。
また、本発明のカチオン界面活性剤では、そのヨウ素価が４０〜１００であり、好ましくは６０〜９０である。ただし、２種以上のジ長鎖アルキル第４級アンモニウム塩を組み合わせて用いる場合には、この範囲に調整しなければならない。ヨウ素価が４０未満の場合、低温での安定性が損なわれ、１００を超えると保存安定性が損なわれる。
これらカチオン界面活性剤の配合量は組成物全量に対して好ましくは１〜１５重量％、より好ましくは２〜１０重量％である。配合量が１重量％未満では、洗浄後の繊維に柔軟性が付与されず、１５重量％を超えて配合すると低温安定性が損なわれ、洗浄力が低下する。特に好ましくは７重量％以下である。
【００２３】
本発明に用いる水難溶性溶剤は式（４）：
【００２６】
【化２６】
式中、［Ｒ７ は炭素数５〜１２の直鎖もしくは分岐アルキル基、炭素数５〜１２の直鎖もしくは分岐のアルキル基をもつアルキルフェニル基のいずれかを表し、Ｒ８ は炭素数２〜５のアルキレン基、またｍは１〜３を表す］で示される水難溶性グリコールエーテル系溶剤から選ばれる１種または２種以上である。
【００２８】
水難溶性グリコールエーテル系溶剤として、エチレングリコールモノヘキシルエーテル、ジエチレングリコールモノ−２−エチルヘキシルエーテル等が例示できる。これら水難溶性溶剤では、水難溶性グリコールエーテル系溶剤が好ましく、中でも、ジエチレングリコールモノ−２−エチルヘキシルエーテル、ジエチレングリコールモノヘキシルエーテル等が特に好ましい。これらの配合量は組成物全量に対して好ましくは１〜４０重量％、より好ましくは１〜２０重量％で、特に５〜２０重量％が好ましい。配合量が１重量％に満たないと、油汚れ落ちが十分でなく、４０重量％を超えて配合すると保存安定性に問題が生じる。本発明に用いる水易溶性溶剤は、式（６）：
【００３１】
【化２８】
式中、［Ｒ１０は炭素数４以下の直鎖もしくは分岐のアルキル基またはアルケニル基、フェニル基、ベンジル基及び水素のいずれかを表し、Ｒ１１は炭素数２〜５のアルキレン、またｌは１〜３を表す］で示される水易溶性グリコールエーテル系溶剤の１種又は２種以上である。
【００３３】
水易溶性グリコールエーテル系溶剤としてエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、イソプロピレングリコールモノメチルエーテル、イソプロピレングリコールモノエチルエーテル、３−メトキシブタノール、３−メチル−３−メトキシブタノールなどが挙げられ、中でも水易溶性グリコールエーテル系溶剤が好ましく、特にイソプロピレングリコールモノメチルエーテル、イソプロピレングリコールモノエチルエーテル、３−メトキシブタノール、３−メチル−３−メトキシブタノールが好ましい。これら水易溶性溶剤の配合量は好ましくは０．１〜３０重量％であり、より好ましくは０．１〜２０重量％、さらに好ましくは２〜２０重量％である。配合量がこれらの範囲以外では保存安定性が損なわれる。特に好ましくは１５重量％以下である。
【００３４】
本発明に用いることができるアミドベタイン系両性界面活性剤としては、ステアリルアミドプロピルジメチルアミノ酢酸ベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノスルホベタイン等が例示でき、特にヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタインが好ましい。その配合量は組成物全量に対して０．０１〜２．０重量％であり、特に０．１〜１．０重量％が好ましい。アミドベタイン系両性界面活性剤を上記の範囲の量添加すると、衣類の仕上がりがより改善される。
【００３５】
本発明に用いることができる水に対する溶解度（標準状態（２５℃））が１０重量％以上である塩は、無機酸の塩及び有機酸の塩の何れであっても良く、塩の形態を用いても、組成物の製造過程で酸とアルカリから調整しても良い。無機酸の塩として、ナトリウム、カリウム、アンモニウム等の塩化塩、硫酸塩、硝酸塩、炭酸塩、炭酸水素塩、硼酸塩等が挙げられ、有機酸の塩としては、クエン酸塩、安息香酸塩、コハク酸塩、乳酸塩等が挙げられ、好適には、無機酸の塩として、塩化ナトリウム、硫酸ナトリウム、また、有機酸の塩としてクエン酸ナトリウムが挙げられる。これら塩は、その１種または２種以上を用いる事ができ、その配合量は０．０１〜５．０重量％、特に２．０重量％以下が好ましい。配合量が５．０重量％以下が安定性の面から好ましい。
【００３６】
本発明の組成物は、常法により製造することができ、衣料用、浴室用などの種々の汚れに対して利用でき、衣料用、特につけ置き洗い用の低粘度（５〜５００ｃｐ；Ｂ型粘度計、スピンドル＃２）液体洗浄剤として用いるのが好適である。
【００３７】
本発明では、本発明の効果を損なわない限り、従来公知のポリビニルアルコール、カルボキシメチルセルローズ、ヒドロキシプロピルメチルセルローズ、ヒドロキシブチルセルローズなどの水溶性ポリマー、アニオン界面活性剤、アミンオキシド等の半極性界面活性剤、香料、酵素（例えば、酵素としてはタンパク質加水分解酵素、脂質加水分解酵素、デンプン加水分解酵素、溶菌酵素等）、殺菌剤、顔料、染料なども適宜配合することができる。
【００３８】
【実施例】
本発明を実施例を用いて、さらに詳しく説明する。言うまでもなく、本発明はこれら実施例に限られるものでなく、又、特に断らない限り［％］は［重量％］を表す。
表１に示す実施例（及び比較例）を常法により調製し、安定性試験、柔軟性試験、原液塗布洗浄試験及びつけ置き洗浄力試験にて評価した。評価方法を示す。なお、各試験には水道水を用いた。
【００３９】
＜評価方法＞
１．安定性試験
各実施例及び比較例を１００ｍｌ容のスクリュー管に取り、−５℃、０℃、５℃及び２５℃の恒温槽に１ヶ月間放置して、その外観を目視により判定した。
評価基準は以下の通りであり、○を良好と判断する。
○ ：透明、流動性あり
△ ：半透明、流動性あり
× ：白濁、結晶析出または固化
【００４０】
２．柔軟性試験
各実施例及び比較例（３０℃、０．１％水溶液５００ｍｌ）の中に、２０ｃｍ ×２０ｃｍ のシルク布（絹１００％の平織布）を１０分間浸漬し、振り濯ぎを２回行った後、１０秒間脱水し風乾する洗浄操作を１サイクルとし、これを５サイクル繰返した。５サイクル終了後、低温のアイロンをかけて試験布とし、官能評価より、未洗浄布との一対比較にて判定した。
評価基準は以下の通りであり、◎、○を合格とする。
◎ ： 未洗浄シルク布より非常に柔らかい。
○ ： 未洗浄シルク布より柔らかい。
△ ： 未洗浄シルク布よりわずかにかたい。
× ： 未洗浄シルク布よりかたい。
【００４１】
３．原液塗布洗浄力試験
５ｃｍ ×５ｃｍのラード汚染布５枚と口紅汚染布５枚に、それぞれ実施例及び比較例を各汚染布１枚当たり１ｍｌずつ塗布し１５分間放置した。次に、これらを水１０リットル中に浸漬し、つけ置き洗浄した。洗浄後、ラード汚染布の洗浄率は、人工汚染布の洗浄前と洗浄後、白布（対照）の各々の反射率を測色色差計ＺＥ−２０００（日本電色工業製）で測定し、次式により洗浄率を算出した。なお、洗浄率は５枚の平均値で示し、６０％以上が有効である。
【００４２】
【数１】
また、口紅汚染布の洗浄率は、５名のモニターにより、洗浄前の汚染布の状態を５点、元の白布を１点として目視判定により１〜５点の点数をつけ、５枚の平均値で評価する。評価基準は下記のとおりであり、２．５以下を合格とする。
１：口紅が完全にとれた。
２：口紅がわずかにのこった。（輪郭がわかる程度。）
３：口紅がのこった。
４：口紅が殆ど落ちていない。
５：口紅が洗浄前と変わらない。
【００４４】
試験に供したラード汚染布と口紅汚染布の作成方法及び洗浄条件は以下の通りである。
＜口紅汚染布の作成方法＞
市販の口紅を５ｃｍ ×５ｃｍ の綿金巾３号布に２５ｍｇ／１枚ずつ薄く塗布する。
＜洗浄条件＞
洗浄時間（つけ置き時間） １５分間
洗浄温度 ２５℃
すすぎ 振りすすぎ
脱水 洗濯乾燥後の白色タオルにはさみ脱水
【００４５】
４．つけ置き洗浄力試験
実施例及び比較例の水溶液１リットル中に５ｃｍ×５ｃｍの洗濯科学協会の湿式人工汚染布５枚を浸漬し、つけ置き洗浄を行った後、洗浄率により洗浄力を評価した。洗浄率は、人工汚染布の洗浄前と洗浄後、白布（対照）を測色色差計ＺＥ−２０００（日本電色工業製）で測定し、次式により洗浄率を算出した。
【００４６】
【数２】
なお、洗浄率は５枚の平均値で示し、１５％以上が有効である。また、洗浄条件は以下の通りである。
＜洗浄条件＞
洗浄時間 １５分間
洗浄剤組成物 ０．１％
洗浄温度 ２５℃
すすぎ 振りすすぎ
脱水 洗濯乾燥後の白色タオルにはさみ脱水
【００４８】
【表１】
本発明の洗浄剤組成物は、表１の実施例と比較例を比較して、安定性、柔軟性、頑固な油汚れに対する洗浄力、及び、つけ置き洗浄による洗浄力とも優れていると認められた。従って本発明ではノニオン界面活性剤、カチオン界面活性剤、水難溶性溶剤、水易溶性溶剤、アミドベタイン系両性界面活性剤、及び無機塩を配合すると、低温でも粘度安定な液体のため簡便に利用でき、頑固な油汚れを簡単に落とすことが出来、実用的な洗浄力、形態保持機能、洗浄後の繊維の柔軟性、風合いなどの諸特性までをも有する洗浄剤組成物を得ることができたと認められた。
【００５０】
【発明の効果】
本発明の洗浄剤組成物はシルク製品、ウ−ル製品、おしゃれ着などの洗浄に際し、実用的な洗浄力と形態保持機能を有し、洗浄後の繊維に優れた柔軟性及び風合いを付与することができ、特に洗浄剤組成物そのものを塗布することにより頑固な油汚れ落ちが良い。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a liquid detergent which has a good detergency even with stubborn oil stains by applying a detergent undiluted solution, and can perform practical washing even with immersion washing, and more particularly, silk products, wool products, fashionable dressing For clothing that needs to be washed even with a slight amount of dirt, it has a practical detergency and form retention function by immersion washing, especially for oily dirt that is difficult to remove by washing with water. The present invention relates to a cleaning composition exclusively used for immersion cleaning, which has a very high detergency when applied and produces a better texture than conventional cleaning compositions.
[0002]
[Prior art]
The conventional soak washing generally refers to pre-washing before washing in a washing machine, hand washing (fir washing) or the like, or to soaking in a detergent solution containing an enzyme to enhance washing power. Therefore, if the clothes were not worn for a long time (for example, overnight), the stains would not be sufficiently removed, and if the clothes such as silk or wool were worn for such a long time, the clothes would often shrink. . Therefore, the soaking washing here can be performed in a very short time of 10 to 30 minutes, so that there is no inconvenience such as shrinkage of delicate clothes such as silk and wool, and that dirt is removed and washing is performed with a good texture. There is an advantage that can be finished.
Washing of clothes at home is conventionally carried out by washing with a cleaning agent containing anionic surfactant or nonionic surfactant as a main component, and then adding a cationic surfactant to impart texture and antistatic ability of the fiber. Further softening treatment is performed with a softener as a main component. However, this method requires two operations, i.e., washing and flexibility, and is complicated. Therefore, Japanese Patent Publication No. 47-4750 and Japanese Patent Application Laid-Open No. 57-126896 disclose a one-pack cleaning method in which the above operations are performed simultaneously, unlike the above-described two-pack cleaning.
This one-pack composition mainly comprises a nonionic surfactant or a semipolar surfactant as a main component, and a monoalkyl or dialkyl cationic surfactant having a long-chain saturated group in a molecule as a softener component. Is what it is. This system is transparent at room temperature at the beginning of the formulation, but when stored for a long period of time, it precipitates insolubilized substances, or becomes cloudy or precipitates at low temperatures, significantly lowering its commercial value. As a result, while maintaining an appropriate detergency and texture in terms of performance, there is a problem in stability, making industrial implementation difficult.
[0003]
Therefore, JP-A-4-4298 and JP-A-4-153300, U.S. Pat. No. 4,222,905, U.S. Pat. No. 4,259,217, U.S. Pat. No. 4,239,659, disclose a nonionic surfactant and a cationic surfactant as a basic skeleton. A neutral clear liquid detergent is disclosed. There is described a neutral transparent liquid detergent which has an appropriate detergency by these one-part cleaning methods, does not impair an excellent texture, and has excellent storage stability. However, fashionable clothes, especially silk products and wool products, are usually washed by a normal washing method (specifically, a washing method with a mild current in a washing machine, or a manual operation such as squeezing or pushing). In the method, the clothing after washing shrinks or loses its shape, thereby significantly reducing the commercial value of the clothing. As a washing method for preventing clothing shrinkage and shape loss, a soaking washing method is known. However, the above-mentioned detergent has insufficient cleaning power, and particularly has an effect of removing partially conspicuous stains such as stain stains. Inferior. In addition, for fashionable clothes, especially silk products and wool products, there has been a demand for a cleaning method and a cleaning agent which are excellent in a function and a function for maintaining the feel and shape of clothing and also excellent in a cleaning function. Therefore, JP-A-7-54264, JP-A-6-313193, JP-A-8-48993, JP-A-8-48994 and JP-A-8-48995 disclose a water-soluble solvent. It is said that by blending, oil stains, which are hard to remove by washing in an aqueous system, can be easily removed.
[0004]
On the other hand, dry cleaning has recently become a major environmental problem due to the use of a large amount of environmentally harmful solvents such as chlorofluorocarbons, perchlorethylene, and petroleum. , Has been attracting attention recently. However, fashionable clothes, especially silk products and wool products, are usually washed by a normal washing method (specifically, a washing method with a mild current in a washing machine, or a manual operation such as squeezing or pushing). Method), dry cleaning must be performed to remove stubborn oil stains. Thus, Japanese Patent Application Laid-Open No. 5-51598 describes a new dry cleaning solvent using a glycol ether-based solvent, and reports that environmental safety and removal of water-soluble stains have been improved more than ever. . However, removal of water-soluble stains is still insufficient as compared with water-based washing, and solvent-based dry cleaning has not yet been sufficiently solved.
For clothes that are not suitable for ordinary washing methods such as fashionable clothes, especially silk products and wool products from the background, only washing methods focusing on either water-soluble stains or stubborn oil stains are performed. Was.
[0005]
Therefore, water-soluble stains and stubborn oils, which have a detergency and texture equal to or higher than those of conventional detergents, and can easily remove stubborn oil stains that could only be removed by dry cleaning until now. There is a need for a detergent composition that has a high soil removal effect for both oil stains.
[0006]
[Problems to be solved by the invention]
INDUSTRIAL APPLICABILITY The present invention has a practical detergency and a shape-retaining function for fashionable clothes, especially silk products and wool products, and imparts excellent flexibility and texture to washed clothes, as well as a stubborn oil. It is an object of the present invention to provide a cleaning composition dedicated to immersion cleaning, which is easy to remove by applying a cleaning stock solution to a contaminated portion, has low viscosity at room temperature and low temperature, and is stable.
[0007]
[Means for Solving the Problems]
The present invention relates to (A) Formula (1):
[0008]
Embedded image
In the formula, [R 1 represents a linear or branched alkyl group and alkenyl group having 10 to 22 carbon atoms, or an alkylphenyl group having an alkyl group having 6 to 12 carbon atoms, and n represents 5 to 15]. Nonionic surfactant,
(B) Equation (2):
[0010]
Embedded image
Wherein R 2 , R 3 , R 4 and R 5 are independent of each other, two of which are alkyl or alkenyl groups having 12 to 24 carbon atoms, and the other two are methyl, ethyl or polyoxyethylene groups. Or X represents a halogen atom, CH 3 SO 4 or C 2 H 5 SO 4 ] or one or more of the above, and the total iodine value is 40 to 100. (C) a cationic surfactant which is Equation (4)
[0014]
Embedded image
In the formula, [R 7 represents any of a linear or branched alkyl group having 5 to 12 carbon atoms and an alkylphenyl group having a linear or branched alkyl group having 5 to 12 carbon atoms, and R 8 represents 2 to 5 alkylene groups, and m represents 1 to 3], and one or more of the poorly water-soluble solvents represented by the formula ( D ) :
[0018]
Embedded image
Wherein, [R 10 is 4 or less of the straight-chain or branched alkyl or alkenyl group carbon atoms, a phenyl group, or an benzyl group and hydrogen, R 11 is straight or branched having 2 to 5 carbon atoms alkylene group, also l is one or more readily water-soluble solvent represented by 'an integer of 1 to 3, the solubility (F) water (E) amide betaine amphoteric surfactant, as further optional components 10 It is intended to provide a detergent composition containing not less than% by weight of a salt.
[0020]
BEST MODE FOR CARRYING OUT THE INVENTION
The nonionic surfactant represented by the formula (1) used in the present invention is a nonionic surfactant of an ethylene oxide addition type, which has an addition mole number of ethylene oxide of 5 to 15 and has an alkyl group or alkenyl group having 10 to 22 carbon atoms. Polyoxyethylene alkyl or alkenyl ether, or a polyoxyethylene alkyl phenyl ether having an alkyl group having 6 to 12 carbon atoms. In the present invention, one or more of these can be used, and the blending amount is preferably from 10 to 50% by weight, more preferably from 15 to 40% by weight, based on the total amount of the composition. If the amount is less than 10% by weight, not only the detergency is weak, but also the stability at low temperatures is reduced. On the other hand, if it is added in an amount of more than 50% by weight, the solubility at room temperature is poor and the composition tends to be gelled. Particularly preferably, the weight is 30% or less.
[0021]
The cationic surfactant represented by the formula (2) used in the present invention is one or more dilong-chain alkyl quaternary ammonium salts, and has an iodine value of 40 to 100 as a whole of the cationic surfactant. . The dilong chain alkyl may be either an alkyl group or an alkenyl group, and has 12 to 24 carbon atoms, preferably 16 to 20 carbon atoms. When the carbon number exceeds 24, the fabric does not melt transparently at low temperatures. The two long-chain alkyls may be the same or different.
Examples of the other alkyl include a methyl group, an ethyl group, and preferably a polyoxyethylene group or a polyoxypropylene group having an addition mole number of 1 to 5, and particularly preferably a methyl group. X is a halogen atom such as chlorine, bromine or iodine, CH 3 SO 4 , or C 2 H 5 SO 4 , and is preferably chlorine.
[0022]
The di-long chain alkyl quaternary ammonium salt is preferably dioleyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride of mixed unsaturated alkyl groups derived from oleic acid or tallow fatty acid or soybean oil fatty acid, and particularly dioleyl dimethyl ammonium chloride. preferable. When two or more kinds are used in combination, those containing a saturated alkyl group such as distearyl dimethyl ammonium chloride may be used in addition to those containing an unsaturated alkyl group such as dioleyl dimethyl ammonium chloride.
The iodine value of the cationic surfactant of the present invention is 40 to 100, preferably 60 to 90. However, when two or more di-long chain alkyl quaternary ammonium salts are used in combination, the content must be adjusted to this range. When the iodine value is less than 40, stability at low temperature is impaired, and when it exceeds 100, storage stability is impaired.
The amount of these cationic surfactants is preferably 1 to 15% by weight, more preferably 2 to 10% by weight, based on the total amount of the composition. If the amount is less than 1% by weight, the fibers after washing will not have flexibility, and if the amount exceeds 15% by weight, the low-temperature stability will be impaired and the detergency will be reduced. Particularly preferably, it is at most 7% by weight.
[0023]
The poorly water-soluble solvent used in the present invention is represented by the formula (4) :
[0026]
Embedded image
In the formula, [R 7 represents a linear or branched alkyl group having 5 to 12 carbon atoms, or an alkylphenyl group having a linear or branched alkyl group having 5 to 12 carbon atoms, and R 8 represents 2 carbon atoms. Or 5 or more, and m represents 1 to 3], or one or more selected from poorly water-soluble glycol ether solvents.
[0028]
As water sparingly soluble glycol ether solvent, ethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether and the like. Among these poorly water-soluble solvents, poorly water-soluble glycol ether solvents are preferable, and among them, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol monohexyl ether and the like are particularly preferable. The amount of these compounds is preferably 1 to 40% by weight, more preferably 1 to 20% by weight, and particularly preferably 5 to 20% by weight, based on the total amount of the composition. If the amount is less than 1% by weight, the removal of oil stains is not sufficient, and if the amount exceeds 40% by weight, there is a problem in storage stability. The water-soluble solvent used in the present invention is represented by the formula (6) :
[0031]
Embedded image
In the formula, [R 10 represents any of a linear or branched alkyl or alkenyl group having 4 or less carbon atoms, a phenyl group, a benzyl group, and hydrogen, R 11 represents an alkylene having 2 to 5 carbon atoms, and 1 represents 1 to 3] of water-soluble glycol ether solvents.
[0033]
Readily water-soluble glycol ether solvent as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, isopropylene glycol monomethyl ether, isopropylene glycol monoethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol Among them, a water-soluble glycol ether solvent is preferable, and isopropylene glycol monomethyl ether, isopropylene glycol monoethyl ether, 3-methoxybutanol, and 3-methyl-3-methoxybutanol are particularly preferable. The compounding amount of these water-soluble solvents is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, and further preferably 2 to 20% by weight. If the amount is outside these ranges, the storage stability is impaired. It is particularly preferably at most 15% by weight.
[0034]
Examples of the amidobetaine-based amphoteric surfactant that can be used in the present invention include stearylamidopropyldimethylaminoacetic acid betaine, coconut fatty acid amidopropyldimethylaminosulfobetaine, and the like, and in particular, coconut fatty acid amidopropyldimethylaminoacetic acid betaine. preferable. The compounding amount is 0.01 to 2.0% by weight based on the total amount of the composition, and particularly preferably 0.1 to 1.0% by weight. When the amidobetaine-based amphoteric surfactant is added in an amount within the above range, the finish of clothes is further improved.
[0035]
The salt having a solubility in water (standard state (25 ° C.)) of 10% by weight or more which can be used in the present invention may be any of an inorganic acid salt and an organic acid salt. Alternatively, it may be adjusted from an acid and an alkali during the production process of the composition. Salts of inorganic acids include salts of sodium, potassium, ammonium, etc., sulfates, nitrates, carbonates, bicarbonates, borates, and the like.As salts of organic acids, citrates, benzoates, Succinate, lactate and the like can be mentioned, and preferably, salts of inorganic acids include sodium chloride and sodium sulfate, and salts of organic acids include sodium citrate. One or more of these salts can be used, and the amount of the salt is preferably 0.01 to 5.0% by weight, particularly preferably 2.0% by weight or less. An amount of 5.0% by weight or less is preferable from the viewpoint of stability.
[0036]
The composition of the present invention can be produced by a conventional method, can be used for various stains such as clothing and bathrooms, and has a low viscosity (5 to 500 cp; Viscometer, spindle # 2) Suitable for use as liquid detergent.
[0037]
In the present invention, as long as the effects of the present invention are not impaired, conventionally known polyvinyl alcohols, water-soluble polymers such as carboxymethyl cellulose, hydroxypropyl methyl cellulose, and hydroxybutyl cellulose, anionic surfactants, and semipolar surfactants such as amine oxides Agents, fragrances, enzymes (for example, enzymes such as protein hydrolase, lipid hydrolase, starch hydrolase, and lytic enzyme), bactericides, pigments, dyes, and the like can also be appropriately compounded.
[0038]
【Example】
The present invention will be described in more detail using examples. Needless to say, the present invention is not limited to these Examples, and unless otherwise specified, [%] represents [% by weight].
Examples (and comparative examples) shown in Table 1 were prepared by a conventional method, and evaluated by a stability test, a flexibility test, a stock solution application cleaning test, and a standing cleaning power test. The evaluation method will be described. In each test, tap water was used.
[0039]
<Evaluation method>
1. Stability Test Each Example and Comparative Example was placed in a 100-ml screw tube, left in a thermostat at -5 ° C, 0 ° C, 5 ° C, and 25 ° C for one month, and its appearance was visually evaluated.
The evaluation criteria are as follows, and ○ is judged to be good.
：: Transparent, with fluidity △: Translucent, with fluidity ×: Cloudy, crystallized or solidified
2. Flexibility test A 20 cm × 20 cm 2 silk cloth (100% silk plain woven cloth) is immersed in each of the examples and comparative examples (30 ° C., 500 ml of 0.1% aqueous solution) for 10 minutes and shake-rinse twice. After that, the washing operation of dehydrating and air-drying for 10 seconds was defined as one cycle, and this cycle was repeated five cycles. After 5 cycles, the test cloth was ironed at a low temperature to make a test cloth, and a sensory evaluation was made to determine a pair with an unwashed cloth.
The evaluation criteria are as follows, and ◎ and ○ are regarded as pass.
◎: Very softer than unwashed silk cloth.
：: Softer than unwashed silk cloth.
Δ: Slightly harder than unwashed silk cloth.
×: Harder than unwashed silk cloth.
[0041]
3. Example solution and comparative example were applied to five lard-contaminated cloths and five lipstick-contaminated cloths each having a size of 5 cm × 5 cm, and each of them was left for 15 minutes. Next, these were immersed in 10 liters of water, immersed and washed. After the washing, the cleaning rate of the lard-contaminated cloth was measured by measuring the reflectance of the white cloth (control) before and after the cleaning of the artificially contaminated cloth with a colorimetric colorimeter ZE-2000 (manufactured by Nippon Denshoku Industries). The cleaning rate was calculated by the equation. The cleaning rate is shown as an average value of five sheets, and 60% or more is effective.
[0042]
(Equation 1)
The cleaning rate of the lipstick contaminated cloth was evaluated by 5 monitors, and the condition of the contaminated cloth before cleaning was 5 points, and the original white cloth was 1 point. Evaluate by value. The evaluation criteria are as follows, and 2.5 or less is regarded as acceptable.
1: Lipstick was completely removed.
2: The lipstick was slightly overlaid. (The outline is understandable.)
3: Lipstick was left.
4: Almost no lipstick is dropped.
5: Lipstick is the same as before washing.
[0044]
The methods for preparing lard-contaminated cloth and lipstick-contaminated cloth and the cleaning conditions used in the test are as follows.
<How to make lipstick contaminated cloth>
A commercially available lipstick is thinly applied to a 5 cm × 5 cm cotton cloth No. 3 cloth at 25 mg / sheet.
<Washing conditions>
Cleaning time (placement time) 15 minutes Cleaning temperature 25 ° C
Rinse, rinse, rinse and dehydrate Wash to dry and dry between white towels [0045]
4. Soaking cleaning power test Five pieces of 5 cm x 5 cm wet artificial contaminated cloth of the Washing Science Association were immersed in 1 liter of the aqueous solution of each of the examples and comparative examples, and after performing soaking cleaning, the cleaning power was evaluated by the cleaning rate. . The cleaning rate was measured by using a colorimeter ZE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) on a white cloth (control) before and after cleaning the artificially stained cloth, and the cleaning rate was calculated by the following equation.
[0046]
(Equation 2)
The cleaning rate is shown as an average value of five sheets, and 15% or more is effective. The cleaning conditions are as follows.
<Washing conditions>
Cleaning time 15 minutes Cleaning composition 0.1%
Washing temperature 25 ℃
Rinse, rinse, rinse, and dehydrate between white towels after washing and drying
[Table 1]
The cleaning composition of the present invention was found to be excellent in stability, flexibility, detergency against stubborn oil stains, and detergency by immersion cleaning, comparing the examples in Table 1 with Comparative Examples. Was done. Therefore, in the present invention, when a nonionic surfactant, a cationic surfactant, a poorly water-soluble solvent, a water-soluble solvent, an amidobetaine-based amphoteric surfactant, and an inorganic salt are blended, a liquid having a viscosity stable even at a low temperature can be easily used. , It was possible to easily remove stubborn oil stains, and to obtain a detergent composition having practical detergency, form retention function, fiber properties after washing, and various properties such as texture. Admitted.
[0050]
【The invention's effect】
The cleaning composition of the present invention has a practical detergency and shape-retaining function when washing silk products, wool products, and fashionable clothes, and imparts excellent flexibility and texture to washed fibers. In particular, stubborn oil stain removal is good by applying the cleaning composition itself.
Claims (6)
（Ｂ）式（２）：
（Ｃ）式（４）：
（Ｄ）式（６）：
（Ｅ）アミドベタイン系両性界面活性剤
を含有することを特徴とする洗浄剤組成物。(A) Equation (1):
(B) Equation (2):
(C) Equation (4):
(D) Equation (6):
A cleaning composition comprising (E) an amidobetaine-based amphoteric surfactant .
（Ｂ）式（２）：
（Ｃ）式（４）：
（Ｄ）式（６）：
（Ｅ）アミドベタイン系両性界面活性剤
を含有する請求項１項記載の洗浄剤組成物。(A) Equation (1):
(B) Equation (2):
(C) Equation (4):
(D) Equation (6):
The cleaning composition according to claim 1, further comprising (E) an amidobetaine-based amphoteric surfactant .
（Ｂ）式（２）：
（Ｃ）式（４）：
（Ｄ）式（６）：
（Ｅ）アミドベタイン系両性界面活性剤
を含有する請求項１項、又は請求項２の何れか１項記載の洗浄剤組成物。(A) Equation (1):
(B) Equation (2):
(C) Equation (4):
(D) Equation (6):
The cleaning composition according to any one of claims 1 and 2, further comprising (E) an amidobetaine-based amphoteric surfactant .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19446397A JP3556806B2 (en) | 1996-07-24 | 1997-07-18 | Detergent composition |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21426996 | 1996-07-24 | ||
| JP8-214268 | 1996-07-24 | ||
| JP21426896 | 1996-07-24 | ||
| JP8-214269 | 1996-07-24 | ||
| JP19446397A JP3556806B2 (en) | 1996-07-24 | 1997-07-18 | Detergent composition |
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| Publication Number | Publication Date |
|---|---|
| JPH1088195A JPH1088195A (en) | 1998-04-07 |
| JP3556806B2 true JP3556806B2 (en) | 2004-08-25 |
Family
ID=27326939
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19446397A Expired - Fee Related JP3556806B2 (en) | 1996-07-24 | 1997-07-18 | Detergent composition |
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| Country | Link |
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| JP (1) | JP3556806B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4089990B2 (en) * | 1998-12-17 | 2008-05-28 | 株式会社Ａｄｅｋａ | Cleaning composition |
| JP3645455B2 (en) * | 1999-09-06 | 2005-05-11 | 花王株式会社 | Cleaning composition |
| ES2596325T3 (en) * | 2002-12-04 | 2017-01-05 | Clariant International Ltd | Quaternary Ammonium Composition |
| JP4965821B2 (en) * | 2005-06-08 | 2012-07-04 | 花王株式会社 | Surfactant composition |
| JP5362173B2 (en) * | 2005-12-28 | 2013-12-11 | ライオン株式会社 | Liquid detergent composition and method for producing liquid detergent composition |
| TWI598437B (en) * | 2012-09-25 | 2017-09-11 | 獅子股份有限公司 | Liquid detergent |
| JP7133954B2 (en) * | 2018-03-20 | 2022-09-09 | ライオン株式会社 | Laundry detergent composition |
| JP7122909B2 (en) * | 2018-08-30 | 2022-08-22 | ライオン株式会社 | Liquid detergent composition for clothes |
| JP7357573B2 (en) * | 2020-03-12 | 2023-10-06 | ライオン株式会社 | Liquid cleaning composition for textile products |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8914602D0 (en) * | 1989-06-26 | 1989-08-16 | Unilever Plc | Liquid detergent composition |
| JPH078991B2 (en) * | 1989-07-18 | 1995-02-01 | 花王株式会社 | Neutral liquid detergent composition |
| US5035826A (en) * | 1989-09-22 | 1991-07-30 | Colgate-Palmolive Company | Liquid crystal detergent composition |
| JP2896218B2 (en) * | 1990-10-17 | 1999-05-31 | 旭電化工業株式会社 | Liquid light detergent composition |
| ZA925727B (en) * | 1991-08-09 | 1993-03-10 | Bristol Myers Squibb Co | Glass cleaning composition. |
| DK0600847T3 (en) * | 1992-11-26 | 1999-06-23 | Procter & Gamble | Purification Composition with Combined Highly Hydrophilic and Highly Hydrophobic Nonionic Surfactants |
| EP0616027A1 (en) * | 1993-03-19 | 1994-09-21 | The Procter & Gamble Company | Concentrated cleaning compositions |
| JP3176756B2 (en) * | 1993-04-30 | 2001-06-18 | サンスター株式会社 | Liquid detergent composition |
| JPH0848995A (en) * | 1994-08-05 | 1996-02-20 | Sunstar Inc | Liquid detergent composition |
| JPH0848994A (en) * | 1994-08-05 | 1996-02-20 | Sunstar Inc | Liquid detergent composition |
| JP3124684B2 (en) * | 1994-08-05 | 2001-01-15 | サンスター株式会社 | Liquid detergent composition |
-
1997
- 1997-07-18 JP JP19446397A patent/JP3556806B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH1088195A (en) | 1998-04-07 |
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