JP4055544B2 - Liquid softener composition - Google Patents

Description

（式中、Ｍ、Ｎ、ａ及びｂは平均重合度であり、Ｒは水素又はアルキル基を表す。）
【００２０】
ここで、Ｍは１０〜１００００、Ｎは１〜１０００、かつＭ＞Ｎであることが好ましく、Ｍは１０〜１０００、Ｎは１〜５０、かつＭ＞Ｎであることが更に好ましい。Ｍが大きいほど柔軟性は良好となるが、シリコーン化合物の粘度が高くなるため柔軟剤組成物製造時の作業性が悪くなる場合がある。ａは２〜１００、ｂは０〜５０が好ましい。Ｒとしては水素又は炭素数１〜４のアルキル基が好ましい。
【００２１】
本発明で用いるポリエーテル変性シリコーンオイルの具体的な例としては、東レ・ダウ コーニング・シリコーン（株）製のＳＨ３７７２Ｍ、ＳＨ３７７５Ｍ、ＳＨ３７４８、ＳＨ３７４９、ＳＦ８４１０、ＳＨ８７００、ＢＹ２２−００８、ＢＹ２２−０１２、ＳＦ８４２１、信越化学工業（株）製のＫＦ３５２Ａ、ＫＦ６００８、ＫＦ６１５Ａ、ＫＦ６０１６、ＫＦ６０１７、ＧＥ東芝シリコーン（株）製のＴＳＦ４４５０、ＴＳＦ４４５２、日本ユニカー（株）製のＳＩＬＷＥＴ Ｌ−７００１、ＳＩＬＷＥＴ Ｌ−７００２、ＳＩＬＷＥＴ Ｌ−７６０２、ＳＩＬＷＥＴ Ｌ−７６０４、ＳＩＬＷＥＴ ＦＺ−２１０４、ＳＩＬＷＥＴ ＦＺ−２１２０、ＳＩＬＷＥＴ ＦＺ−２１６１、ＳＩＬＷＥＴ ＦＺ−２１６２、ＳＩＬＷＥＴ ＦＺ−２１６４、ＳＩＬＷＥＴ ＦＺ−２１７１等が挙げられ、これらを１種単独で又は２種以上の混合物として用いることができる。
【００２２】
本発明で用いる（Ａ）成分のシリコーン化合物の配合量は特に限定されないが、柔軟性、滑らかさ、ドレープ性及び組成物の粘度の点から、配合量の下限は、液体柔軟剤組成物中の３質量％、特に５質量％、更に６質量％が好ましく、上限としては、７０質量％、特に５０質量％、更に４０質量％が好ましい。配合量が３質量％未満では、柔軟性、滑らかさ、ドレープ性などの効果が不充分になる場合があり、７０質量％を超えると組成物の粘度が高くなり、使用性が低下する場合がある。
【００２３】
本発明の（Ｂ）成分は、（Ａ）成分のシリコーン化合物を繊維へ吸着させる効果を有するものである。カチオン性を有する水溶性高分子化合物としては、水に溶解した時にカチオン性を有するものが使用し得るが、特にカチオン性を有する水溶性高分子化合物としては、アミノ基、アミン基、第４級アンモニウム基から選ばれる１種又は２種以上のカチオン性基を有する水溶性高分子化合物が好ましい。なお、本発明において、水溶性高分子とは、２５℃の水１００ｇに対し、水溶性高分子化合物１ｇを加えたときに、その液が濁らず透明であるものをいう。
【００２４】
（Ｂ）成分のカチオン性を有する水溶性高分子化合物は、カチオン化度が０．１％以上のものが好ましく、特に２．５％以上が好ましい。カチオン化度が０．１％未満のものでは、共存するシリコーン化合物を繊維へ吸着させる効果が小さくなり、多量の配合が必要となって経済的でない場合がある。また、高分子化合物自身が繊維製品に対し剛性を付与する性質を持っている場合は、多量に配合されると柔軟効果の低下がともなう場合がある。
【００２５】
ここで、カチオン化度とは、高分子化合物がカチオン性モノマーの重合体、カチオン性モノマーとノニオン性モノマーの共重合体、及びノニオン性重合体の一部をカチオン性基で変性又は置換したもの（カチオン化セルロースなど）の場合には下記式（１）により、また、高分子化合物がカチオン性モノマーとアニオン性モノマーの共重合体、及びカチオン性モノマーとアニオン性モノマーとノニオン性モノマーの共重合体の場合には、下記式（２）により算出される値と定義する。
カチオン化度（％）＝Ｘ×Ｙ×１００ …式（１）
（Ｘ：高分子化合物のカチオン性基中のカチオン化された原子（窒素等）の原子量
Ｙ：高分子化合物１ｇ中に含まれるカチオン性基のモル数）
カチオン化度（％）＝Ｘ×（Ｙ−Ｚ）×１００ …式（２）
[Ｘ：高分子化合物のカチオン性基中のカチオン化された原子（窒素等）の原子量
Ｙ：高分子化合物１ｇ中に含まれるカチオン性基のモル数
Ｚ：高分子化合物１ｇ中に含まれるアニオン性基のモル数
（Ｚのアニオン性基とは、高分子鎖中のモノマー単位に含まれるカルボキシル基、スルホン酸基などが挙げられる。具体的には、アクリル酸中のカルボン酸などである。ただし、カチオン性基の対イオンは含まない。）］
【００２６】
カチオン化度の算出例として、下記式で表されるＭＥＲＱＵＡＴ２８０（ｃａｌｇｏｎ社製）の場合を示す。
Ｘ：１４（窒素原子の原子量）
Ｙ：４．９５×１０^-3（カチオン性基の１ｇ中の重量：０．８ｇとカチオン性基の分子量より算出）
Ｚ：２．７８×１０^-3（アニオン性基の１ｇ中の重量：０．２ｇとアニオン性基の分子量より算出）
式（２）より、
カチオン化度（％）＝
１４×（４．９５×１０^-3−２．７８×１０^-3）×１００＝３．０
である。
【００２７】
【化２】

（ＭＥＲＱＵＡＴ２８０）
塩化ジメチルジアリルアンモニウムとアクリル酸との質量比＝８０：２０
【００２８】
よって、上記記載のカチオン化度の算出法によれば、ノニオン性モノマーの重合体やアニオン性モノマーの重合体のカチオン化度は０となる。
【００２９】
（Ｂ）成分の水溶性高分子は、ポリエチレングリコールを標準物質としてゲルパーメーションクロマトグラフィ法で測定される重量平均分子量が、１，０００〜５，０００，０００であることが好ましく、より好ましくは３，０００〜１，０００，０００であり、更に好ましくは５，０００〜５００，０００である。１，０００未満だと臭気の点で好ましくない場合があり、５，０００，０００を超えると組成物の粘性が高くなり、使用性が低下する場合がある。
【００３０】
（Ｂ）成分の例としては、ＭＥＲＱＵＡＴ１００（Ｃａｌｇｏｎ社製）、アデカカチオエースＰＤ−５０（旭電化工業（株）製）、ダイドールＥＣ−００４、ダイドールＨＥＣ、ダイドールＥＣ（大同化成工業（株）製）等の塩化ジメチルジアリルアンモニウムの重合体、ＭＥＲＱＵＡＴ５５０ ＪＬ５（Ｃａｌｇｏｎ社製）等の塩化ジメチルジアリルアンモニウム・アクリルアミド共重合体、ＭＥＲＱＵＡＴ２８０（Ｃａｌｇｏｎ社製）等の塩化ジメチルジアリルアンモニウム・アクリル酸共重合体、レオガードＫＧＰ（ライオン（株）製）等のカチオン化セルロース、ＬＵＶＩＱＵＡＴ−ＦＣ９０５（Ｂ・Ａ・Ｓ・Ｆ社製）等の塩化イミダゾリウム・ビニルピロリドン共重合体、ＬＵＧＡＬＶＡＮ−Ｇ１５０００（Ｂ・Ａ・Ｓ・Ｆ社製）等のポリエチレンイミン、ポバールＣＭ３１８（（株）クラレ製）等のカチオン化ポリビニルアルコール、キトサン等のアミノ基を有する天然系の高分子誘導体、ジエチルアミノメタクリレート・エチレンオキシド等が付加された親水基を有するビニルモノマーとの共重合体等が挙げられるが、本発明においては、塩化ジメチルジアリルアンモニウム重合体又は塩化イミダゾリウム・ビニルピロリドン共重合体を用いる。
【００３１】
この中で、シリコーンの付与する柔軟性などの風合いを妨げない観点から、（Ｂ）成分単独で吸着した時に繊維に付与する剛性の小さいものが好ましい。
【００３２】
特に好ましい高分子としては、下記一般式(ＩＩ)に示すジメチルジアリルアンモニウム塩を重合して得られるカチオン性高分子である。この高分子の構造は、通常、下記一般式（ＩＩＩ−１）又は下記一般式（ＩＩＩ−２）で表わされる。また、一般式（ＩＩＩ−１）の構造単位と一般式（ＩＩＩ−２）の構造単位が共に含まれていてもよい。
【００３３】
【化３】

（式中Ｘ^-は、塩化物イオン、臭化物イオンなどの任意のマイナスイオンを示す。）
【００３４】
【化４】

【００３５】
【化５】

（式中、ｃ、ｄは、各々平均重合度であり、各々６〜３００００の範囲であることが好ましく、より好ましくは２０〜６，０００、更に好ましくは３０〜３，０００の範囲である。）
【００３６】
このような高分子の例としては、ＭＥＲＱＵＡＴ１００（Ｃａｌｇｏｎ社製）、アデカカチオエースＰＤ−５０（旭電化工業（株）製）、ダイドールＥＣ−００４、ダイドールＨＥＣ、ダイドールＥＣ（大同化成工業（株）製）等が挙げられる。
【００３７】
本発明の（Ｂ）成分としては、上記のカチオン性を有する水溶性高分子化合物を１種単独で用いてもよいし、２種以上を混合物として用いることもできる。
【００３８】
（Ｂ）成分の配合量は特に限定されないが、繊維製品に剛性を付与しない範囲で、液体製品の場合は組成物中に０．１〜３０質量％配合され、更に好ましくは０．５〜１０質量％配合される。０．１質量％未満ではシリコーンの吸着促進効果が小さくなるため柔軟性、滑らかさ、ドレープ性などの効果が不充分であり、３０質量％を超えると組成物の粘度が高くなり使用性の面で好ましくない。
【００３９】
本発明の液体柔軟剤組成物中において、（Ａ）成分：（Ｂ）成分の質量比は、９９：１〜５０：５０の範囲内である。好ましくは９５：５〜６０：４０、更に好ましくは９０：１０〜７０：３０の範囲であり、この範囲内で、ポリエステル、綿等の衣類に対し柔軟性、滑らかさ、ドレープ性等の優れた機能が得られる。（Ｂ）成分の割合がこの範囲を超えて多くなる場合は、シリコーン化合物の付与する柔軟性、滑らかさ等の風合いが損なわれ、好ましくない。特に、（Ｂ）成分単独で繊維に対し剛性を付与する高分子の場合は、シリコーン化合物の付与する柔軟性、滑らかさを損なわせないため、この範囲内で（Ｂ）成分の割合はできる限り少ないほうが好ましい。一方、（Ｂ）成分の割合がこの範囲より少ない場合は、シリコーンの繊維への吸着性が低下し、好ましくない。
【００４０】
また、本発明の液体柔軟剤組成物は、実際に繊維製品の柔軟仕上げを行う際の全使用水量に対し、（Ａ）成分の濃度が５ｐｐｍ〜０．５質量％となるような量で使用するのが好ましく、更に好ましくは１０ｐｐｍ〜３００ｐｐｍとなるような量で使用される。また、（Ｂ）成分の濃度は０．５ｐｐｍ〜１００ｐｐｍとなるような量で使用するのが好ましく、更に好ましくは３ｐｐｍ〜３０ｐｐｍとなるような量で使用される。
【００４１】
（Ｃ）成分は、酸性染料及び直接染料からなる群から選ばれる１種又は２種以上の染料であれば、特に制限はない。添加できる染料の具体例としては、例えば染料便覧（有機合成化学協会編，昭和４５年７月２０日発行，丸善（株））、染料ノート第２２版（（株）色染社）、法定色素ハンドブック（日本化粧品工業連合会編、１９８８年１１月２８日発行、（株）薬事日報社）などに記載されているものが挙げられる。この中で、液体柔軟剤組成物の保存安定性や繊維に対する染着性の観点からは、下記（Ｃ−１）〜（Ｃ−３）群に属する１種又は２種以上の染料を用いることが好ましい。
【００４２】
（Ｃ−１）群は、スルホン酸基を有し、かつトリフェニルメタン構造、インジゴ構造、ジフェニル構造、アントラキノン構造を有する青色、紫色、緑色染料、及びフタロシアニン構造を有する青色染料である。このうち、トリフェニルメタン構造、フタロシアニン構造、アントラキノン構造を有する染料が好ましく、トリフェニルメタン構造、フタロシアニン構造をもつ染料がより好ましい。（Ｃ−１）群の具体例を以下に示す。
【００４３】
［青色染料］
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ １、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ７、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ９、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ １５、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ２２、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ２３、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ２５、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ２７、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ４０、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ４１、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ４３、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ４５、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ６２、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ７４、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ７８、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ８０、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ８２、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ８３、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ９０、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ９３、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ １００、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ １０３、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ １０４、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ １１２、
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ １２７、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ １３８、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ １、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ２、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ６、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ１５、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ２２、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ２５、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ４１、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ７６、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ８６、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ９０、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ９８、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ１２０、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ１５８、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ１６５、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ１６８、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ２２６
【００４４】
［緑色染料］
Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ ３、Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ ９、
Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ １６、Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ ３６、
Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ ２５、Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ ２７、
Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ ４１、Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ ４４、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｇｒｅｅｎ １、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｇｒｅｅｎ ６、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｇｒｅｅｎ ８
【００４５】
［紫色染料］
Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ １５、
Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ ４３、
Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ ３４、
Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ ４１、
Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ ４９、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｖｉｏｌｅｔ １、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｖｉｏｌｅｔ １２、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｖｉｏｌｅｔ ２２
【００４６】
この中で、保存安定性、染着性の観点から、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ８６、Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ２５、Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ ４３、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ７、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｖｉｏｌｅｔ １、Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ ３、Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ ９、Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ １５がより好ましい。
【００４７】
（Ｃ−２）群は、スルホン酸基を有しかつピアゾロンアゾ構造を有する黄色染料、スルホン酸基を有しかつキノリン構造を有する黄色染料、スルホン酸基を有しかつアゾ基を２つ以上有する黄色染料、及びスルホン酸基を有しかつトリアジン構造を有する黄色染料である。この中でスルホン酸基を有しかつピアゾロンアゾ構造を有する染料、スルホン酸基を有しかつトリアジン構造を有する染料、及びスルホン酸基を有しかつキノリン構造を有する染料が好ましい。（Ｃ−２）群の具体例を以下に示す。
【００４８】
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ３、
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ １１、
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ １７、
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ２３、
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ２５、
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ２９、
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ３８、
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ４０、
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ４２、
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ４４、
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ７６、
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ １４１、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ １１、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ １２、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ ２４、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ ３３、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ ４４、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ ５０
【００４９】
この中で、保存安定性、染着性の観点から、Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ３、Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ １４１、Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ２３がより好ましい。
【００５０】
（Ｃ−３）群は、スルホン酸基とアミド基を有しかつアゾ基を１つ有する赤色染料、スルホン酸基を有しかつアゾ基を２つ以上有する赤色染料、及びキサンテン構造を１つ有する赤色染料である。（Ｃ−３）群の具体例を以下に示す。
【００５１】
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ６、
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ３２、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ３５、
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ３７、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ５１、
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ５２、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ８７、
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ８９、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ９２、
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ９４、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ９７、
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １１１、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １１４、
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １１５、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １３３、
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １３４、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １３８、
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １４５、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １５４、
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １５８、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ １、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ２、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ４、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ １３、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ １７、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ２３、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ２４、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ２８、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ３１、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ３３、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ３７、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ３９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ４４、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ４６、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ６２、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ６３、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ７５、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ７９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８０、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８１、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８３、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８４、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ １１３、
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ２２９
【００５２】
この中で、保存安定性、染着性の観点から、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １３８、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ １ 、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ５２、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ６、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ３５、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ３７、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ２３、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ２４がより好ましい。
【００５３】
（Ｃ）成分の配合量は、組成物中に好ましくは０．０１〜５０ｐｐｍ、より好ましくは０．１〜３０ｐｐｍである。０．０１ｐｐｍ未満では、液体柔軟剤組成物に着色された色が非常に薄くなり、計量性向上効果が不充分となる場合がある。また、５０ｐｐｍを超えると、液体柔軟剤組成物に着色された色が濃くなりすぎる場合がある。
【００５４】
（Ｄ）成分の酸化防止剤としては、一般に知られている天然系酸化防止剤、合成系酸化防止剤ともに使用できる。酸化防止剤としては、アスコルビン酸、アスコルビン酸パルミテート、没食子酸プロピル、ＢＨＴ（ブチル化ヒドロキシトルエン）、ＢＨＡ（ブチル化ヒドロキシアニソール）、ハイドロキノン、三級ブチルハイドロキノン、天然のトコフェロール系化合物、没食子酸の長鎖（Ｃ８〜Ｃ２２）エステル（例えば没食子酸ドデシル）、チバスペシャルティケミカル（株）から入手可能なイルガノックス系化合物、４，５−ジヒドロキシ−ｍ−ベンゼンスルホン酸又はそのナトリウム塩、ジメトキシフェノール、カテコール、メトキシフェノール、カロチノイド、フラン類、アミノ酸類などが挙げられる。これらの１種を単独で又は２種以上を組合せて用いることができる。
【００５５】
この中で、液体柔軟剤組成物の外観や保存安定性の観点から、ＢＨＴ（ブチル化ヒドロキシトルエン）、メトキシフェノール、トコフェロール系化合物などが好ましい。
【００５６】
（Ｄ）成分の配合量は、組成物中に０．０１〜１質量％の範囲で使用されることが好ましい。０．０１質量％未満では退色防止効果が不充分となる場合があり、１質量％を超えると効果が一定となるためそれ以上の使用は不経済となる場合がある。
【００５７】
更に、本発明には、液体柔軟剤組成物の保存安定性を確保するため、上記成分に加えて、（Ｅ）成分のノニオン性界面活性剤と（Ｆ）成分の低級アルコール、グリコールエーテル系溶剤、及び多価アルコールからなる群から選ばれる１種又は２種以上の水溶性溶剤を含有することが好ましい。
【００５８】
（Ｅ）成分のノニオン性界面活性剤としては、例えば炭素数８〜２０のアルキル基又はアルケニル基を１つ以上有するポリオキシアルキレンアルキルエーテルが好ましく、特にオキシアルキレン基が平均２〜５０モル付加されたものが好ましい。更に下記一般式（ＩＶ）で表されるノニオン性界面活性剤が好ましい。
Ｒ¹−Ｔ−［（Ｒ²Ｏ）_p−Ｈ］_q （ＩＶ）
（式中、Ｒ¹は、炭素数１０〜１８、好ましくは１２〜１８のアルキル基又はアルケニル基であり、Ｒ²は炭素数２又は３のアルキレン基であり、好ましくはエチレン基である。ｐは平均付加モル数であり、２〜５０、好ましくは５〜３０、特に好ましくは５〜２０の数を示す。Ｔは−Ｏ−、−Ｎ−、−ＮＨ−、−Ｎ（Ｃ₂Ｈ₄ＯＨ）−、−ＣＯＮ−、−ＣＯＮＨ−又は−ＣＯＮ（Ｃ₂Ｈ₄ＯＨ）−であり、Ｔが−Ｏ−、−ＮＨ−、−Ｎ（Ｃ₂Ｈ₄ＯＨ）−、−ＣＯＮＨ−、又は−ＣＯＮ（Ｃ₂Ｈ₄ＯＨ）−の場合は、ｑは１であり、Ｔが−Ｎ−又は−ＣＯＮ−の場合は、ｑは２である。）
【００５９】
上記一般式（ＩＶ）の化合物の具体例として、下記一般式（Ｖ）、（ＶＩ）で表される化合物を挙げることができる。
Ｒ¹−Ｏ−（Ｃ₂Ｈ₄Ｏ）_r−Ｈ （Ｖ）
（式中、Ｒ¹は前記と同じ意味であり、ｒは平均付加モル数であり、２〜５０、好ましくは５〜３０の数である。）
Ｒ¹−Ｏ−（Ｃ₂Ｈ₄Ｏ）_s（Ｃ₃Ｈ₆Ｏ）_t−Ｈ （ＶＩ）
（式中、Ｒ¹は前記と同じ意味であり、ｓ及びｔは平均付加モル数であり、ｓは２〜４０、好ましくは５〜３０の数であり、ｔは１〜２０、好ましくは１〜１０の数である。（Ｃ₂Ｈ₄Ｏ）と（Ｃ₃Ｈ₆Ｏ）はランダム又はブロック付加体であってもよい。）
【００６０】
（Ｅ）成分のノニオン性界面活性剤としては、これらの１種を単独で又は２種以上を組合せて用いることができる。
【００６１】
（Ｅ）成分の配合量は、組成物中に０．１〜２０質量％、特に０．５〜１５質量％、更に０．５〜１０質量％が好ましい。０．１質量％未満だと保存安定性の向上効果が小さくなる場合があり、２０質量％を超えて配合しても、保存安定性の向上効果が一定となるため、２０質量％より多く配合することは不経済であり、更に柔軟処理時の泡立ちの点からも好ましくない場合がある。
【００６２】
（Ｆ）成分は低級（炭素数１〜４）アルコール、グリコールエーテル系溶剤、及び多価アルコールからなる群から選ばれる１種又は２種以上の水溶性溶剤である。具体的には、エタノール、イソプロパノール、グリセリン、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、ヘキシレングリコール、ポリオキシエチレンフェニルエーテル、及び下記一般式（ＶＩＩ）で表わされる水溶性溶剤を配合することが好ましい。
Ｒ³−Ｏ−（Ｃ₂Ｈ₄Ｏ）_y−（Ｃ₃Ｈ₆Ｏ）_z−Ｈ （ＶＩＩ）
（式中、Ｒ³は、炭素数１〜８、好ましくは２〜６のアルキル基又はアルケニル基である。ｙ及びｚは平均付加モル数であり、ｙは１〜５０、好ましくは１〜３０、ｚは０〜５０、好ましくは０〜２０の数を示す。）
【００６３】
中でも好ましい例としては、エタノール、エチレングリコール、ブチルカルビトール、プロピレングリコール、エチレングリコールポリプロオキシプロピレン（２）モノブチルエーテル［Ｃ₄Ｈ₉Ｏ（Ｃ₂Ｈ₄Ｏ）（Ｃ₃Ｈ₆Ｏ）₂Ｈ］などが挙げられる。
【００６４】
これらの（Ｆ）成分は、組成物中に０．１〜３０質量％、好ましくは２〜２０質量％配合される。
【００６５】
更に、本発明には、泡立ちを抑制し柔軟剤の計量性を向上させるために、（Ｇ）成分の消泡剤を含有することが好ましい。消泡剤としては、例えばシリコーン系消泡剤、アルコール系消泡剤、エステル系消泡剤、鉱油系消泡剤、植物油系消泡剤、及び合成油系消泡剤などが挙げられるが、柔軟剤計量時の泡立ちを抑えて計量性を向上させる観点から、シリコーン系の消泡剤が好ましい。本発明に使用されるシリコーン系消泡剤としては、オイル型消泡剤、コンパウンド型消泡剤、自己乳化型消泡剤、エマルション型消泡剤、粉末型消泡剤及び固形型消泡剤などが挙げられる。この中でも、計量性向上効果の点で、自己乳化型消泡剤及びエマルション型消泡剤がより好ましく、エマルション型消泡剤が特に好ましい。
【００６６】
消泡剤の具体例としては、ダウ コーニング アジア（株）製のＦＳアンチフォームシリーズのＤＫ Ｑ１−０７１、ＤＫ Ｑ１−１２０８、ＤＫ Ｑ１−１０８６、５４４、００１、８０、８１、０２６Ａ、５４５、０１３Ｂ、ＤＫ Ｑ１−０７２、ＡＦＥ、ＢＥ、ＤＢ−３１、ＤＢ−１１０Ｎ、Ｈ−１０、０２５、ＥＰＬ、Ｆ−１８、Ｆ−２０、Ｆ−５１、ＣＥ、９０、９１、９２、１１２２、ＤＫ Ｑ１−１０８９、ＤＫ Ｑ１−１０５６、ＤＫ Ｑ１−１０１４、ＤＫ Ｑ１−１０７４、信越化学工業（株）製のＫＳ４９６Ａ、ＫＳ５０２，ＫＳ５０６、ＫＳ５０８、ＫＳ５３０、ＫＳ５３１、ＫＳ５３６、ＫＳ５３７、ＫＳ５３８、ＫＭ７３、ＫＭ７３Ａ、ＫＭ７３Ｂ、ＫＭ７３Ｅ、ＫＭ７２、ＫＭ７２Ａ、ＫＭ７２Ｆ、ＫＭ７０、ＫＭ７１、ＫＭ７５、ＫＭ８０、ＫＭ８３、ＫＭ８３Ａ、ＫＭ８５、ＫＭ８７Ａ、ＫＭ８９、ＫＭ９０、ＫＭ９３、ＫＭ６８−１Ｆ、ＫＭ６８−２Ｆ、東レ・ダウ コーニングシリコーン（株）製のＱ２−３１８３Ａ、ＢＹ２８−５０３、ＳＤ５５９１、ＳＨ７ＰＡ、ＳＨ５５０３、ＳＨ５５１０、ＳＭ５５１３、ＳＨ５５６１、ＳＨ５５０７、ＢＹ２２−５１７、ＳＭ５５１１、ＳＭ５５１２、ＳＭ５５１５、ＳＭ５５１７、ＳＭ５５７１、ＳＭ５５７２Ｆ、ＳＭ５５７３、ＧＥ東芝シリコーン（株）製のＹＳＡ６４０６、ＴＳＡ７８０、ＴＳＡ７３４１、ＴＳＡ７３４３、ＴＳＡ７３９、ＴＳＡ７３２、ＴＳＡ７３２Ａ、ＴＳＡ７７２、ＴＳＡ７３０、ＴＳＡ７７０、ＴＳＡ７７５、ＴＳＡ７７６、ＹＭＡ６５０９、ＴＳＡ７３７、ＴＳＡ７３７Ｂ、ＴＳＡ７３７Ｓ、ＴＳＡ７３７Ｆ、ＴＳＡ７３７Ｋなどが挙げられる。
【００６７】
（Ｇ）成分の消泡剤としては、これらの１種を単独で又は２種以上を組合せて用いることができる。
【００６８】
（Ｇ）成分の配合量は特に限定されないが、液体柔軟剤組成物の外観を損なわない範囲で、組成物中に０．１ｐｐｍ〜１質量％配合され、更に好ましくは１ｐｐｍ〜０．０５質量％配合される。０．１ｐｐｍ未満では消泡効果が小さくなるため計量性向上効果が不充分である場合があり、１質量％を超えると、特に組成物の外観が透明な場合に、外観を損なうおそれがある。
【００６９】
本発明では、組成物の芳香のために香料を添加することができる。使用される香料原料のリストは、様々な文献、例えば「Ｐｅｒｆｕｍｅ ａｎｄ Ｆｌａｖｏｒ Ｃｈｅｍｉｃａｌｓ 」，Ｖｏｌ．Ｉａｎｄ ＩＩ，Ｓｔｅｆｆｅｎ Ａｒｃｔａｎｄｅｒ，Ａｌｌｕｒｅｄ Ｐｕｂ．Ｃｏ．（１９９４）及び「合成香料 化学と商品知識」、印藤元一著、化学工業日報社（１９９６）及び「Ｐｅｒｆｕｍｅ ａｎｄ Ｆｌａｖｏｒ Ｍａｔｅｒｉａｌｓ ｏｆ ＮａｔｕｒａｌＯｒｉｇｉｎ 」，Ｓｔｅｆｆｅｎ Ａｒｃｔａｎｄｅｒ，Ａｌｌｕｒｅｄ Ｐｕｂ．Ｃｏ．（１９９４）及び「香りの百科」、日本香料協会編、朝倉書店（１９８９）及び「Ｐｅｒｆｕｍｅｒｙ Ｍａｔｅｒｉａｌ Ｐｅｒｆｏｒｍａｎｃｅ Ｖ．３．３」，Ｂｏｅｌｅｎｓ Ａｒｏｍａ Ｃｈｅｍｉｃａｌ Ｉｎｆｏｒｍａｔｉｏｎ Ｓｅｒｖｉｃｅ（１９９６）及び「Ｆｌｏｗｅｒ ｏｉｌｓａｎｄ Ｆｌｏｒａｌ Ｃｏｍｐｏｕｎｄｓ Ｉｎ Ｐｅｒｆｕｍｅｒｙ」，Ｄａｎｕｔｅ Ｌａｊａｕｊｉｓ Ａｎｏｎｉｓ，Ａｌｌｕｒｅｄ Ｐｕｂ．Ｃｏ．（１９９３）などで見られ、それぞれを引用することにより本明細書の開示の一部とされる。
【００７０】
本発明の液体柔軟剤組成物には、防腐力、殺菌力を強化する目的で、防腐・殺菌剤として、イソチアゾロン系の有機硫黄化合物、ベンズイソチアゾリン系の有機硫黄化合物、安息香酸類、フェノール化合物、カチオン系化合物、及びその他化合物の中から１種を単独で又は２種以上を組合せて混合して用いることができる。
【００７１】
イソチアゾロン系の有機硫黄化合物としては、３−イソチアゾロン基を含む抗微生物性の有機防腐・殺菌剤が好ましい。これらの化合物は、１９８１年５月５日発行のＬｅｗｉｓらの米国特許第４，２６５，８９９号明細書に開示されている。その例としては、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、２−ｎ−ブチル−３−イソチアゾロン、２−ベンジル−３−イソチアゾロン、２−フェニル−３−イソチアゾロン、２−メチル−４，５−ジクロロイソチアゾロン、５−クロロ−２−メチル−３−イソチアゾロン、２−メチル−４−イソチアゾリン−３−オン、及びそれらの混合物が挙げられる。より好ましい防腐・殺菌剤は、５−クロロ−２−メチル−４−イソチアゾリン−３−オンと２−メチル−４−イソチアゾリン−３−オンとの水溶性混合物であり、更に好ましくは約７７質量％の５−クロロ−２−メチル−４−イソチアゾリン−３−オンと約２３質量％の２−メチル−４−イソチアゾリン−３−オンとの水溶性混合物である。イソチアゾロン系の有機硫黄化合物としては、ローム・アンド・ハース社のケーソンＣＧ／ＩＣＰ（約１．５質量％水溶液）、純正化学（株）製のジュンサイド５（約５質量％エチレングリコール溶液）などのジュンサイドシリーズに例示される市販されているものを使用することができる。
【００７２】
ベンズイソチアゾリン系の有機硫黄化合物としては、１，２−ベンズイソチアゾリン−３−オン、２−メチル−４，５−トリメチレン−４−イソチアゾリン−３−オンなどが挙げられ、類縁化合物として、ジチオ−２，２−ビス（ベンズメチルアミド）なども使用でき、それらを任意の混合比で使用することができる。このような化合物としては、アビシア（株）製のプロキセルシリーズ〔ＢＤＮ（有効分３３質量％）、ＢＤ２０（有効分２０質量％）、ＸＬ−２（有効分１０質量％）、ＧＸＬ（有効分２０質量％）、ＬＶ（有効分２０質量％）、ＴＮ（有効分６０質量％）〕、デニサイドＢＩＴ・ＮＩＰＡなどの市販品を用いることができる。
【００７３】
安息香酸類、フェノール化合物としては、安息香酸又はその塩、サリチル酸又はその塩、パラヒドロキシ安息香酸又はその塩、パラオキシ安息香酸メチル、パラオキシ安息香酸エチル、パラオキシ安息香酸プロピル、パラオキシ安息香酸ブチル、パラオキシ安息香酸ベンジル、３−メチル−３−イソプロピルフェノール、ｏ−フェニルフェノール、２−イソプロピル−５−メチルフェノール、レゾルシン、クレゾール、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾールなどを使用することができる。
【００７４】
カチオン系化合物としては、塩化ベンザルコニウム、塩化ベンゼトニウム、アルキルトリメチルアンモニウム塩、アルキルキノリニウム塩、アルキルアミノプロピルジメチルベンジルアンモニウム塩、アルキルピリジニウム塩、ジアルキルジメチルアンモニウム塩、ポリオキシアルキレントリアルキルアンモニウム塩、アルキルフェノキシエチルジメチルベンジルアンモニウム塩、アルキルイソキノリニウム塩、アルキルジメチルベンジルアンモニウム塩、ポリオキシエチレントリメチルアンモニウム塩、アルキルジメチルフェノキシエチルアンモニウム塩、アルキルイミダゾリウム塩、クロルヘキシジングルコン酸塩などが挙げられる。
【００７５】
また、その他化合物として、５−ブロモ−５−ニトロ−１，３−ジオキサン、２−ブロモ−２−ニトロプロパン−１，３−ジオール、５−クロロ−５−ニトロ−１，３−ジオキサン、２−クロロ−２−ニトロプロパン−１，３−ジオールなども使用でき、Ｈｅｎｋｅｌ社製Ｂｒｏｎｉｄｏｘ Ｌ、Ｉｎｏｌｅｘ社製Ｂｒｏｎｏｐｏｌ、吉富製薬（株）製ブロノポール、ブーツ社製マイアサイドＢＴなどの市販品を用いることができる。
【００７６】
これらの防腐・殺菌剤は、組成物に対して０〜０．１質量％配合されるのが好ましく、更に好ましい配合量は、０．００００１〜０．０３質量％、より好ましくは０．００００５〜０．０２質量％である。但し、安息香酸類又はフェノール化合物を用いる場合は、組成物に対して０〜３質量％配合されるのが好ましく、更に好ましくは０．０１〜１．５質量％である。
【００７７】
上記の防腐・殺菌剤の内、ケーソンＣＧ／ＩＣＰ、プロキセルシリーズＢＤＮ、マイアサイドＢＴ、安息香酸、ジデシルジメチルアンモニウム塩及び塩化ベンザルコニウムの中から選ばれる１種又は２種以上を用いることが特に好ましく、これらを用いた場合の配合量は０．００００１〜２質量％が好ましい。更に好ましくは、０．００００１〜１質量％、より好ましくは０．００００５〜０．５質量％である。
【００７８】
また、防腐・殺菌力を向上する目的で、更に以下の化合物の１種又は２種以上を、組成物に対して０〜０．５質量％、好ましくは０．００００１〜０．１質量％用いることができる。化合物としては、ピリチオンナトリウム、１，３−ビス（ヒドロキシメチル）−５，５−ジメチル−２，４−イミダゾリジンジオン、ジメチロールジメチルヒダントイン、ＤＭＤＭヒダントイン（Ｌｏｎｚａ社製Ｇｌｙｄａｎｔ、又はＧｌｙｄａｎ Ｐｌｕｓ）、Ｎ−［１，３−ビス（ヒドロキシメチル）２，５−ジオキソ−４−イミダゾリジニル］−Ｎ，Ｎ′−ビス（ヒドロキシメチル）尿素（一般にジアゾリジニル尿素名で発売されている）、Ｎ，Ｎ″−メチレンビス｛Ｎ′−［１−（ヒドロキシメチル）−２，５−ジオキソ−４−イミダゾリジニル］尿素｝、一般にイミダゾリジニル尿素として知られているイミダゾリジンジオン化合物、ポリメトキシド二環性オキサゾリジン化合物、ホルムアルデヒド、グルタルアルデヒドなどの低分子量アルデヒド、一般式ＨＣｌ・ＮＨ₂−（ＣＨ₂）₃−［−（ＣＨ₂）₃−ＮＨ−Ｃ（＝ＮＨ）−ＮＨ−Ｃ（＝ＮＨ・ＨＣｌ）−ＮＨ−（ＣＨ₂）₃−］_x−（ＣＨ₂）₃−ＮＨ−Ｃ（＝ＮＨ）−ＮＨ・ＣＮを有するポリヘキサメチレンビグアニドとしても知られているポリアミノプロピルビグアニド、ポリアミノプロピルビグアニド、クロルヘキシジンとして一般に知られている１，１′−ヘキサメチレンビス（５−（ｐ−クロロフェニル）ビグアニド）、酢酸及びジグルコン酸などの塩である二グルコン酸塩やその二酢酸塩、アビシア（株）製Ｐｒｏｘｅｌ ＩＢ、１−（３−クロラリル）−３，５，７−トリアザ−１−アゾニアアダマンタンクロリド（例えばＤｏｗ ＣｈｅｍｉｃａｌからＤｏｗｉｃｉｌ ２００の商品名で発売）、デヒドロ酢酸、一般にプロパミジンイセチオネートとして知られている４，４′−ジアミジノ−α，ω−ジフェノキシプロパンジイセチオネート、一般にヘキサミジンイセチオネートとして知られている４，４′−ジアミジノ−α，ω−ジフェノキシヘキサンジイセチオネート、１２−（４′−チアゾリル）−ベンズイミダゾール、２−（４−チオシアノメチルチオ）ベンゾチアゾール、メチル−２−ベンズイミダゾールカルバミドなどのイミダゾール系又はチアゾール系抗菌剤、クロロブタノールとして一般に知られている１，１，１−トリクロロ−２−メチルプロパン−２−オール、クロロブタノール、４，４′−（トリメチレンジオキシ）ビス−（３−ブロモベンズアミジン）ジイセチオネート、ジブロモプロパミジン、ジブロモプロパミジン、３，４，４′−トリクロロカルバニリド、トリクロカルバンとしても知られているＮ−（４−クロロフェニル）−Ｎ′−（３，４−ジクロロフェニル）尿素、トリクロサンとして一般的に知られている２，４，４′−トリクロロ−２′−ヒドロキシジフェニルエーテル、４，４′−ジクロロ−２−ヒドロキシジフェニルエーテル、チバスペシャルティケミカルズ（株）製チノサンＨＰ１００（商品名）、塩化亜鉛などの亜鉛化合物が挙げられる。
【００７９】
本発明の液体柔軟剤組成物では、更にキレート剤を配合することにより、液体柔軟仕上げ剤組成物の香気などの安定性を向上させることができる。キレート剤として具体的には、ヒドロキシエタンジホスホン酸（ライオン化学（株）フェリオックスＣＹ−１１５）、エチレンジアミンテトラホスホン酸（モンサント社 Ｄｅｑｕｅｓｔ２０４１）、Ｄ−２０００、２０１０、２０６６などのホスホン酸系キレート剤、エチレンジアミン四酢酸、ニトリロトリ酢酸、クエン酸、カプトカテキュ酸、エチレンジアミンジコハク酸、メチルグリシンジ酢酸、イミノジコハク酸、ヒドロキシイミノジコハク酸、アスパラギン酸、及びそれらのナトリウムなどの塩などが挙げられる。キレート剤は、本発明の効果を妨げない範囲で組成物中に０〜３質量％配合できる。
【００８０】
本発明の液体柔軟剤組成物には、上記の成分以外に本発明の効果を妨げない範囲で、通常の家庭用仕上げ剤に使用されている添加剤などを使用することができる。そのような添加剤として、具体的には、カチオン性界面活性剤、アニオン性界面活性剤、アニオン性高分子化合物、ヘキサン酸とグリセリン又はペンタエリスリトールとの部分エステル化物や、食塩、塩化アンモニウム、塩化カルシウム、塩化マグネシウム、塩化カリウムなどの水溶性塩、流動パラフィン、高級アルコールなどの油剤、尿素、炭化水素、非イオン性セルロース誘導体、紫外線吸収剤、蛍光増白剤、後述するｐＨ調整剤などが挙げられる。なお、アニオン性界面活性剤、アニオン性高分子化合物は、（Ｂ）成分のカチオン性高分子化合物の含有量よりも多く配合された場合、シリコーン化合物の吸着効果を著しく低下させるため、（Ｂ）成分のカチオン性高分子化合物の含有量よりも多く配合されることは好ましくない。
【００８１】
本発明の液体柔軟剤組成物のｐＨは特に限定されないが、３〜１０の範囲であることが好ましく、４〜７の範囲であることがより好ましい。必要に応じて、塩酸、硫酸、リン酸、アルキル硫酸、安息香酸、パラトルエンスルホン酸、クエン酸、リンゴ酸、コハク酸、乳酸、グリコール酸、ヒドロキシエタンジホスホン酸、フィチン酸、エチレンジアミン四酢酸、トリエタノールアミン、ジエタノールアミン、ジメチルアミン、Ｎ−メチルエタノールアミン、Ｎ−メチルジエタノールアミンなどの短鎖アミン化合物、水酸化ナトリウムなどのアルカリ金属水酸化物、アルカリ金属炭酸塩、アルカリ金属珪酸塩などのｐＨ調整剤を用いることができる。
【００８２】
本発明の液体柔軟剤組成物は、上記（Ａ）〜（Ｄ）成分、必要に応じて（Ｅ）〜（Ｇ）成分及び任意成分を含有し、通常、残部は水である。また、本発明の液体柔軟剤組成物は、適度な濃度に希釈して使用される。使用方法は特に限定されないが、衣料を通常の洗濯を行い、すすぎの段階ですすぎ水に本発明の組成物を溶解させて処理をしたり、また、たらいのような容器を用い本発明の組成物を水に溶解させ、更に衣料を入れて浸漬処理する方法などが挙げられる。繊維製品の処理はいずれの方法で行ってもよいが、浴比（繊維製品に対する処理液の比率）は３〜１００倍、特に５〜５０倍であることが好ましい。
【００８３】
本発明の液体柔軟剤組成物は、通常市販されている仕上げ剤や洗浄剤に使用されている計量キャップつき容器や詰め替え用容器などに充填することができる。これら容器の材質は、特に限定されないが、ガラス、紙、プラスチックなどが挙げられ、中でも使用性の点からプラスチックが好適である。容器に用いられるプラスチックとしてはポリエチレン、ポリプロピレン、ナイロン、ポリエチレンテレフタレート、塩化ビニルなどが挙げられ、これらの１種又は２種以上が使用される。また、これらプラスチックには、顔料や紫外線吸収剤や静電気防止剤などの添加剤が適宜添加される。更に、このプラスチック容器の外観は、透明又は半透明、更に不透明であってもよいが、内容物の残量の分かりやすさの観点から、透明又は半透明であることが好ましく、特に液体柔軟剤組成物が透明な外観を有する場合には、製品の価値を高めるために無着色又は有色の透明な容器の使用が好ましい。
【００８４】
【発明の効果】
本発明によれば、シリコーン化合物とカチオン性を有する高分子化合物を特定の比率で併用し、更に染料及び酸化防止剤を併用することで、各種繊維製品に優れた柔軟性、滑らかさ、ドレープ性を付与すると共に、光などによる色調安定性の良好な液体柔軟剤が得られる。更に、ノニオン性界面活性剤と特定の水溶性溶剤を併用することで良好な保存安定性が得られ、シリコーンとしてポリエーテル基を有するシリコーンを用いることで、透明感の高い外観を有し、容器などへの固着物が発生しない液体柔軟剤が得られ、更に消泡剤を添加することで計量性が良好となる。
【００８５】
【実施例】
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において％は質量％を示す。
【００８６】
［実施例１、２、４〜１４、１６〜３３、比較例１、２、５〜６］
〔柔軟剤組成物の調製〕
表１〜７に示す（Ａ）〜（Ｇ）成分を、以下の表８〜１０に示す組成に応じ（（Ｃ）、（Ｇ）成分、共通成分を除き純分換算、％、（Ｃ）、（Ｇ）成分、共通成分は有姿、％）、（Ａ）、（Ｄ）、（Ｅ）、（Ｆ）成分、及び下記記載の共通成分を１０００ｍＬビーカーにとり、攪拌羽根を用いて充分に攪拌した。次に、攪拌しながらイオン交換水を添加し、更に攪拌しながら（Ｂ）成分を添加し攪拌後、更に、（Ｃ）成分を添加し攪拌後、（Ｇ）成分を添加し、均一になるまで充分に攪拌して、８００ｇの液体柔軟剤組成物を調製した。得られた液体柔軟剤組成物の柔軟性及び滑らかさ、ドレープ性、色調安定性、液の外観、保存安定性、キャップ汚れ、計量性について評価した。結果を表８〜１０に併記する。
【００８７】
［実施例３、１５、比較例３］
以下の表８、９に示す組成に応じ（（Ｃ）成分、共通成分を除き純分換算、％、（Ｃ）成分、共通成分は有姿、％）、（Ｄ）、（Ｅ）、（Ｆ）成分、及び下記記載の共通成分を１０００ｍＬビーカーにとり、攪拌羽根を用いて充分に攪拌した。次に、攪拌しながらイオン交換水を添加し、更に攪拌しながら（Ａ）、（Ｂ）成分を添加し攪拌後、（Ｃ）成分を添加し、均一になるまで充分に攪拌して、８００ｇの液体柔軟剤組成物を調製した。得られた液体柔軟剤組成物の柔軟性及び滑らかさ、ドレープ性、色調安定性、液の外観、保存安定性、キャップ汚れ、計量性について評価した。結果を表８〜９に併記する。
【００８８】
［比較例４］
以下の表９に示す組成に応じ（（Ｃ）成分を除き純分換算、％、（Ｃ）成分は有姿、％）、ジステアリルジメチルアンモニウムクロライド（ライオンアクゾ（株）製）、（Ｃ）、（Ｅ）及び（Ｆ）成分を５００ｍＬビーカーにとり、充分に攪拌した。次にこれを６０℃に加温したイオン交換水に攪拌しながら添加した。この時、イオン交換水は、内径１１０ｍｍ、高さ１９０ｍｍのガラス容器に収納し、攪拌機（アジターＳＪ型、（株）島崎製作所製）を用い、回転数１０００ｒｐｍで充分に攪拌した。なお、サンプル調製量は１０００ｇとし、これら工程は全て６０℃以上で行った。
【００８９】
下記に実施例及び比較例で使用した成分、共通成分、及び評価方法を示す。
〔シリコーン化合物〕
表１に記載のシリコーン化合物（Ａ−１〜４）を使用した。
【００９０】
【表１】

【００９１】
〔カチオン性を有する水溶性高分子〕
表２に記載のカチオン性を有する水溶性高分子化合物（Ｂ−１〜３）を使用した。
【００９２】
【表２】

【００９３】
〔染料〕
表３に記載の染料（Ｃ−１〜３）を使用した。
【００９４】
【表３】

【００９５】
〔酸化防止剤〕
表４に記載の酸化防止剤（Ｄ−１〜３）を使用した。
【００９６】
【表４】

【００９７】
〔ノニオン性界面活性剤〕
表５に記載のノニオン性界面活性剤（Ｅ−１〜３）を使用した。
【００９８】
【表５】

【００９９】
〔水溶性溶剤〕
表６に記載の水溶性溶剤（Ｆ−１〜３）を使用した。
【０１００】
【表６】

【０１０１】
〔消泡剤〕
表７に記載のシリコーン系消泡剤（Ｇ−１〜３）を使用した。
【０１０２】
【表７】

【０１０３】
（共通成分１）
下記の成分は、〔 〕内に示した量（有姿での配合量）を添加した。
１−１：ケーソンＣＧ−ＩＣＰ（ローム＆ハース社製） 〔１００ｐｐｍ〕
１−２：香料組成物Ａ （表１１〜２１記載） 〔０．３％〕
【０１０４】
（共通成分２）
下記の成分は、〔 〕内に示した量（有姿での配合量）を添加した。
２−１：プロキセルＢＤＮ（アビシア（株）製） 〔５ｐｐｍ〕
２−２：香料組成物Ｂ （表１１〜２１記載） 〔０．３％〕
【０１０５】
（共通成分３）
下記の成分は、〔 〕内に示した量（有姿での配合量）を添加した。
３−１：ブロノポール（吉富製薬（株）製） 〔２０ｐｐｍ〕
３−２：香料組成物Ｃ （表１１〜２１記載） 〔０．３％〕
【０１０６】
（共通成分４）
下記の成分は、〔 〕内に示した量（有姿での配合量）を添加した。
４−１：ジュンサイド５（純正化学（株）製） 〔３０ｐｐｍ〕
４−２：香料組成物Ｄ （表１１〜２１記載） 〔０．３％〕
【０１０７】
（共通成分５）
下記の成分は、〔 〕内に示した量（有姿での配合量）を添加した。
５−１：マイアサイドファーマＢＰ（Ｂ．Ａ．Ｓ．Ｆジャパン（株）製）〔５０ｐｐｍ〕
５−２：香料組成物Ｄ （表１１〜２１記載） 〔０．３％〕
【０１０８】
〔柔らかさ、滑らかさ、ドレープ性評価方法〕
（１）柔軟剤組成物による処理方法
（試験布の調製）
市販の綿ニット（綿１００％）とポリエステルジャージ（ポリエステル１００％）を市販衣料用洗剤「トップ」［ライオン（株）製、成分：界面活性剤（アルファオレフィンスルホ脂肪酸エステルナトリウム、脂肪酸ナトリウム、直鎖アルキルベンゼン系、ポリオキシエチレンアルキルエーテル）、水軟化剤、アルカリ剤、酵素、蛍光増白剤］により、家庭用二槽式洗濯機を用いて洗浄１５分（洗剤は標準量使用、浴比３０倍、４５℃水道水）→脱水５分の工程を２サイクル繰り返した後、流水すすぎ１５分→脱水５分の工程を５回繰り返し、自然乾燥したものを試験布とした。
【０１０９】
（柔軟剤による処理）
上記処理を行った、綿ニット７００ｇとポリエステルジャージ３００ｇを市販衣料用洗剤「トップ」［ライオン（株）製、成分：界面活性剤（アルファオレフィンスルホ脂肪酸エステルナトリウム、脂肪酸ナトリウム、直鎖アルキルベンゼン系、ポリオキシエチレンアルキルエーテル）、水軟化剤、アルカリ剤、酵素、蛍光増白剤］で１５分洗浄し（洗剤は標準使用量、浴比３０倍、２５℃の水道水使用）、ためすすぎ２回目に、表８〜１０に示す柔軟剤組成物を水量３０リットルに対して１０ｇ（ただし、実施例２６は６．６ｇ、実施例２７は５ｇ）加えて、衣料の柔軟処理（浴比３０倍、２５℃の水道水使用、３分）を行った。その後、２０℃、４０％ＲＨの条件で自然乾燥し、以下の評価を行った。
【０１１０】
（２）評価方法
▲１▼柔軟性及び滑らかさの評価
柔軟剤を使用せずに処理した綿ニット、ポリエステルジャージを対照として専門パネラー１０人による官能一対比較を行い、以下に示す評価基準により評価を行った。
＋２：対照よりはっきり良好
＋１：対照よりやや良好
０：対照とほぼ同じ
−１：対照の方がやや良好
−２：対照の方がはっきり良好
その評点の平均をとり、１．５〜２．０点を◎、１．０以上〜１．４点を○、０．５〜０．９点を△、０．４点以下を×とした。
【０１１１】
▲２▼ドレープ性の評価
市販フリース（ＵＮＩＱＬＯ製 ＳＰ Ｎｏ．６Ａ０１８ ポリエステル１００％）を以下の方法で処理したものを用いて行った。このフリース１枚を市販の長袖シャツ（ＵＮＩＱＬＯ製、綿１００％）３枚とともに家庭用全自動洗濯機を用いて、市販衣料用洗剤「トップ」（ライオン（株）製）で１５分洗浄し（洗剤は標準使用量、浴比３０倍、２５℃の水道水使用）、ためすすぎ２回目に、表８〜１０に示す柔軟剤組成物を水量４５リットルに対して１５ｇ（ただし、実施例２６は１０ｇ、実施例２７は７．５ｇ）加えて、衣料の柔軟処理（浴比３０倍、２５℃の水道水使用、３分）を行った。この洗浄〜柔軟処理の工程を７回繰り返して行った後、２０℃、４０％ＲＨの条件で自然乾燥し、実際にフリースを着用して、その際のドレープ性を以下に示す評価基準により目視で判定した。
【０１１２】
ドレープ性とは、第２版繊維便覧（社団法人繊維学会編、平成６年３月２５日発行、丸善（株））、繊維の百科事典（本宮達也ら編、平成１４年３月２５日発行、丸善（株））などの文献で一般的に述べられているように、自重などによる布の変形状態（ドレープ）を形成する性能であるが、評価法は多岐にわたる。ここでは、着用時における衣料のシルエットの美しさとして、下記基準で評価を行った。
○：新品と同等もしくはそれ以上の美しいシルエットを有する
△：新品の方が、やや美しいシルエットを有する（比較例４とほぼ同等）
×：新品の方が、はっきりと美しいシルエットを有する（柔軟剤を使用せずに処理したものとほぼ同等）
【０１１３】
〔保存安定性評価方法〕
以下の表９及び表１０に示す組成に準じ、上記〔柔軟剤組成物の調製〕に基づき調製した液体柔軟剤組成物を、実施例１３〜１８、２５〜２８についてはポリエチレンテレフタレート（ＰＥＴ）容器１※に、実施例１９〜２４、２９〜３３、比較例４〜６についてはポリエチレンテレフタレート（ＰＥＴ）容器２※に入れて密栓し、液の外観（透明感）及び保存安定性を評価した。なお、保存安定性は、上記ポリエチレンテレフタレート（ＰＥＴ）容器に密栓したまま２５℃、４０℃、５℃の各条件下で１ヶ月放置し、その外観変化を観察し、下記評価基準により評価した。
（液の外観評価基準）
◎：透明である
○：透明感はないが、均一に分散
△：わずかにオリを生じる
×：沈澱もしくは分離を生じる
（保存安定性評価基準）
○：初期品と変化がなく、透明で均一又は均一に分散
△：わずかにオリもしくはわずかに分離を生じる
×：沈澱もしくは分離を生じる
容器１※：ポリエチレンテレフタレート（ＰＥＴ）樹脂（コダック Ａ−１２）をブロー成形法により、成形された容器。容器の容量は、３００ｍＬ、樹脂の厚さは０．４ｍｍ、外観は無色透明、顔料、紫外線吸収剤は未添加である。
容器２※：ポリエチレンテレフタレート（ＰＥＴ）樹脂（コダック Ａ−１２）をブロー成形法により、成形された容器。容器の容量は、３００ｍＬ、樹脂の厚さは０．４ｍｍ、外観は青色透明、顔料（ＰＴ−ＲＭ ＡＺ ＭＢ０９８０（Ａ）ブルー ３１Ｘ）０．０２％含有、紫外線吸収剤は未添加である。
【０１１４】
〔透明容器における色調安定性評価〕
以下の表８〜１０に示す組成に準じ、上記〔柔軟剤組成物の調製〕に基づき調製した液体柔軟剤組成物２００ｍＬを、ポリエチレンテレフタレート（ＰＥＴ）容器１※に入れて密栓し、ＩＲＩＥ ＵＶ ＩＬＬＵＭＩＮＡＴＥＲ（入江製作所製）を用いて約８ｃｍの距離から紫外線を１４．７ＭＪ／ｍ²照射し、色調の変化を目視で観察し、下記評価基準により評価した。
（色調安定性評価基準）
○：初期品と変化がない
△：初期品に比べてわずかに退色し、色調がやや変化している
×：初期品に比べかなり退色し、色調が著しく変化している
【０１１５】
〔計量性評価方法〕
以下の表１０に示す組成に準じ、上記〔柔軟剤組成物の調製〕に基づき調製した液体柔軟剤組成物を、「しわすっきりソフランＣ」（ライオン（株）製）の計量キャップつきプラスチック容器（計量キャップ：半透明のポリプロピレン製、ボトル：不透明のポリエチレン・ポリプロピレン製）に、７００ｍＬ充填後密栓し、上下に５回軽く振った後、５分後に計量キャップにボトルから液体柔軟剤組成物をキャップの２０（ｍＬ）の目盛り線と液面が重なるように注いだ。その際の計量のし易さを下記評価基準により評価した。
（計量性評価基準）
○：液面にわずかに泡が絡むものの、目盛り線の通りに正確に計量できる
△：液面に泡が絡んで、液面が把握しづらくなるものの、計量することは可能
×：液面にかなり泡が絡み、計量が困難
【０１１６】
〔キャップ汚れ評価法〕
以下の表９〜１０に示す組成に準じ、上記〔柔軟剤組成物の調製〕に基づき調製した液体柔軟剤組成物を計量キャップ（３０ｍＬ用、半透明のポリプロピレン製）に、キャップの２０（ｍＬ）の目盛り線まで注ぎ、２日間放置後、液を捨てた。その際のキャップ汚れを下記評価基準により評価した。なお、キャップ汚れは、液体柔軟剤組成物がキャップに付いた時の皮膜形成や固化のしやすさに起因する。従って、本方法は、実際の家庭で長期間繰り返し使用した際のキャップ汚れの加速試験である。
（キャップ汚れ評価基準）
○：固着物がほとんどついていない
△：わずかに固着物が付着している
×：かなり固着物が付着している
【０１１７】
【表８】

＊ややキシミ感
【０１１８】
なお、本発明品により処理された綿ニット・ポリエステル布は、柔軟性、滑らかさ、ドレープ性に優れた仕上がりが得られ、更に色調安定性も良好であった。
【０１１９】
【表９】

＊ややキシミ感、＊＊ややぬめり感
【０１２０】
【表１０】

【０１２１】
ノニオン性界面活性剤及び水溶性溶剤を組み合わせることで、低温から高温まで保存安定性が良好になり、シリコーン化合物としてポリエーテル基を有するシリコーンを用いることにより、低温から高温まで透明な液外観を有しかつ容器などへの固着物発生がなくなり、更に、消泡剤を組み合わせることで、計量性が良好な柔軟剤組成物を得ることができた。
【表１１】

【０１２２】
【表１２】

【０１２３】
【表１３】

【０１２４】
【表１４】

【０１２５】
【表１５】

【０１２６】
【表１６】

【０１２７】
【表１７】

【０１２８】
【表１８】

【０１２９】
【表１９】

【０１３０】
【表２０】

【０１３１】
【表２１】

＊１：［Ｆｌｏｗｅｒ ｏｉｌｓ ａｎｄ Ｆｌｏｒａｌ ＣｏｍｐｏｕｎｄｓＩｎ Ｐｅｒｆｕｍｅｒｙ］ Ｄａｎｕｔｅ Ｌａｊａｕｊｉｓ Ａｎｏｎｉｓ，Ａｌｌｕｒｅｄ Ｐｕｂ．Ｃｏ．[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid softener used for textile products such as clothing. In particular, the present invention relates to a silicone-based liquid softener composition that can impart excellent flexibility, smoothness, and drape to various textiles, clothing, and the like, and does not discolor due to light or the like.
[0002]
[Prior art]
Conventionally, softeners containing various quaternary ammonium salts as main components have been used for the purpose of adding flexibility during rinsing after washing and imparting flexibility to textiles. As the quaternary ammonium salt, a di-long-chain quaternary ammonium salt is generally used. However, the softener mainly composed of a di-long chain type quaternary ammonium salt has a good softness-imparting effect for cotton products, but it may cause a slimy feeling or may be chemically treated with polyester or the like depending on conditions. The softening effect on textiles is small, and the effect of imparting smoothness and draping to various textiles is also small.
[0003]
On the other hand, silicone compounds are known to impart unique flexibility, flexibility and smoothness to fiber products, particularly chemical fibers, unlike di-long-chain quaternary ammonium salts. However, silicone is poor in adsorptivity to fibers in finishing treatment in a water bath, and must be treated from a high concentration bath in order to obtain a sufficient effect. In order to remedy such drawbacks, the present inventors have previously proposed a small amount of cationic surface activity as a means for efficiently adsorbing silicone from fibers in a water bath as described in JP-A No. 2000-154476. A fashionable finish composition using a combination with an agent was proposed. However, this finish composition exhibits excellent performance when used after a fashionable nonionic detergent, but when used after an anionic detergent used in normal laundry, the anion remaining in the rinse bath There is a problem that the performance is lowered due to the influence of the activator.
[0004]
As a method for solving this problem, the present inventors have proposed a liquid flexibility that gives an excellent texture by using a silicone compound and a cationic polymer compound in a specific ratio as described in Japanese Patent Application No. 2002-268927. An agent composition was proposed.
[0005]
Japanese Patent Application Laid-Open No. 10-183472 discloses a finishing agent for clothing containing a water-insoluble / non-curing silicone mainly composed of a water-soluble polymer that has been used for the purpose of imparting elasticity to clothing. A composition is disclosed. Furthermore, JP-A-2000-129777 and JP-A-2000-129578 are mainly composed of a water-soluble polymer that has been used for the purpose of imparting elasticity to clothes, and includes silicone compounds and nonionic substances. Disclosed is a fiber composition treating composition containing a surfactant. However, when a textile product is processed using these compositions, the rigidity value is increased, which is not preferable as a softening agent that requires flexibility.
[0006]
Furthermore, Japanese Patent Application Laid-Open No. 2000-239970 discloses a fiber product treating agent mainly composed of a water-soluble polymer that has been used for the purpose of imparting elasticity to clothing and containing amino-modified silicone. However, when a textile product is treated with this composition, not only is it not preferable as a softening agent to increase the rigidity value, but the textile product may be yellowed by amino-modified silicone depending on storage conditions.
[0007]
On the other hand, recently, for the purpose of resource saving and waste saving, a simple disposal type refill container has appeared, and after using the content liquid in the main body container, the content liquid in the refill container is refilled into the main body container and used. It was way. Observing the actual consumer behavior pattern revealed that refilling was being carried out when the liquid content still remained, not when it was finished using. Due to this behavior pattern, it is difficult to determine the time when refilling is difficult for opaque containers used in liquid softeners on the market, because it is difficult to see the remaining amount of the liquid, and how far the liquid is contained. Therefore, there is a problem that the liquid overflows during refilling. In order to solve such a problem, it is desired to make it easy to see the remaining amount of the content liquid by using a transparent main body container or a main body container with a transparent slit in part, and the content liquid is further colored. If so, the remaining amount can be grasped more accurately. However, when a partially or wholly transparent bottle is filled with a colored liquid softening agent, there is a problem that fading due to light or the like occurs depending on storage conditions.
[0008]
Also, liquid softeners are usually weighed using a transparent or translucent measuring cap attached to the container, but if the liquid level is difficult to see when the content liquid is poured, it will be difficult to measure with the scale line of the measuring cap. There was a problem. For example, if many nonionic surfactants are used for the purpose of enhancing the storage stability of the softener composition, the liquid tends to foam, and it becomes difficult to see the liquid level because many bubbles are entangled with the liquid surface. There was a case where the sex decreased.
[0009]
Furthermore, in the case of liquid softeners mainly composed of di-long-chain quaternary ammonium salts, if the metering cap is repeatedly measured over a long period of time as used in an actual home, the metering cap and the bottle body cap joint There was a problem that the fixed liquid was dried and solidified in the part and gradually increased in size, making it difficult to weigh, making it difficult to open and close the cap, and worsening the appearance. And such a fixed thing generate | occur | produced also in the softener insertion port incorporated in the electric washing machine, and had a problem that it became difficult to remove.
[0010]
[Patent Document 1]
JP 2000-154476 A
[Patent Document 2]
JP-A-10-183472
[Patent Document 3]
Japanese Patent Application No. 2002-268927
[Patent Document 4]
JP 2000-129577 A
[Patent Document 5]
JP 2000-239970 A
[0011]
[Problems to be solved by the invention]
The present invention can impart excellent flexibility, smoothness, and drape to various textile products, and even when filled in a container having a transparent part, it does not change color due to light, etc., and further has storage stability. An object of the present invention is to provide a water-based liquid softening agent composition that is good, has a highly transparent liquid appearance, is excellent in meterability, and does not generate a fixed substance in a container or the like.
[0012]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the present inventors have used silicone and a polymer compound having a specific cationic property in a specific ratio, and also used a dye and an antioxidant in combination. Gives excellent flexibility, smoothness and drape, eliminates discoloration due to light, etc., and further improves storage stability by using a nonionic surfactant and a water-soluble solvent together. A liquid softening agent that has a liquid appearance with high transparency and does not generate a fixed substance on a container can be obtained by using silicone, and that excellent meterability can be obtained by using an antifoaming agent in combination. And the present invention has been completed.
[0013]
Therefore, the present invention comprises (A) a silicone compound, (B) a dimethyldiallylammonium chloride polymer or an imidazolium / vinylpyrrolidone copolymer, (C) an acid dye and / or a direct dye, and (D) an antioxidant. A liquid softening agent composition comprising: (A) :( B) (mass ratio) is 99: 1 to 50:50.
[0014]
In this case, it is preferable to blend one or more water-soluble solvents selected from the group consisting of (E) a nonionic surfactant and (F) a lower alcohol, a glycol ether solvent, and a polyhydric alcohol. is there. In addition, as a (A) component, the silicone compound which has a polyether group is preferable, and also it is preferable to mix | blend (G) antifoamer.
[0015]
Hereinafter, the present invention will be described in more detail.
The component (A) of the present invention is a silicone compound. The silicone compound is not particularly limited as long as it can impart flexibility, smoothness, and drapeability when adsorbed on a textile product. Silicone compounds generally used for fiber treatment include dimethyl silicone, polyether modified silicone, methylphenyl silicone, alkyl modified silicone, higher fatty acid modified silicone, methyl hydrogen silicone, fluorine modified silicone, epoxy modified silicone, carboxy Examples thereof include modified silicone, carbinol-modified silicone, and amino-modified silicone, and one of these can be used alone or as a mixture of two or more.
[0016]
The molecular structure of the silicone compound may be linear or branched or cross-linked. The modified silicone compound may be modified with one kind of organic functional group or may be modified with two or more kinds of organic functional groups.
[0017]
The silicone compound can be used as an oil or as an emulsion dispersed by any emulsifier. In particular, a silicone compound containing no amino group is preferable in order to prevent yellowing of the fiber product subjected to softening treatment. Furthermore, the silicone compound of the component (A) is nonionic because it enhances the effect of adsorbing the silicone compound of the component (A) on the fiber by the component (B), which will be described later, and improves flexibility, smoothness, and drapeability. More preferable examples include dimethyl silicone, carbinol-modified silicone, epoxy-modified silicone, and polyether-modified silicone.
[0018]
Among these, as a particularly preferable silicone compound, a softening and liquid softening agent composition is made transparent, and no sticking matter is generated in a container (especially a cap joint portion) or an automatic charging port of a household electric washing machine, thereby increasing the commercial value. From the standpoint that it can be increased, polyether-modified silicone can be exemplified. The silicone is suitable for obtaining a transparent liquid softening agent composition with less flexibility and good flexibility as compared with dimethyl silicone having no polyether group. Furthermore, it is suitable for obtaining antistatic properties and water absorption. Preferred polyether-modified silicones include copolymers of alkyl (C1-3) siloxane and polyoxyalkylene (alkylene groups preferably having 2-5 carbon atoms). Of these, a copolymer of dimethylsiloxane and polyoxyalkylene is preferred. In addition, polyoxyalkylene shows the random or block polymer of polyoxyethylene, polyoxypropylene, polyoxyethylene, and polyoxypropylene. Examples of such a compound include compounds represented by the following general formula (I).
[0019]
[Chemical 1]

(In the formula, M, N, a and b are average polymerization degrees, and R represents hydrogen or an alkyl group.)
[0020]
Here, M is preferably 10 to 10,000, N is preferably 1 to 1000, and M> N, and M is preferably 10 to 1000, N is 1 to 50, and M> N. The larger M is, the better the flexibility is, but the viscosity of the silicone compound is increased, so that the workability at the time of producing the softening agent composition may be deteriorated. a is preferably 2 to 100, and b is preferably 0 to 50. R is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
[0021]
Specific examples of the polyether-modified silicone oil used in the present invention include SH3772M, SH3775M, SH3748, SH3749, SF8410, SH8700, BY22-008, BY22-012, SF8421, manufactured by Toray Dow Corning Silicone Co., Ltd. KF352A, KF6008, KF615A, KF6016, KF6017 manufactured by Shin-Etsu Chemical Co., Ltd., TSF4450, TSF4452, manufactured by GE Toshiba Silicone Co., Ltd., SILWET L-7001, SILWET L-7002, SILWET L- 7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-21 64, SILWET FZ-2171 and the like, and these can be used alone or as a mixture of two or more.
[0022]
The blending amount of the silicone compound of component (A) used in the present invention is not particularly limited, but the lower limit of the blending amount is within the liquid softener composition from the viewpoints of flexibility, smoothness, drapeability and composition viscosity. 3% by mass, particularly 5% by mass, and further 6% by mass are preferable, and the upper limit is preferably 70% by mass, particularly 50% by mass, and further 40% by mass. If the blending amount is less than 3% by mass, effects such as flexibility, smoothness, and drapeability may be insufficient, and if it exceeds 70% by mass, the viscosity of the composition may increase and the usability may decrease. is there.
[0023]
The component (B) of the present invention has an effect of adsorbing the silicone compound of the component (A) to the fiber. As the water-soluble polymer compound having a cationic property, those having a cationic property when dissolved in water can be used. Particularly, the water-soluble polymer compound having a cationic property includes an amino group, an amine group, a quaternary compound. A water-soluble polymer compound having one or two or more cationic groups selected from ammonium groups is preferred. In the present invention, the water-soluble polymer means that when 1 g of the water-soluble polymer compound is added to 100 g of water at 25 ° C., the liquid is not turbid and transparent.
[0024]
The cationic water-soluble polymer compound (B) preferably has a degree of cationization of 0.1% or more, particularly preferably 2.5% or more. If the degree of cationization is less than 0.1%, the effect of adsorbing the coexisting silicone compound to the fiber becomes small, and a large amount of compounding is required, which may not be economical. In addition, when the polymer compound itself has a property of imparting rigidity to the fiber product, if it is blended in a large amount, the softening effect may be lowered.
[0025]
Here, the degree of cationization means that a polymer compound is a polymer of a cationic monomer, a copolymer of a cationic monomer and a nonionic monomer, and a part of a nonionic polymer modified or substituted with a cationic group. In the case of (cationized cellulose, etc.), the polymer compound is a copolymer of a cationic monomer and an anionic monomer, and a copolymer of a cationic monomer, an anionic monomer and a nonionic monomer. In the case of coalescence, it is defined as a value calculated by the following formula (2).
Cation degree (%) = X × Y × 100 (1)
(X: atomic weight of a cationized atom (such as nitrogen) in the cationic group of the polymer compound
Y: mole number of cationic group contained in 1 g of the polymer compound)
Degree of cationization (%) = X × (Y−Z) × 100 Formula (2)
[X: atomic weight of a cationized atom (such as nitrogen) in a cationic group of a polymer compound
Y: Number of moles of cationic group contained in 1 g of the polymer compound
Z: Number of moles of anionic group contained in 1 g of the polymer compound
(The anionic group of Z includes a carboxyl group and a sulfonic acid group contained in a monomer unit in the polymer chain. Specifically, it is a carboxylic acid in acrylic acid. However, a cationic group Is not included.)]
[0026]
As an example of calculating the degree of cationization, the case of MERQUAT280 (made by calgon) represented by the following formula is shown.
X: 14 (atomic weight of nitrogen atom)
Y: 4.95 × 10 ^-3 (Weight in 1 g of the cationic group: calculated from 0.8 g and the molecular weight of the cationic group)
Z: 2.78 × 10 ^-3 (Weight in 1 g of anionic group: calculated from 0.2 g and the molecular weight of the anionic group)
From equation (2)
Cation degree (%) =
14 × (4.95 × 10 ^-3 -2.78 × 10 ^-3 ) × 100 = 3.0
It is.
[0027]
[Chemical 2]

(MERQUAT280)
Mass ratio of dimethyldiallylammonium chloride to acrylic acid = 80: 20
[0028]
Therefore, according to the cationization degree calculation method described above, the cationization degree of the nonionic monomer polymer or the anionic monomer polymer is zero.
[0029]
The water-soluble polymer of component (B) preferably has a weight average molecular weight of 1,000 to 5,000,000, more preferably 3 as measured by gel permeation chromatography using polyethylene glycol as a standard substance. , 1,000 to 1,000,000, more preferably 5,000 to 500,000. If it is less than 1,000, it may be unpreferable in terms of odor, and if it exceeds 5,000,000, the viscosity of the composition increases, and the usability may decrease.
[0030]
Examples of the component (B) include MERQUAT100 (manufactured by Calgon), Adeka thioace PD-50 (manufactured by Asahi Denka Kogyo Co., Ltd.), DAIDOL EC-004, DAIDOL HEC, and DAIDOL EC (manufactured by Daido Kasei Kogyo Co., Ltd.). ) Dimethyldiallylammonium chloride polymer such as MERQUAT550 JL5 (manufactured by Calgon), dimethyldiallylammonium chloride / acrylic acid copolymer such as MERQUAT280 (manufactured by Calgon), and Leogard Cationized cellulose such as KGP (manufactured by Lion Corporation), imidazolium chloride / vinylpyrrolidone copolymer such as LUVIQUAT-FC905 (manufactured by B.A.S.F), LUGALVAN-G15000 (B.A.S. F) etc. Polyethyleneimine, cationized polyvinyl alcohol such as POVAL CM318 (manufactured by Kuraray Co., Ltd.), natural polymer derivatives having amino groups such as chitosan, vinyl monomers having hydrophilic groups with addition of diethylaminomethacrylate / ethylene oxide, etc. In the present invention, a dimethyldiallylammonium chloride polymer or an imidazolium chloride / vinylpyrrolidone copolymer is used.
[0031]
Among these, from the viewpoint of not hindering the texture such as flexibility imparted by the silicone, those having low rigidity imparted to the fiber when adsorbed by the component (B) alone are preferable.
[0032]
A particularly preferable polymer is a cationic polymer obtained by polymerizing a dimethyldiallylammonium salt represented by the following general formula (II). The structure of this polymer is usually represented by the following general formula (III-1) or the following general formula (III-2). Moreover, both the structural unit of general formula (III-1) and the structural unit of general formula (III-2) may be contained.
[0033]
[Chemical 3]

(Where X ^- Represents an arbitrary negative ion such as chloride ion or bromide ion. )
[0034]
[Formula 4]

[0035]
[Chemical formula 5]

(In the formula, c and d are average polymerization degrees, respectively, preferably in the range of 6 to 30,000, more preferably in the range of 20 to 6,000, still more preferably in the range of 30 to 3,000. )
[0036]
Examples of such a polymer include MERQUAT100 (Calgon), Adekathioace PD-50 (Asahi Denka Kogyo Co., Ltd.), Daidole EC-004, Daidole HEC, Daido Kagaku Kogyo Co., Ltd. Manufactured) and the like.
[0037]
As the component (B) of the present invention, the above water-soluble polymer compound having a cationic property may be used alone, or two or more kinds may be used as a mixture.
[0038]
(B) Although the compounding quantity of a component is not specifically limited, 0.1-30 mass% is mix | blended in a composition in the case of a liquid product in the range which does not provide rigidity to a fiber product, More preferably, it is 0.5-10. It is blended by mass%. If it is less than 0.1% by mass, the effect of promoting the adsorption of silicone becomes small, so the effects such as flexibility, smoothness, and drape are insufficient. If it exceeds 30% by mass, the viscosity of the composition increases and the usability is increased. It is not preferable.
[0039]
In the liquid softening agent composition of the present invention, the mass ratio of component (A): component (B) is in the range of 99: 1 to 50:50. Preferably in the range of 95: 5 to 60:40, more preferably in the range of 90:10 to 70:30, and within this range, excellent flexibility, smoothness, drapeability, etc. with respect to clothing such as polyester and cotton. Function is obtained. When the ratio of (B) component exceeds this range, textures, such as a softness | flexibility and a smoothness which a silicone compound provides, are impaired, and it is not preferable. In particular, in the case of a polymer that imparts rigidity to the fiber by component (B) alone, the flexibility and smoothness imparted by the silicone compound are not impaired, so the proportion of component (B) is within this range as much as possible. Less is preferable. On the other hand, when the proportion of the component (B) is less than this range, the adsorptivity of silicone to fibers is lowered, which is not preferable.
[0040]
Further, the liquid softener composition of the present invention is used in such an amount that the concentration of the component (A) is 5 ppm to 0.5% by mass with respect to the total amount of water used when the textile product is actually subjected to soft finishing. It is preferably used in an amount such that it is 10 ppm to 300 ppm. Further, the concentration of the component (B) is preferably used in such an amount as to be 0.5 ppm to 100 ppm, more preferably 3 ppm to 30 ppm.
[0041]
The component (C) is not particularly limited as long as it is one or more dyes selected from the group consisting of acid dyes and direct dyes. Specific examples of dyes that can be added include, for example, Dye Handbook (edited by the Society of Synthetic Organic Chemistry, published on July 20, 1970, Maruzen Co., Ltd.), Dye Note 22nd Edition (Shokusha Co., Ltd.), legal dyes Those described in the handbook (edited by the Japan Cosmetic Industry Association, published on November 28, 1988, Yakuji Nippo Co., Ltd.) can be mentioned. Among these, from the viewpoint of the storage stability of the liquid softening agent composition and the dyeing property to fibers, one or more dyes belonging to the following groups (C-1) to (C-3) should be used. Is preferred.
[0042]
Group (C-1) is a blue dye having a sulfonic acid group and having a triphenylmethane structure, an indigo structure, a diphenyl structure, and an anthraquinone structure, and a blue, purple, green dye, and a phthalocyanine structure. Among these, a dye having a triphenylmethane structure, a phthalocyanine structure, or an anthraquinone structure is preferable, and a dye having a triphenylmethane structure or a phthalocyanine structure is more preferable. Specific examples of the group (C-1) are shown below.
[0043]
[Blue dye]
C. I. Acid Blue 1, C.I. I. Acid Blue 7,
C. I. Acid Blue 9, C.I. I. Acid Blue 15,
C. I. Acid Blue 22, C.I. I. Acid Blue 23,
C. I. Acid Blue 25, C.I. I. Acid Blue 27,
C. I. Acid Blue 40, C.I. I. Acid Blue 41,
C. I. Acid Blue 43, C.I. I. Acid Blue 45,
C. I. Acid Blue 62, C.I. I. Acid Blue 74,
C. I. Acid Blue 78, C.I. I. Acid Blue 80,
C. I. Acid Blue 82, C.I. I. Acid Blue 83,
C. I. Acid Blue 90, C.I. I. Acid Blue 93,
C. I. Acid Blue 100, C.I. I. Acid Blue 103,
C. I. Acid Blue 104, C.I. I. Acid Blue 112,
C. I. Acid Blue 127, C.I. I. Acid Blue 138,
C. I. Direct Blue 1, C.I. I. Direct Blue 2,
C. I. Direct Blue 6,
C. I. Direct Blue 15,
C. I. Direct Blue 22,
C. I. Direct Blue 25,
C. I. Direct Blue 41,
C. I. Direct Blue 76,
C. I. Direct Blue 86,
C. I. Direct Blue90,
C. I. Direct Blue 98,
C. I. Direct Blue 120,
C. I. Direct Blue 158,
C. I. Direct Blue 165,
C. I. Direct Blue 168,
C. I. Direct Blue 226
[0044]
[Green dye]
C. I. Acid Green 3, C.I. I. Acid Green 9,
C. I. Acid Green 16, C.I. I. Acid Green 36,
C. I. Acid Green 25, C.I. I. Acid Green 27,
C. I. Acid Green 41, C.I. I. Acid Green 44,
C. I. Direct Green 1,
C. I. Direct Green 6,
C. I. Direct Green 8
[0045]
[Purple dye]
C. I. Acid Violet 15,
C. I. Acid Violet 43,
C. I. Acid Violet 34,
C. I. Acid Violet 41,
C. I. Acid Violet 49,
C. I. Direct Violet 1,
C. I. Direct Violet 12,
C. I. Direct Violet 22
[0046]
Among these, from the viewpoint of storage stability and dyeing property, C.I. I. Acid Blue 9, C.I. I. Direct Blue 86, C.I. I. Acid Green 25, C.I. I. Acid Violet 43, C.I. I. Acid Blue 7, C.I. I. Direct Violet 1, C.I. I. Acid Green 3, C.I. I. Acid Green 9, C.I. I. Acid Violet 15 is more preferable.
[0047]
Group (C-2) is a yellow dye having a sulfonic acid group and having a piazolone azo structure, a yellow dye having a sulfonic acid group and having a quinoline structure, a sulfonic acid group and having two or more azo groups A yellow dye and a yellow dye having a sulfonic acid group and a triazine structure. Among these, a dye having a sulfonic acid group and a piazolone azo structure, a dye having a sulfonic acid group and a triazine structure, and a dye having a sulfonic acid group and a quinoline structure are preferable. Specific examples of the group (C-2) are shown below.
[0048]
C. I. Acid Yellow 3,
C. I. Acid Yellow 11,
C. I. Acid Yellow 17,
C. I. Acid Yellow 23,
C. I. Acid Yellow 25,
C. I. Acid Yellow 29,
C. I. Acid Yellow 38,
C. I. Acid Yellow 40,
C. I. Acid Yellow 42,
C. I. Acid Yellow 44,
C. I. Acid Yellow 76,
C. I. Acid Yellow 141,
C. I. Direct Yellow 11,
C. I. Direct Yellow 12,
C. I. Direct Yellow 24,
C. I. Direct Yellow 33,
C. I. Direct Yellow 44,
C. I. Direct Yellow 50
[0049]
Among these, from the viewpoint of storage stability and dyeing property, C.I. I. Acid Yellow3, C.I. I. Acid Yellow 141, C.I. I. Acid Yellow 23 is more preferable.
[0050]
Group (C-3) has a red dye having a sulfonic acid group and an amide group and one azo group, a red dye having a sulfonic acid group and two or more azo groups, and one xanthene structure. A red dye. Specific examples of the group (C-3) are shown below.
[0051]
C. I. Acid Red 1, C.I. I. Acid Red 6,
C. I. Acid Red 32, C.I. I. Acid Red 35,
C. I. Acid Red 37, C.I. I. Acid Red 51,
C. I. Acid Red 52, C.I. I. Acid Red 87,
C. I. Acid Red 89, C.I. I. Acid Red 92,
C. I. Acid Red 94, C.I. I. Acid Red 97,
C. I. Acid Red 111, C.I. I. Acid Red 114,
C. I. Acid Red 115, C.I. I. Acid Red 133,
C. I. Acid Red 134, C.I. I. Acid Red 138,
C. I. Acid Red 145, C.I. I. Acid Red 154,
C. I. Acid Red 158, C.I. I. Direct Red 1,
C. I. Direct Red 2, C.I. I. Direct Red 4,
C. I. Direct Red 13, C.I. I. Direct Red 17,
C. I. Direct Red 23, C.I. I. Direct Red 24,
C. I. Direct Red 28, C.I. I. Direct Red 31,
C. I. Direct Red 33, C.I. I. Direct Red 37,
C. I. Direct Red 39, C.I. I. Direct Red 44,
C. I. Direct Red 46, C.I. I. Direct Red 62,
C. I. Direct Red 63, C.I. I. Direct Red 75,
C. I. Direct Red 79, C.I. I. Direct Red 80,
C. I. Direct Red 81, C.I. I. Direct Red 83,
C. I. Direct Red 84,
C. I. Direct Red 113,
C. I. Direct Red 229
[0052]
Among these, from the viewpoint of storage stability and dyeing property, C.I. I. Acid Red 138, C.I. I. Acid Red 1, C.I. I. Acid Red 52, C.I. I. Acid Red 6, C.I. I. Acid Red 35, C.I. I. Acid Red 37, C.I. I. Direct Red 23, C.I. I. Direct Red 24 is more preferred.
[0053]
The amount of component (C) is preferably 0.01 to 50 ppm, more preferably 0.1 to 30 ppm in the composition. If it is less than 0.01 ppm, the color colored by the liquid softening agent composition will become very thin, and the measurement improvement effect may become inadequate. Moreover, when it exceeds 50 ppm, the color colored by the liquid softening agent composition may become too dark.
[0054]
As the antioxidant of component (D), generally known natural antioxidants and synthetic antioxidants can be used. Antioxidants include ascorbic acid, ascorbyl palmitate, propyl gallate, BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), hydroquinone, tertiary butylhydroquinone, natural tocopherol compounds, gallic acid length Chain (C8-C22) ester (for example, dodecyl gallate), Irganox compound available from Ciba Specialty Chemicals, 4,5-dihydroxy-m-benzenesulfonic acid or its sodium salt, dimethoxyphenol, catechol, Examples include methoxyphenol, carotenoids, furans, and amino acids. These 1 type can be used individually or in combination of 2 or more types.
[0055]
Among these, BHT (butylated hydroxytoluene), methoxyphenol, tocopherol compounds, and the like are preferable from the viewpoint of the appearance and storage stability of the liquid softening agent composition.
[0056]
(D) It is preferable that the compounding quantity of a component is used in the range of 0.01-1 mass% in a composition. If the amount is less than 0.01% by mass, the anti-fading effect may be insufficient. If the amount exceeds 1% by mass, the effect becomes constant, and further use may be uneconomical.
[0057]
Further, in the present invention, in order to ensure the storage stability of the liquid softening agent composition, in addition to the above components, the (E) component nonionic surfactant and the (F) component lower alcohol, glycol ether solvent. And one or more water-soluble solvents selected from the group consisting of polyhydric alcohols.
[0058]
As the nonionic surfactant of component (E), for example, polyoxyalkylene alkyl ethers having at least one alkyl group or alkenyl group having 8 to 20 carbon atoms are preferable, and in particular, an average of 2 to 50 moles of oxyalkylene group is added. Are preferred. Furthermore, the nonionic surfactant represented by the following general formula (IV) is preferable.
R ¹ -T-[(R ² O) _p -H] _q (IV)
(Wherein R ¹ Is an alkyl or alkenyl group having 10 to 18 carbon atoms, preferably 12 to 18 carbon atoms, and R ² Is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. p is an average addition mole number, and shows the number of 2-50, Preferably it is 5-30, Most preferably, it is 5-20. T is -O-, -N-, -NH-, -N (C ₂ H _Four OH)-, -CON-, -CONH- or -CON (C ₂ H _Four OH)-and T is -O-, -NH-, -N (C ₂ H _Four OH)-, -CONH-, or -CON (C ₂ H _Four In the case of OH)-, q is 1, and when T is -N- or -CON-, q is 2. )
[0059]
Specific examples of the compound of the general formula (IV) include compounds represented by the following general formulas (V) and (VI).
R ¹ -O- (C ₂ H _Four O) _r -H (V)
(Wherein R ¹ Has the same meaning as above, and r is the average number of moles added, and is a number from 2 to 50, preferably from 5 to 30. )
R ¹ -O- (C ₂ H _Four O) _s (C _Three H ₆ O) _t -H (VI)
(Wherein R ¹ Has the same meaning as above, s and t are the average number of moles added, s is a number from 2 to 40, preferably from 5 to 30, and t is a number from 1 to 20, preferably from 1 to 10. . (C ₂ H _Four O) and (C _Three H ₆ O) may be random or block adducts. )
[0060]
(E) As a nonionic surfactant of a component, these 1 type can be used individually or in combination of 2 or more types.
[0061]
(E) The compounding quantity of a component is 0.1-20 mass% in a composition, Especially 0.5-15 mass%, Furthermore, 0.5-10 mass% is preferable. If the amount is less than 0.1% by mass, the effect of improving the storage stability may be reduced. Even if the amount exceeds 20% by mass, the effect of improving the storage stability is constant. This is uneconomical and may be undesirable from the standpoint of foaming during flexible processing.
[0062]
Component (F) is one or more water-soluble solvents selected from the group consisting of lower (C1-4) alcohols, glycol ether solvents, and polyhydric alcohols. Specifically, ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and a water-soluble solvent represented by the following general formula (VII) Is preferred.
R ^Three -O- (C ₂ H _Four O) _y -(C _Three H ₆ O) _z -H (VII)
(Wherein R ^Three Is an alkyl or alkenyl group having 1 to 8 carbon atoms, preferably 2 to 6 carbon atoms. y and z are average addition mole numbers, y is 1-50, Preferably it is 1-30, z shows the number of 0-50, Preferably it is 0-20. )
[0063]
Among them, preferred examples include ethanol, ethylene glycol, butyl carbitol, propylene glycol, ethylene glycol polyprooxypropylene (2) monobutyl ether [C _Four H ₉ O (C ₂ H _Four O) (C _Three H ₆ O) ₂ H] and the like.
[0064]
These components (F) are blended in the composition in an amount of 0.1 to 30% by mass, preferably 2 to 20% by mass.
[0065]
Further, the present invention preferably contains an antifoaming agent as component (G) in order to suppress foaming and improve the meterability of the softening agent. Examples of antifoaming agents include silicone-based antifoaming agents, alcohol-based antifoaming agents, ester-based antifoaming agents, mineral oil-based antifoaming agents, vegetable oil-based antifoaming agents, and synthetic oil-based antifoaming agents. A silicone-based antifoaming agent is preferable from the viewpoint of suppressing foaming during measurement of the softening agent and improving meterability. Examples of silicone-based antifoaming agents used in the present invention include oil-type antifoaming agents, compound-type antifoaming agents, self-emulsifying antifoaming agents, emulsion-type antifoaming agents, powder-type antifoaming agents, and solid-type antifoaming agents. Etc. Among these, the self-emulsification type antifoaming agent and the emulsion type antifoaming agent are more preferable, and the emulsion type antifoaming agent is particularly preferable in terms of the effect of improving meterability.
[0066]
Specific examples of the antifoaming agent include DK Q1-071, DK Q1-1208, DK Q1-1086, 544, 001, 80, 81, 026A, 545A, and 013B of FS Antifoam series manufactured by Dow Corning Asia Co., Ltd. , DK Q1-072, AFE, BE, DB-31, DB-110N, H-10, 025, EPL, F-18, F-20, F-51, CE, 90, 91, 92, 1122, DK Q1 -1089, DK Q1-1056, DK Q1-1014, DK Q1-1014, KS496A, KS502, KS506, KS508, KS530, KS531, manufactured by Shin-Etsu Chemical Co., Ltd., KS536, KS537, KS538, KM73, KM73B, KM73B, KM73E, KM72, KM72A, KM72F, KM70, KM71, K M75, KM80, KM83, KM83A, KM85, KM87A, KM89, KM90, KM93, KM68-1F, KM68-2F, Q2-3183A manufactured by Toray Dow Corning Silicone Co., Ltd., BY28-503, SD5591, SH7PA, SH5503, SH5510, SM5513, SH5561, SH5507, BY22-517, SM5511, SM5512, SM5515, SM5517, SM5571, SM5572F, SM5573, GE Toshiba Silicones Co., Ltd. YSA6406, TSA780, TSA7341, TSA7343, TSA732A, TSA732A TSA730, TSA770, TSA775, TSA776, YMA6509, TSA737, TSA737B, T SA737S, TSA737F, TSA737K, etc. are mentioned.
[0067]
(G) As an antifoamer of a component, these 1 type can be used individually or in combination of 2 or more types.
[0068]
Although the compounding quantity of (G) component is not specifically limited, 0.1 ppm-1 mass% is mix | blended in a composition in the range which does not impair the external appearance of a liquid softening agent composition, More preferably, 1 ppm-0.05 mass% Blended. If the amount is less than 0.1 ppm, the defoaming effect is small and the effect of improving the meterability may be insufficient. If the amount exceeds 1% by mass, the appearance may be impaired particularly when the appearance of the composition is transparent.
[0069]
In the present invention, a fragrance can be added for the fragrance of the composition. A list of perfume ingredients used can be found in various publications such as “Perfume and Flavor Chemicals”, Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic fragrance chemistry and commercial knowledge", Motoichi Into, Chemical Industry Daily (1996) and "Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allred Pub. Co. (1994) and "Encyclopedia of Scents", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Performer Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oils". Danute Lajaujis Anonis, Allured Pub. Co. (1993), etc., each of which is incorporated herein by reference.
[0070]
The liquid softener composition of the present invention has an isothiazolone-based organic sulfur compound, a benzisothiazoline-based organic sulfur compound, a benzoic acid, a phenolic compound, a cation as an antiseptic / disinfectant for the purpose of enhancing antiseptic and sterilizing power. One of the system compounds and other compounds may be used alone or in combination of two or more.
[0071]
As the isothiazolone-based organic sulfur compound, an antimicrobial organic antiseptic / bactericidal agent containing a 3-isothiazolone group is preferable. These compounds are disclosed in Lewis et al., US Pat. No. 4,265,899, issued May 5, 1981. Examples include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, 2-phenyl-3-isothiazolone, 2-methyl. -4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof. A more preferred antiseptic / disinfectant is a water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, more preferably about 77% by mass. Water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and about 23% by weight of 2-methyl-4-isothiazolin-3-one. Examples of isothiazolone-based organic sulfur compounds include Rohm &Haas's Caisson CG / ICP (approximately 1.5% by weight aqueous solution), Junsei 5 (approximately 5% by weight ethylene glycol solution) manufactured by Pure Chemical Co., Ltd. Commercially available products exemplified in the Junside Series of No. 1 can be used.
[0072]
Examples of benzisothiazoline-based organic sulfur compounds include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and related compounds include dithio-2. , 2-bis (benzmethylamide) and the like can be used, and they can be used in any mixing ratio. Examples of such compounds include Proxel series [BDN (effective content 33% by mass), BD20 (effective content 20% by mass), XL-2 (effective content 10% by mass), GXL (effective content) manufactured by Avicia Co., Ltd. 20 mass%), LV (effective mass 20 mass%), TN (effective mass 60 mass%)], and commercially available products such as Denide BIT / NIPA.
[0073]
Benzoic acids and phenolic compounds include benzoic acid or a salt thereof, salicylic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, paraoxybenzoic acid Benzyl, 3-methyl-3-isopropylphenol, o-phenylphenol, 2-isopropyl-5-methylphenol, resorcin, cresol, 2,6-di-tert-butyl-p-cresol, and the like can be used.
[0074]
As the cationic compound, benzalkonium chloride, benzethonium chloride, alkyltrimethylammonium salt, alkylquinolinium salt, alkylaminopropyldimethylbenzylammonium salt, alkylpyridinium salt, dialkyldimethylammonium salt, polyoxyalkylenetrialkylammonium salt, Examples thereof include alkylphenoxyethyldimethylbenzylammonium salt, alkylisoquinolinium salt, alkyldimethylbenzylammonium salt, polyoxyethylenetrimethylammonium salt, alkyldimethylphenoxyethylammonium salt, alkylimidazolium salt, chlorhexidine gluconate and the like.
[0075]
Other compounds include 5-bromo-5-nitro-1,3-dioxane, 2-bromo-2-nitropropane-1,3-diol, 5-chloro-5-nitro-1,3-dioxane, 2 -Chloro-2-nitropropane-1,3-diol can also be used, and commercially available products such as Henkel's Bronidox L, Inolex's Bronopol, Yoshitomi Pharmaceutical's Bronopol, Boots' Myaside BT, etc. Can do.
[0076]
These preservatives / bactericides are preferably blended in an amount of 0 to 0.1% by weight, more preferably 0.00001 to 0.03% by weight, and more preferably 0.00005 to 0.00005%. 0.02% by mass. However, when using a benzoic acid or a phenol compound, it is preferable to mix | blend 0-3 mass% with respect to a composition, More preferably, it is 0.01-1.5 mass%.
[0077]
Among the above-mentioned preservatives and fungicides, use one or more selected from caisson CG / ICP, proxel series BDN, myaside BT, benzoic acid, didecyldimethylammonium salt and benzalkonium chloride. Is particularly preferable, and the blending amount when these are used is preferably 0.00001 to 2% by mass. More preferably, it is 0.00001-1 mass%, More preferably, it is 0.00005-0.5 mass%.
[0078]
In addition, for the purpose of improving the antiseptic and bactericidal power, 0 to 0.5% by mass, preferably 0.00001 to 0.1% by mass, of one or more of the following compounds are used with respect to the composition. be able to. Examples of the compound include sodium pyrithione, 1,3-bis (hydroxymethyl) -5,5-dimethyl-2,4-imidazolidinedione, dimethyloldimethylhydantoin, DMDM hydantoin (Glydant or Glydan Plus manufactured by Lonza), N [1,3-bis (hydroxymethyl) 2,5-dioxo-4-imidazolidinyl] -N, N′-bis (hydroxymethyl) urea (generally sold under the name of diazolidinyl urea), N, N ″ — Methylenebis {N '-[1- (hydroxymethyl) -2,5-dioxo-4-imidazolidinyl] urea}, an imidazolidinedione compound commonly known as imidazolidinylurea, polymethoxide bicyclic oxazolidine compound, formaldehyde, glutaraldehyde And so on Molecular aldehyde, general formula HCl · NH ₂ -(CH ₂ ) _Three -[-(CH ₂ ) _Three -NH-C (= NH) -NH-C (= NH.HCl) -NH- (CH ₂ ) _Three -] _x -(CH ₂ ) _Three 1,1′-hexamethylene bis (5- (5), commonly known as polyaminopropyl biguanide, polyaminopropyl biguanide, chlorhexidine, also known as polyhexamethylene biguanide having —NH—C (═NH) —NH · CN (P-chlorophenyl) biguanide), digluconate and its diacetate which are salts of acetic acid and digluconic acid, Proxel IB, 1- (3-chloralyl) -3,5,7-triaza, manufactured by Avicia Co., Ltd. -1-Azonia adamantane chloride (for example, sold under the trade name Dowil 200 from Dow Chemical), dehydroacetic acid, commonly known as propamidine isethionate, 4,4'-diamidino-α, ω-diphenoxypropane di Isethionate, generally hexamidine isethione 4,4′-diamidino-α, ω-diphenoxyhexanediisethionate, 12- (4′-thiazolyl) -benzimidazole, 2- (4-thiocyanomethylthio) benzothiazole, known as Imidazole or thiazole antibacterial agents such as methyl-2-benzimidazolecarbamide, 1,1,1-trichloro-2-methylpropan-2-ol generally known as chlorobutanol, chlorobutanol, 4,4'- N- (4-), also known as (trimethylenedioxy) bis- (3-bromobenzamidine) diisethionate, dibromopropamidine, dibromopropamidine, 3,4,4'-trichlorocarbanilide, triclocarban Chlorophenyl) -N '-(3,4-dichlorophenyl) urea, triclosa 2,4,4′-trichloro-2′-hydroxydiphenyl ether, 4,4′-dichloro-2-hydroxydiphenyl ether, which is generally known as N, and Chinosan HP100 (trade name) manufactured by Ciba Specialty Chemicals, Examples include zinc compounds such as zinc chloride.
[0079]
In the liquid softener composition of the present invention, the stability of the liquid softener composition such as aroma can be improved by further blending a chelating agent. Specific examples of the chelating agent include phosphonic acid-based chelating agents such as hydroxyethanediphosphonic acid (Lion Chemical Co., Ltd. Ferriox CY-115), ethylenediaminetetraphosphonic acid (Monsant Dequest 2041), D-2000, 2010, and 2066. , Ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid, captocatecic acid, ethylenediamine disuccinic acid, methylglycine diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, aspartic acid, and salts thereof such as sodium. The chelating agent can be blended in the composition in an amount of 0 to 3% by mass within the range not impeding the effects of the present invention.
[0080]
In the liquid softening agent composition of the present invention, additives that are used in ordinary household finishing agents can be used in addition to the above components, as long as the effects of the present invention are not hindered. Specific examples of such additives include cationic surfactants, anionic surfactants, anionic polymer compounds, partially esterified products of hexanoic acid and glycerin or pentaerythritol, sodium chloride, ammonium chloride, chloride Water-soluble salts such as calcium, magnesium chloride and potassium chloride, oils such as liquid paraffin and higher alcohol, urea, hydrocarbons, nonionic cellulose derivatives, UV absorbers, fluorescent brighteners, pH adjusters described later It is done. In addition, since an anionic surfactant and an anionic polymer compound mix | blend more than content of the cationic polymer compound of (B) component, in order to reduce the adsorption effect of a silicone compound remarkably, (B) It is not preferable to add more than the content of the component cationic polymer compound.
[0081]
Although the pH of the liquid softening agent composition of this invention is not specifically limited, It is preferable that it is the range of 3-10, and it is more preferable that it is the range of 4-7. As necessary, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, paratoluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethanediphosphonic acid, phytic acid, ethylenediaminetetraacetic acid, PH adjustment of short chain amine compounds such as triethanolamine, diethanolamine, dimethylamine, N-methylethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, alkali metal silicates An agent can be used.
[0082]
The liquid softener composition of the present invention contains the above components (A) to (D), and optionally (E) to (G) components and optional components, and the balance is usually water. In addition, the liquid softener composition of the present invention is used after being diluted to an appropriate concentration. The method of use is not particularly limited, but the clothes of the present invention are treated by washing the clothes normally, and the composition of the present invention is dissolved in water at the rinse stage, and the composition of the present invention is used using a container such as a tub. Examples include a method in which an object is dissolved in water, and further, clothing is added to perform immersion treatment. The fiber product may be treated by any method, but the bath ratio (ratio of the treatment liquid to the fiber product) is preferably 3 to 100 times, particularly preferably 5 to 50 times.
[0083]
The liquid softening agent composition of the present invention can be filled into a container with a measuring cap or a refilling container, which is usually used for a finishing agent or a cleaning agent that is commercially available. The material of these containers is not particularly limited, and examples thereof include glass, paper, and plastic. Among these, plastic is preferable from the viewpoint of usability. Examples of the plastic used for the container include polyethylene, polypropylene, nylon, polyethylene terephthalate, and vinyl chloride, and one or more of these are used. In addition, additives such as pigments, ultraviolet absorbers and antistatic agents are appropriately added to these plastics. Further, the appearance of the plastic container may be transparent or translucent, and may be opaque. However, from the viewpoint of easy understanding of the remaining amount of the contents, it is preferably transparent or translucent, particularly a liquid softener. When the composition has a transparent appearance, it is preferable to use an uncolored or colored transparent container in order to increase the value of the product.
[0084]
【The invention's effect】
According to the present invention, a silicone compound and a cationic polymer compound are used in a specific ratio, and further, a dye and an antioxidant are used in combination, thereby providing excellent flexibility, smoothness, and drape in various textile products. In addition, a liquid softener having good color tone stability due to light or the like can be obtained. Furthermore, by using a nonionic surfactant and a specific water-soluble solvent in combination, good storage stability is obtained, and by using a silicone having a polyether group as the silicone, it has a highly transparent appearance and is a container. A liquid softening agent that does not generate a sticking substance on the surface is obtained, and the meterability is improved by adding an antifoaming agent.
[0085]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples,% indicates mass%.
[0086]
[Examples 1, 2, 4-14, 16-33, Comparative Examples 1, 2, 5-6]
(Preparation of softener composition)
The components (A) to (G) shown in Tables 1 to 7 are converted according to the compositions shown in Tables 8 to 10 below (excluding (C), (G) components and common components, pure conversion,%, (C) , (G) component, common component is solid,%), (A), (D), (E), (F) component, and the following common components are placed in a 1000 mL beaker and thoroughly mixed with a stirring blade. Stir. Next, ion-exchanged water is added with stirring, and component (B) is added while stirring. After stirring, component (C) is further added and stirred, and then component (G) is added to become uniform. The liquid softener composition of 800 g was prepared with sufficient stirring. The obtained liquid softener composition was evaluated for softness and smoothness, drape, color tone stability, liquid appearance, storage stability, cap dirt, and meterability. The results are also shown in Tables 8-10.
[0087]
[Examples 3 and 15, Comparative Example 3]
According to the composition shown in the following Tables 8 and 9 (except for the (C) component and common component, converted into a pure component,%, (C) component, common component is solid,%), (D), (E), ( The component F) and the common components described below were placed in a 1000 mL beaker and sufficiently stirred using a stirring blade. Next, ion-exchanged water is added with stirring, components (A) and (B) are added with stirring, and after stirring, component (C) is added and stirred well until uniform, and 800 g A liquid softener composition was prepared. The obtained liquid softener composition was evaluated for softness and smoothness, drape, color tone stability, liquid appearance, storage stability, cap dirt, and meterability. The results are also shown in Tables 8-9.
[0088]
[Comparative Example 4]
According to the composition shown in Table 9 below (% (excluding component (C)), pure conversion,%, component (C) is solid,%), distearyldimethylammonium chloride (manufactured by Lion Akzo Co., Ltd.), (C) , (E) and (F) were placed in a 500 mL beaker and stirred thoroughly. Next, this was added to ion-exchanged water heated to 60 ° C. with stirring. At this time, the ion-exchanged water was stored in a glass container having an inner diameter of 110 mm and a height of 190 mm, and sufficiently stirred at a rotation speed of 1000 rpm using an agitator (Agitator SJ type, manufactured by Shimazaki Seisakusho Co., Ltd.). The sample preparation amount was 1000 g, and all these steps were performed at 60 ° C. or higher.
[0089]
The components, common components, and evaluation methods used in Examples and Comparative Examples are shown below.
[Silicone compound]
Silicone compounds (A-1 to 4) shown in Table 1 were used.
[0090]
[Table 1]

[0091]
[Water-soluble polymer having cationic properties]
The water-soluble polymer compounds (B-1 to 3) having cationic properties shown in Table 2 were used.
[0092]
[Table 2]

[0093]
〔dye〕
The dyes (C-1 to 3) described in Table 3 were used.
[0094]
[Table 3]

[0095]
〔Antioxidant〕
Antioxidants (D-1 to 3) described in Table 4 were used.
[0096]
[Table 4]

[0097]
[Nonionic surfactant]
Nonionic surfactants (E-1 to 3) listed in Table 5 were used.
[0098]
[Table 5]

[0099]
(Water-soluble solvent)
The water-soluble solvents (F-1 to 3) described in Table 6 were used.
[0100]
[Table 6]

[0101]
[Defoamer]
Silicone antifoaming agents (G-1 to 3) listed in Table 7 were used.
[0102]
[Table 7]

[0103]
(Common ingredient 1)
The following components were added in the amount shown in [] (the amount in solid form).
1-1: Caisson CG-ICP (Rohm & Haas) [100ppm]
1-2: Fragrance composition A (Table 11-21 description) [0.3%]
[0104]
(Common component 2)
The following components were added in the amount shown in [] (the amount in solid form).
2-1: Proxel BDN (Avisia Co., Ltd.) [5 ppm]
2-2: Perfume composition B (described in Tables 11 to 21) [0.3%]
[0105]
(Common component 3)
The following components were added in the amount shown in [] (the amount in solid form).
3-1: Bronopol (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) [20 ppm]
3-2: Fragrance composition C (Tables 11 to 21) [0.3%]
[0106]
(Common component 4)
The following components were added in the amount shown in [] (the amount in solid form).
4-1: Junside 5 (manufactured by Pure Chemical Co., Ltd.) [30ppm]
4-2: Fragrance composition D (described in Tables 11 to 21) [0.3%]
[0107]
(Common component 5)
The following components were added in the amount shown in [] (the amount in solid form).
5-1: Myaside Pharma BP (manufactured by BASF Japan Ltd.) [50 ppm]
5-2: Fragrance composition D (described in Tables 11 to 21) [0.3%]
[0108]
[Method for evaluating softness, smoothness, and drape]
(1) Treatment method with softener composition
(Preparation of test cloth)
Commercial cotton knit (100% cotton) and polyester jersey (100% polyester), commercial detergent "Top" [manufactured by Lion Co., Ltd., ingredients: surfactant (sodium alpha olefin sulfofatty acid ester, fatty acid sodium, straight chain] Alkylbenzene, polyoxyethylene alkyl ether), water softener, alkali agent, enzyme, fluorescent whitening agent], using a two-tank washing machine for home use for 15 minutes (standard amount of detergent used, bath ratio 30 times) , 45 ° C. tap water) → Dehydration 5 minutes step was repeated 2 cycles, then rinsed with running water 15 minutes → dehydration 5 minutes was repeated 5 times, and naturally dried to obtain a test cloth.
[0109]
(Treatment with softener)
Cotton gnit 700 g and polyester jersey 300 g subjected to the above-mentioned treatment are commercially available detergent “Top” [manufactured by Lion Co., Ltd., component: surfactant (alpha olefin sulfofatty acid ester sodium, fatty acid sodium, linear alkylbenzene series, poly Oxyethylene alkyl ether), water softener, alkali agent, enzyme, fluorescent whitening agent] for 15 minutes (detergent is used in standard amount, bath ratio 30 times, using tap water at 25 ° C) In addition, 10 g of the softener composition shown in Tables 8 to 10 per 30 liters of water (however, 6.6 g in Example 26 and 5 g in Example 27) were added, and the fabric was softened (30 times the bath ratio, 25 Using tap water at 0 ° C., 3 minutes). Then, it air-dried on the conditions of 20 degreeC and 40% RH, and performed the following evaluation.
[0110]
(2) Evaluation method
(1) Evaluation of flexibility and smoothness
A sensory pair comparison was performed by 10 expert panelists using cotton knit and polyester jersey treated without using a softener as a control, and evaluation was performed according to the following evaluation criteria.
+2: clearly better than the control
+1: slightly better than control
0: almost the same as the control
-1: The control is slightly better
-2: The control is clearly better
The average of the scores was taken, and 1.5 to 2.0 points were rated as ◎, 1.0 to 1.4 points as ◯, 0.5 to 0.9 points as △, and 0.4 points or less as ×. .
[0111]
(2) Evaluation of drape
A commercially available fleece (SP No. 6A018 100% polyester manufactured by UNIQLO) was treated by the following method. Wash one fleece with three commercially available long-sleeved shirts (made by UNIQLO, 100% cotton) with a commercially available laundry detergent “Top” (manufactured by Lion Corporation) for 15 minutes using a fully automatic washing machine for home use ( Standard amount of detergent used, bath ratio 30 times, 25 ° C. tap water), and for the second rinse, 15 g of softener composition shown in Tables 8-10 to 45 liters of water (however, Example 26 is 10 g, 7.5 g in Example 27), and the clothing was softened (30 times the bath ratio, using tap water at 25 ° C., 3 minutes). After repeating this washing-softening process 7 times, it is naturally dried under the conditions of 20 ° C. and 40% RH, actually wearing a fleece, and the drapeability at that time is visually checked according to the evaluation criteria shown below. Judged by.
[0112]
Drapability refers to the 2nd edition Textile Handbook (edited by the Textile Society of Japan, published on March 25, 1994, Maruzen Co., Ltd.), Encyclopedia of textiles (edited by Tatsuya Motomiya et al., Published on March 25, 2002) As described generally in documents such as Maruzen Co., Ltd.), it is the ability to form a deformed state (drape) of the fabric due to its own weight, etc., but there are a wide variety of evaluation methods. Here, the following criteria were used to evaluate the beauty of clothing silhouettes when worn.
○: Have a beautiful silhouette equal to or better than new
△: The new one has a slightly beautiful silhouette (almost equivalent to Comparative Example 4)
×: The new one has a clear and beautiful silhouette (almost the same as that processed without using a softener)
[0113]
[Storage stability evaluation method]
In accordance with the composition shown in Table 9 and Table 10 below, the liquid softening agent composition prepared based on the above [Preparation of softening agent composition] and polyethylene terephthalate (PET) containers for Examples 13-18 and 25-28. In 1 *, Examples 19 to 24, 29 to 33, and Comparative Examples 4 to 6 were put in a polyethylene terephthalate (PET) container 2 * and sealed, and the appearance (transparency) and storage stability of the liquid were evaluated. In addition, the storage stability was evaluated by the following evaluation criteria by observing changes in appearance after leaving it for 1 month under the conditions of 25 ° C., 40 ° C., and 5 ° C. while being sealed in the polyethylene terephthalate (PET) container.
(Liquid appearance evaluation criteria)
A: Transparent
○: There is no transparency, but it is uniformly dispersed
Δ: Slightly produced
X: Precipitation or separation occurs
(Storage stability evaluation criteria)
○: There is no change from the initial product, and it is transparent and uniformly or uniformly dispersed.
Δ: Slightly or slightly separated
X: Precipitation or separation occurs
Container 1 *: A container formed by blow molding a polyethylene terephthalate (PET) resin (Kodak A-12). The capacity of the container is 300 mL, the thickness of the resin is 0.4 mm, the appearance is colorless and transparent, and the pigment and ultraviolet absorber are not added.
Container 2 *: A container formed by blow molding a polyethylene terephthalate (PET) resin (Kodak A-12). The capacity of the container is 300 mL, the thickness of the resin is 0.4 mm, the appearance is blue and transparent, the pigment (PT-RM AZ MB0980 (A) Blue 31X) is contained in 0.02%, and the UV absorber is not added.
[0114]
[Evaluation of color stability in transparent containers]
According to the composition shown in Tables 8 to 10 below, 200 mL of the liquid softening agent composition prepared based on the above [Preparation of softening agent composition] is put in a polyethylene terephthalate (PET) container 1 * and sealed, and IRIE UV ILLUMINATOR is used. 14.7 MJ / m from a distance of about 8 cm using (Irie Seisakusho) ² Irradiated, the change in color tone was visually observed, and evaluated according to the following evaluation criteria.
(Color Stability Evaluation Criteria)
○: No change from initial product
Δ: Slightly faded compared to the initial product and slightly changed in color tone
×: Fading significantly compared to the initial product, and the color tone has changed remarkably
[0115]
[Measuring method]
In accordance with the composition shown in Table 10 below, a liquid softener composition prepared based on the above [Preparation of softener composition] was used as a plastic container with a measuring cap of “Wrinkle Refreshing Soflan C” (manufactured by Lion Corporation) ( 700ml filling cap (made of translucent polypropylene, bottle: opaque polyethylene / polypropylene), sealed tightly, shaken lightly up and down 5 times, cap liquid softener composition from bottle into measuring cap 5 minutes later The 20 (mL) scale line was poured so that the liquid level overlapped. The ease of measurement at that time was evaluated according to the following evaluation criteria.
(Measuring standard)
○: Although the bubbles are slightly entangled with the liquid surface, it can be measured accurately as indicated by the scale line.
Δ: Bubbles are entangled in the liquid surface, making it difficult to grasp the liquid surface, but it is possible to measure
×: Bubbles are considerably entangled in the liquid surface, making weighing difficult
[0116]
[Cap dirt evaluation method]
In accordance with the composition shown in Tables 9 to 10 below, the liquid softening agent composition prepared on the basis of the above [Preparation of softening agent composition] is placed on a measuring cap (for 30 mL, made of translucent polypropylene) and 20 (mL ) To the graduation line, and left for 2 days. The cap dirt at that time was evaluated according to the following evaluation criteria. Cap dirt is caused by the ease of film formation and solidification when the liquid softener composition is attached to the cap. Therefore, this method is an accelerated test for cap dirt when used repeatedly for a long time in an actual home.
(Cap dirt evaluation criteria)
○: There is almost no sticking matter.
Δ: Slightly adhered matter is attached
×: Adherent matter is considerably attached
[0117]
[Table 8]

* Slight creaking
[0118]
In addition, the cotton knit / polyester cloth treated with the product of the present invention had a finish excellent in flexibility, smoothness and drape, and also had good color stability.
[0119]
[Table 9]

* Slightly creased, ** Slightly slimy
[0120]
[Table 10]

[0121]
By combining a nonionic surfactant and a water-soluble solvent, storage stability is improved from low temperature to high temperature, and by using silicone having a polyether group as a silicone compound, it has a transparent liquid appearance from low temperature to high temperature. In addition, there was no occurrence of sticking matter on the container or the like, and a softener composition with good meterability could be obtained by combining an antifoaming agent.
[Table 11]

[0122]
[Table 12]

[0123]
[Table 13]

[0124]
[Table 14]

[0125]
[Table 15]

[0126]
[Table 16]

[0127]
[Table 17]

[0128]
[Table 18]

[0129]
[Table 19]

[0130]
[Table 20]

[0131]
[Table 21]

* 1: [Flowers oils and Floral Compounds In Performance] Dante Lajaujis Anonis, Allured Pub. Co.

Claims (6)

  (A) a silicone compound, (B) a dimethyldiallylammonium chloride polymer or an imidazolium chloride / vinylpyrrolidone copolymer, (C) an acid dye and / or a direct dye, and (D) an antioxidant, and ( A): (B) (mass ratio) is 99: 1-50: 50, The liquid softener composition characterized by the above-mentioned.   (C) Acid dyes and / or direct dyes may be C.I. I. Acid Red 52, C.I. I. Acid Blue 9 and C.I. I. The liquid softener composition according to claim 1, wherein the composition is one or more selected from Acid Yellow 3.   (D) The liquid softener composition according to claim 1 or 2, wherein the antioxidant is one or more selected from butylated hydroxytoluene, p-methoxyphenol and tocopherol acetate.   And (E) a nonionic surfactant and (F) one or more water-soluble solvents selected from the group consisting of lower alcohols, glycol ether solvents, and polyhydric alcohols. The liquid softening agent composition according to any one of claims 1 to 3.   The liquid softener composition according to any one of claims 1 to 4, wherein the component (A) is a silicone compound having a polyether group, and the liquid softener composition is transparent.   Furthermore, (G) antifoamer is contained, The liquid softening agent composition of any one of Claims 1-5 characterized by the above-mentioned.