JP4672245B2 - Liquid softener composition - Google Patents

Description

【００１２】
〔式中、Ｒ¹、Ｒ²、Ｒ⁶及びＲ⁷は、それぞれに独立に、炭素数１０〜１４のアルキル基又はアルカノイル基であり、Ｒ⁴、Ｒ⁵、Ｒ¹⁰及びＲ¹¹は、それぞれ独立に、炭素数１〜６のアルキレン基であり、Ｒ³、Ｒ⁸及びＲ⁹は、それぞれ独立に、炭素数１〜３のアルキル基もしくはヒドロキシアルキル基又はＲ^12'−Ｅ−Ｙ−であり（ここでＲ^12'は炭素数６〜１４のアルキル基又はアルカノイル基であり、Ｙは炭素数１〜６のアルキレン基である）、Ａ、Ｂ、Ｃ、Ｄ及びEは、それぞれ独立に、Ｒ¹、Ｒ²、Ｒ⁶、Ｒ⁷及びＲ^12'がアルキル基の時は、−ＯＣＯ−及び−ＮＨＣＯ−から選ばれる基であり、Ｒ¹、Ｒ²、Ｒ⁶、Ｒ⁷及びＲ^12'がアルカノイル基の時は、−Ｏ−及び−ＮＨ−から選ばれる基である。ａ、bは、それぞれ独立に、０又は１の数である。Ｘ^-は陰イオン基である。〕
【００１３】
本発明では、特に（ａ）成分として、下記（１−１）〜（１−３）の化合物及び下記（２−１）〜（２−４）の化合物から選ばれる１種以上の化合物が好適である。
【００１４】
【化３】

【００１５】
〔式中、Ｒ¹²は炭素数９〜１３のアルキル基、Ｒ¹³、Ｒ¹⁴は、それぞれ独立して、メチル基、エチル基、ヒドロキシエチル基、又はＲ¹²−ＣＯＯ−(ＣＨ₂)_a−、Ｒ¹⁵は炭素数１０〜１４のアルキル基、ａ、ｂは、それぞれ独立に２又は３の数、Ｘ^-は陰イオン基である。〕
【００１６】
通常（ａ）成分はパーム油、パーム核油、ひまわり油、大豆油等の油脂から蒸留などの精製工程を経て得られる、ラウリン酸、ミリスチン酸（又はその低級アルキルエステル）、ラウリルアルコール、ミリスチルアルコールを原料として製造される。
【００１７】
（ａ）成分の好ましい製造法としては、脂肪酸とメチルジエタノールとの脱水エステル化反応により、上記（１−１）の化合物を得ることができ、さらに（１−１）の化合物をメチルクロリド、ジメチル硫酸、ジエチル硫酸などのアルキル化剤でアルキル化することで（２−１）の化合物を得ることができる。また、脂肪酸とトリエタノールアミンをエステル化することで（１−１）の化合物を得ることができ、アルキル化することで（２−１）の化合物を得ることができる。また、脂肪酸とＮ−ヒドロキシエチル−Ｎ−アミノプロピル−Ｎ−メチルアミンとのエステル化、アミド化反応により（１−２）の化合物を得ることができ、アルキル化することで（２−２）の化合物を得ることができる。また、脂肪酸とＮ，Ｎ−ジアミノプロピル−Ｎ−メチルアミンとのアミド化反応により（１−３）の化合物を得ることができ、アルキル化することで（２−３）の化合物を得ることができる。また、脂肪酸の替りに脂肪酸のメチルエステル化物を用いてエステル交換反応により、エステル化又はアミド化することもできる。好ましくは一般式（１−２）、（１−３）、（２−１）、及び（２−２）の化合物であり、最も好ましくは一般式（２−１）、（２−２）の化合物である。
【００１８】
本発明では、洗剤残留量が多いすすぎ水で処理した場合の柔軟性能の観点から、（ａ）成分と共に、炭素数１０〜１４の炭化水素基、特に炭素数１０〜１４のアルキル基及び炭素数１０〜１４のアルキル基アルカノイル基から選ばれる基を１つ有する３級アミン又はその塩、並びに炭素数１０〜１４の炭化水素基、特に炭素数１０〜１４のアルキル基及び炭素数１０〜１４のアルキル基アルカノイル基から選ばれる基を１つ有する第４級アンモニウム塩から選ばれる１種以上の化合物〔以下、（ａ_m）成分という〕を併用することもできる。
【００１９】
（ａ_m）成分としては、下記一般式（１−４）〜（１−６）及び一般式〜（２−５）〜（２−８）から選ばれる化合物〔以下、（ａ_m）成分という〕が好ましく、Ｒ¹³基がヒドロキシエチル基の場合には、（ａ_m）成分／（ａ）成分は、質量比で、好ましくは１／９９〜１／１、より好ましくは３／９７〜４０／６０、特に好ましくは５／９５〜３０／７０である。またＲ¹³基がメチル基、エチル基の場合には、（ａ_m）成分／（ａ）成分は、好ましくは０．５／９９．５〜１／１、より好ましくは１／９９〜３０／７０、さらに好ましくは１／９９〜２０／８０、特に好ましくは２／９８〜１５／８５、である。また、Ｒ¹³基がＲ¹²−ＣＯＯ−(ＣＨ₂)_a−基の場合には、（ａ_m）成分／（ａ）成分は、質量比で、好ましくは１／９９〜１／１、より好ましくは３／９７〜４０／６０、特に好ましくは５／９５〜３０／７０である。
【００２０】
【化４】

【００２１】
〔式中、Ｒ¹²、ａ、ｂ、Ｘ^-は前述と同一の意味である。Ｒ¹⁶、Ｒ¹⁷は、それぞれ独立して、炭素数１〜３のアルキル基又はヒドロキシアルキル基、Ｒ¹⁸は炭素数１６〜２２のアルキル基を示す。〕
【００２２】
本発明の（ａ）成分が３級アミンの場合には、無機又は有機の酸で中和した塩の方が好ましい。塩として使用する場合には、柔軟剤組成物に配合する前にアミノ基を酸剤により中和したものを用いることもでき、柔軟剤組成物に（ａ）成分を配合した後、アミノ基を酸剤で中和してもよい。中和のための酸としては塩酸、硫酸、リン酸などの無機酸、グリコール酸、クエン酸、分子内に芳香族基を有するスルホン酸又はカルボン酸、炭素数１〜３のアルキル硫酸が好ましい。特に塩酸、硫酸、グリコール酸、クエン酸、ｐ−トルエンスルホン酸、クメンスルホン酸、メタキシレンスルホン酸が好ましい。中和に用いるこれらの酸剤は、単独で用いても複数で用いてもよい。
【００２３】
本発明では、（ａ）成分の様に、特定範囲の炭素数の炭化水素基（好ましくはアルキル基又はアルカノイル基）を２個有する柔軟基剤を使用することで、洗剤が通常よりも多めに存在する濯ぎ水に添加して使用される場合でも、柔軟性が向上する。これは、本発明の（ａ）成分は、洗剤成分、特にアニオン界面活性剤とコンプレックスを形成しても、水に不溶化せず、アニオン界面活性剤が柔軟成分の一部として利用されているためと考えられる。
【００２４】
＜（ｂ）成分＞
（ｂ）成分は、通常、柔軟剤組成物の柔軟基剤等として使用される長鎖型の化合物であり、本発明ではこのような化合物（ｂ）が化合物（ａ）と化合物（ｂ）の質量比（ｂ）／（ａ）が２／９以下という極少量であっても良好な柔軟効果が得られ、かつ節水コースのようにすすぎを簡略化した場合でも柔軟効果が維持される。この質量比を満たした上で、（ｂ）成分は、組成物中、０〜５質量％、更に０〜２質量％の範囲で含有されることができる。
【００２５】
（ｂ）成分としては、例えば、下記一般式（３−１）、（３−３）、（３−４）から選ばれる１種又は２種以上のアミン化合物またはその無機酸もしくは有機酸による塩、一般式（３−２）、（３−５）〜（３−８）から選ばれる１種又は２種以上の第４級アンモニウム化合物が挙げられる。
【００２６】
【化５】

【００２７】
〔式中、Ｒ^18a、Ｒ^19a、Ｒ^21a、Ｒ^22aは、それぞれ独立に、炭素数１６〜２２のアルキル基又はアルカノイル基であり、Ｒ^4a、Ｒ^5a、Ｒ^10a、Ｒ^11aは、それぞれ独立に、炭素数１〜６のアルキレン基であり、Ｒ^20a、Ｒ^23a、Ｒ^24aは、それぞれ独立に炭素数１〜３のアルキル基もしくはヒドロキシアルキル基、又はＲ^25a−Ｅ−Ｙ−であり（ここで、Ｒ^25aは炭素数１６〜２２のアルキル基又はアルカノイル基であり、Ｙは炭素数１〜６のアルキレン基である）。Ｒ^26a、Ｒ^27aは、それぞれ独立に、炭素数１５〜２１のアルキル基である。Ｒ^28aは炭素数１〜３のアルキル基であり、Ｒ^29a、Ｒ^30aは、それぞれ独立に炭素数１６〜２１のアルキル基であり、Ａ、Ｂ、Ｃ、Ｄ及びＥは、それぞれ独立に、Ｒ^18a、Ｒ^19a、Ｒ^21a、Ｒ^22a及びＲ^25aがアルキル基の時は、−ＯＣＯ−、−ＮＨＣＯ−から選ばれる基であり、Ｒ^18a、Ｒ^19a、Ｒ^21a、Ｒ^22a及びＲ^25aがアルカノイル基の時は、−Ｏ−、−ＮＨ−から選ばれる基である。ａ、ｂは、それぞれ独立に０又は１の数である。Ｘ^-は陰イオン基である。〕
【００２８】
上記の通り、本発明の組成物は（ｂ）成分を含有しなくてもよく、（ｂ）／（ａ）質量比が２／９以下であればよい。（ｂ）／（ａ）質量比は、好ましくは１／１０以下、更に好ましくは１／２０以下、特に好ましくは１／１００以下、最も好ましくは１／５５０以下である。
【００２９】
（ｂ）成分の量が少なく且つ（ａ）成分が主体であることで、本発明の組成物は、通常の工程よりも洗剤残留量が多いすすぎ水で処理した場合でも優れた柔軟付与効果を示し、かつ水で希釈される過程で増粘せず分散性にも優れた液体柔軟剤組成物となる。
【００３０】
＜液体柔軟剤組成物＞
本発明の液体柔軟剤組成物は、上記（ａ）成分、（ｂ）成分と共に、ＣｌｏｇＰが０．５〜３である溶剤（ｃ）〔以下、（ｃ）成分という〕を含有することが好ましい。（ｃ）成分を用いることで、透明で且つ水で希釈されても増粘しない組成物が得られる。ここで透明とは、光路長が１ｃｍで測定した場合に６６０ｎｍの光透過率が３０％以上、好ましくは５０％以上、より好ましくは７０％以上であることをいう。
【００３１】
（ｃ）成分はＣｌｏｇＰが０．５〜３、好ましくは０．５〜２．５、より好ましくは０．７〜２．２、特に好ましくは０．９〜２．０である。ここでｌｏｇＰとは、有機化合物の水と１−オクタノールに対する親和性を示す係数である。１−オクタノール／水分配係数Ｐは、１−オクタノールと水の２液相の溶媒に微量の化合物が溶質として溶け込んだときの分配平衡で、それぞれの溶媒中における化合物の平衡濃度の比であり、底１０に対するそれらの対数ｌｏｇＰの形で示すのが一般的である。多くの化合物のｌｏｇＰ値が報告され、Daylight Chemical Information Systems, Inc. (Daylight CIS)などから入手しうるデータベースには多くの値が掲載されているので参照できる。実測のｌｏｇＰ値がない場合には、Daylight CISから入手できるプログラム“CLOGP”で計算すると最も便利である。このプログラムは、実測のｌｏｇＰ値がある場合にはそれと伴に、Hansch, Leoのフラグメントアプローチにより算出される“計算ｌｏｇＰ（ＣｌｏｇＰ）”の値を出力する。フラグメントアプローチは化合物の化学構造に基づいており、原子の数及び化学結合のタイプを考慮している(cf. A. Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, P.G. Sammens, J.B. Taylor and C.A. Ramsden, Eds., p.295, Pergamon Press, 1990)。このＣｌｏｇＰ値は現在最も汎用的で信頼できる推定値であるので、化合物の選択に際して実測のｌｏｇＰ値の代わりに用いることができる。本発明では、プログラムCLOGP v4.01により計算したＣｌｏｇＰ値を用いた。
【００３２】
このようなＣｌｏｇＰを有する有機溶剤としては下記一般式（４）、一般式（５）及び一般式（６）の化合物が好適である。
【００３３】
Ｒ²⁵−ＯＨ （４）
〔式中Ｒ²⁵は、炭素数４〜８の炭化水素基、好ましくはアルキル基、アリ−ル基、又はアリ−ルアルキル基である。〕
Ｒ²⁶−（Ｏ−Ｒ²⁷）ｇ−Ｏ−Ｒ²⁸ （５）
〔式中、Ｒ²⁶、Ｒ²⁸は、それぞれ独立して、水素原子、Ｒ²⁹ＣＯ−、炭素数１〜７の炭化水素基、好ましくは水素原子、炭素数３〜７のアルキル基、総炭素数６〜８のアリール基またはアリールアルキル基であり、Ｒ²⁶、Ｒ²⁸の両者が水素原子である場合を除く。Ｒ²⁷は分岐鎖を有していてもよい炭素数２〜９のアルキレン基である。ｇは１〜５の数である。ここでＲ²⁹は炭素数１〜３のアルキル基である。〕
Ｒ³⁰−Ｏ−ＣＨ₂ＣＨ（Ｏ−Ｒ³¹）ＣＨ₂−Ｏ−Ｒ³² （６）
〔式中Ｒ³⁰は、炭素数３〜８のアルキル基であり、Ｒ³¹、Ｒ³²は、それぞれ独立して、水素原子又はヒドロキシ基で置換していてもよい炭素数１〜３のアルキル基である。〕
【００３４】
より具体的に好ましい化合物としては、ｎ−ブタノール、イソブタノール、２−ブタノール、ｎ−ヘキサノール、シクロヘキサノール、フェノール、ベンジルアルコール、フェネチルアルコール、２−フェノキシエタノール、２−ベンジルオキシエタノール、ジエチレングリコールモノベンジルエーテル、ジエチレングリコールモノフェニルエーテル、トリエチレングリコールモノフェニルエーテル、テトラエチレングリコールモノフェニルエーテル、２−エチルヘキサン−１，３−ジオール、ノナン−１，６−ジオール、２−メチルオクタン−１，８−ジオール、２−ブトキシエタノール、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、２−（２−メチル）プロポキシエタノール、ジエチレングリコールモノ−２−メチルプロピルエーテル、２−プロポキシ−１−プロパノール、ジプロピレングリコールモノプロピルエーテル、２−ブトキシ−１−プロパノール、ジプロピレングリコールモノブチルエーテル、２−ｔ−ブトキシ−１−プロパノール、２−フェノキシ−１−プロパノール、２−エトキシプロピル−１−アセテート、２−プロポキシプロピル−１−アセテート、１，２−ジアセトオキシプロパン、３−ジメチル−３−メトキシ−１−プロパノール、１，３−ジメチルブチルグリセリルエーテル、ペンチルグリセリルエーテル、ヘキシルグルセチルエーテルを挙げることができる。
【００３５】
これらの中でも特にｎ−ヘキサノール、ベンジルアルコール、２−フェノキシエタノール、２−ベンジルオキシエタノール、ジエチレングリコールモノベンジルエーテル、ジエチレングリコールモノフェニルエーテル、トリエチレングリコールモノフェニルエーテル、テトラエチレングリコールモノフェニルエーテル、ノナン−１，６−ジオール、２−プロポキシ−１−プロパノール、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテルが好ましく、組成物の透明化及び貯蔵安定性の点から、最も好ましい（ｃ）成分は２−フェノキシエタノール、及びジエチレングリコールモノフェニルエーテル、トリエチレングリコールモノフェニルエーテルから選ばれる１種以上である。
【００３６】
＜液体柔軟剤組成物＞
本発明の柔軟剤組成物は、（ａ）成分を好ましくは１〜４０質量％、より好ましくは３〜３０質量％、更に好ましくは１５〜３０質量％、最も好ましくは２０〜３０質量％含有する。
【００３７】
また、（ｃ）成分を使用する場合、（ａ）成分と（ｃ）成分の質量比は、１／５〜５／１、更に１／３〜３／１、更に１／３〜２／１、特に１／２〜２／１が好ましい。
【００３８】
本発明の柔軟剤組成物は、（ａ）成分、（ｂ）成分、更に必要に応じて配合される（ｃ）成分を水で希釈した水溶液の形態であり、使用する水は蒸留水、イオン交換水、又は次亜塩素酸塩を１〜５ｍｇ／ｋｇの量で添加したイオン交換水が好ましい。
【００３９】
さらに、本発明では、貯蔵安定性、匂いの点から、組成物の２０℃におけるｐＨを２〜８．５、更に２〜７．５、特に２〜５に調整することが好ましい。
【００４０】
本発明においては、組成物の粘度又は透明化度を調節する為に、（ｄ）成分として適度な無機又は有機電解質を含むことが出来る。しかしながら、高濃度に含有した電解質は本組成物の製造設備材質（一般的にはステンレス鋼を用いることが多い）への腐食、あるいは近年一般的になっている洗濯槽のステンレス材質への腐食を引き起こす為、多量に含有することは好ましくない。含有量としては０〜２質量％、好ましくは０〜０．５質量％、さらに好ましくは０〜０．４質量％である。無機電解質としては、塩化ナトリウム、塩化マグネシウム、塩化カリウム、硫酸ナトリウム、硫酸マグネシウムから選ばれる１種以上が好ましい。有機電解質としては、ｐ−トルエンスルホン酸塩、クメンスルホン酸塩、ｍ−キシレンスルホン酸塩、メチル硫酸塩、エチル硫酸塩、トリエタノールアミン塩、Ｎ−メチル−Ｎ，Ｎ，Ｎ−トリ（２−ヒドロキシエチル）アンモニウム塩、Ｎ−メチル−Ｎ，Ｎ−ジ（２−ヒドロキシエチル）アミン塩、Ｎ，Ｎ−ジメチル−Ｎ，Ｎ−ジ（２−ヒドロキシエチル）アンモニウム塩が好ましい。
【００４１】
組成物の柔軟性を向上させる目的で、（ｅ）成分として、分子内に炭素数１０〜３６、好ましくは炭素数１２〜１６の直鎖のアルキル基又はアルケニル基、或いは炭素数２０〜２８の分岐鎖のアルキル基又はアルケニル基、さらに好ましくは炭素数１２〜１４の直鎖のアルキル基又はアルケニル基、或いは炭素数２０〜２４の分岐鎖のアルキル基又はアルケニル基と−ＳＯ₃Ｍ基及び／又は−ＯＳＯ₃M基［M：対イオン］とを有する陰イオン性界面活性剤を含有することが好ましい。具体的には、アルキル基又はアルケニル基が上記炭素数を有するアルキルベンゼンスルホン酸、アルキル（又はアルケニル）硫酸エステル、ポリオキシエチレンアルキル（又はアルケニル）エーテル硫酸エステル、オレフィンスルホン酸、アルカンスルホン酸、α−スルホ脂肪酸、α−スルホ脂肪酸エステル及びこれらの塩が好ましい。これらの中でも、特にアルキル（又はアルケニル）硫酸エステル、アルキル基（又はアルケニル基）を有し、エチレンオキシド（以下、ＥＯと表記する）平均付加モル数が１〜６、好ましくは１〜４、特に好ましくは１〜３であるポリオキシエチレンアルキル（又はアルケニル）エーテル硫酸エステル及びこれらの塩から選ばれる一種以上を配合することが好ましい。アルキル（又はアルケニル）硫酸エステル及びこれらの塩から選ばれる一種以上を配合することが最も好ましい。塩としては、ナトリウム塩、カリウム塩、アンモニウム塩、アルカノールアミン塩が貯蔵安定性の点から良好である。（ａ）成分／（ｅ）成分のモル比は、９９／１〜５０／５０、更に９８／２〜６０／４０、更に９５／５〜６５／３５、特に９５／５〜７０／３０が好ましい。
【００４２】
組成物の柔軟性を向上させるもう一つの方法として、（ｆ）成分として炭素数６〜１８の脂肪酸又は塩、炭素数６〜１８の脂肪酸のアルキル（炭素数１〜４）エステル化物、炭素数６〜１８の脂肪アルコール、炭素数６〜１８の脂肪アルコールもしくは炭素数２〜１０の多価アルコールと炭素数８〜１８の脂肪酸とのエステル化物（平均エステル化度０．５〜３）を含有することができる。含有量は組成物の透明化を困難にさせない、又は保存安定性を悪化させない程度であることが好ましく、具体的には、組成物中、好ましくは５質量％以下、より好ましくは３質量％以下、特に好ましくは１質量％以下である。
【００４３】
組成物の透明化の調節、及び／又は香り立ちを良くする目的で、（ｃ）成分以外の溶剤を用いても差し支えない。（ｃ）成分以外で用いることができる溶剤〔以下、（ｇ）成分という〕としては、エタノール、イソプロパノール、エチレングリコール、グリセリン、プロピレングリコール、ソルビトールから選ばれる溶媒であり、特にエタノール、エチレングリコール、グリセリンが好ましい。これら（ｇ）成分がエチレングリコール、グリセリン、ソルビトールの場合には、組成物中に０〜２０質量％、特に０．５〜１０質量％配合することができる。またエタノール、イソプロパノールの場合には組成物中に０〜８質量％、好ましくは０．１〜４質量％、特に好ましくは０．１以上、３質量％未満、最も好ましくは０．１〜２．５質量％である。
【００４４】
組成物の保存安定性を向上させる目的で、（ｈ）成分として、アルキレンオキシド付加型非イオン界面活性剤を含有させることが好ましい。非イオン界面活性剤として好ましくは、炭素数８〜１８のアルコール、アミン、又は脂肪酸にアルキレンオキシドを平均８〜４０モル付加させた化合物、油脂、もしくは油脂の部分加水分解物、炭素数８〜１８の脂肪酸と炭素数３〜８の多価アルコールとの縮合物にアルキレンオキシドを平均８〜４０モル付加させた非イオン界面活性剤を含有させることが好ましい。
【００４５】
組成物の貯蔵時の色目変化、匂い変化を抑制する目的で、（ｉ）成分として酸化防止剤、キレート剤を含有することが好ましい。酸化防止剤としては２，６−ｔ−ブチル−４−メチルフェノール、２，６−ｔ−ブチル−４−エチルフェノールが好ましく、キレート剤としてはエチレンジアミン４酢酸塩、ジエチレントリアミン五酢酸塩などに代表されるアミノカルボン酸類、トリポリリン酸塩、ピロリン酸塩に代表される無機リン化合物、１−ヒドロキシエタン−１，１−ジホスホン酸塩やポリホスホン酸類、フィチン酸に代表される有機リン酸類が挙げられる。これらは酸でも塩として配合してもよい。これら酸化防止剤は、（ａ）成分に対して１〜１０００ｍｇ／（ａ）成分ｋｇ配合することが好ましい。また、金属封鎖剤は、本発明の柔軟剤組成物中に１〜１０００ｍｇ／ｋｇの範囲で配合されるのが好ましい。
【００４６】
本発明の柔軟剤組成物には、通常繊維処理剤に配合されるシリコーン、香料組成物、あるいは色素等の成分を配合しても差し支えない。
【００４７】
本発明の液体柔軟剤組成物を用いて繊維製品を柔軟処理する場合、本発明の組成物と水とを含有する処理媒体を調製し、該媒体中の化合物（ａ）と繊維製品の質量比が、繊維製品／化合物（ａ）＝３０００／１〜５０／１、更に２０００／１〜２００／１となるように用いることが好ましい。
【００４８】
【実施例】
合成例１（ａ−１）の合成
ラウリン酸／ミリスチン酸を５０／５０（質量比）で混合した混合脂肪酸とＮ−メチル−Ｎ，Ｎ−ジエタノールアミンとを脂肪酸／アミン＝１．９／１のモル比で通常の方法により脱水縮合反応してＮ，Ｎ−ジアルカノイルオキシエチル−Ｎ−メチルアミンを得た。次に、この化合物をメチルクロリドを用いて通常の方法によりアルキル化してＮ，Ｎ−ジアルカノイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウムクロリド（ａ−１）を得た。（尚、反応溶媒はエタノールを使用し、合成品中にエタノール含有量は１０質量％であった。）（ａ−１）は、（ａ_m）／（ａ）の質量比が７／９３であり、未反応脂肪酸含有量が４％であった。また、（ａ−１）中の（ａ）成分に該当する化合物の含有量は８０質量％であった。
【００４９】
合成例２（ａ−２）の合成
ラウリルアルコール／ミリスチルアルコールを５０／５０（質量比）で混合した混合アルコールとメチルアミンを用いて通常の方法により、Ｎ，Ｎ−ジアルキル−Ｎ，Ｎ−ジメチルアミンを得た。次にこの化合物をメチルクロリドを用いてアルキル化してＮ，Ｎ−ジアルキル−Ｎ，Ｎ−ジメチルアンモニウムクロリドを得た。（尚反応溶媒はエタノールを使用し、合成品中にエタノール含有量は８質量％であった。）（ａ−２）は、（ａ_m）／（ａ）の質量比が２／９８であった。また、（ａ−２）中の（ａ）成分に該当する化合物の含有量は８９質量％であった。
【００５０】
合成例３（ａ−３）の合成
ラウリン酸／ミリスチン酸を５０／５０（質量比）で混合した混合脂肪酸とトリエタノールアミンとをし混合脂肪酸／アミン＝１．９／１のモル比で通常の方法により脱水縮合してＮ，Ｎ−ジアルカノイルオキシエチル−Ｎ−（２−ヒドロキシエチル）アミンを得た。次に、この化合物をジメチル硫酸を用いて通常の方法によりアルキル化して、Ｎ，Ｎ−ジアルカノイルオキシエチル−Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルアンモニウムメチルサルフェート（ａ−３）を得た。（尚、反応溶媒はエタノールを使用し、合成品中にエタノール含有量は７質量％であった）（ａ−３）は、（ａ_m）／（ａ）の質量比が１７／８３であり、未反応脂肪酸含有量が５質量％であった。また、（ａ−３）中の（ａ）成分に該当する化合物の含有量は７０質量％であった。
【００５１】
比較合成例（ｂ−１）の合成
牛脂組成脂肪酸とトリエタノールアミンとを脂肪酸／アミン＝１．９／１のモル比で通常の方法により脱水縮合反応してＮ，Ｎ−ジアルカノイルオキシエチル−Ｎ−（２−ヒドロキシエチル）アミンを得た。次に、この化合物をジメチル硫酸を用いて通常の方法によりアルキル化して、Ｎ，Ｎ−ジアルカノイルオキシエチル−Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルアンモニウムメチルサルフェート（ｂ−１）を得た。（尚、反応溶媒はエタノールを使用し、合成品中にエタノール含有量は７質量％であった）（ｂ−１）の（ｂ_m）／（ｂ）の質量比は１６／８４であり〔ここで、（ｂ_m）はＮ−モノアルカノイルオキシエチル体、（ｂ）はＮ，Ｎ−ジアルカノイルオキシエチル体〕、未反応脂肪酸は５質量％であった。（ｂ−１）中のＮ，Ｎ−ジアルカノイルオキシエチル体の含有量は７０質量％であった。
【００５２】
以下に実施例及び配合例に用いた成分を示す。
（ａ−１）：合成例１で得たＮ，Ｎ−ジアルカノイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウムクロリド
（ａ−２）：合成例２で得たＮ，Ｎ−ジアルキル−Ｎ，Ｎ−ジメチルアンモニウムクロリド
（ｂ−１）：比較合成例で得た、Ｎ，Ｎ−ジアルカノイルオキシエチル−Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルアンモニウムメチルサルフェート
（ｃ−１）：ジエチレングリコールモノフェニルエーテル（ＣｌｏｇＰ＝１．２５）
（ｃ−２）：トリエチレングリコールモノフェニルエーテル（ＣｌｏｇＰ＝１．３２）
（ｃ−３）：２−フェノキシエタノール（ＣｌｏｇＰ＝１．１９）
（ｃ’−１）：ヘキシレングリコール（ＣｌｏｇＰ＝−０．０２）
（ｃ’−２）：２，２，４−トリメチル−１，３−ペンタンジオール（ＣｌｏｇＰ＝１．０）
（ｄ−１）：塩化マグネシウム
（ｅ−１）：ラウリル硫酸エステルナトリウム塩
（ｅ−２）：２−デシル−テトラデシル硫+酸エステルナトリウム塩
（ｈ−１）：ラウリルアルコールのＥＯ付加物（平均ＥＯ付加モル数２０モル）
（ｉ−１）：エチレンジアミン４酢酸４ナトリウム塩
【００５３】
実施例１〜７及び比較例１〜４
＜液体柔軟剤組成物の調製方法＞
上記成分を用いて表１に示す液体柔軟剤組成物を調製した。３００ｍＬビーカーに、液体柔軟剤組成物の出来上がり質量が２００ｇになるのに必要な量の９５％相当量の、予め次亜塩素酸ナトリウムを３ｍｇ／ｋｇ添加したイオン交換水を入れ、ウォーターバスで６０℃に昇温した。一つの羽根の長さが２ｃｍの攪拌羽根が４５℃の角度で３枚ついたタービン型の攪拌羽根で攪拌羽根で攪拌しながら（３００ｒ／ｍｉｎ）、所要量の（ｃ）成分〔（ｃ’）成分〕〜（ｄ）成分を添加した。そのまま５分攪拌後、次に６０℃で溶融させた（ａ）成分〔又は更に（ｂ）成分〕を添加した。そのまま５分攪拌した。次に、３５％塩酸水溶液、４８％水酸化ナトリウム水溶液で目標のｐＨに調整し、必要に応じて香料成分を添加した。（ｃ’）成分は場合によっては（ａ）成分とプレミックスして添加してもよい。その後出来上がり質量にするのに必要な量の６０℃のイオン交換水（次亜塩素酸ナトリウムを予め３ｍｇ／ｋｇ添加）を添加した。その後１０分間攪拌し、５℃の水を入れたウォーターバスにビーカーを移し、攪拌しながら２０℃に冷却した。尚、表１に示すｐＨは冷却後（２０℃）のｐＨである。
【００５４】
＜木綿タオルの柔軟性評価＞
（１）柔軟処理タオルＡの調製
市販の木綿タオル（白色、綿１００％）２ｋｇを市販の衣料用洗剤（花王（株）アタック）を用いて洗濯機で洗浄した（東芝製２槽式洗濯機ＶＨ−３６０Ｓ１、洗剤濃度０．０６６７質量％、水道水３０Ｌ（水温２０℃）使用、水温２０℃、１０分間）。その後洗浄液を排出し、３分間脱水後、３０Ｌの水道水（水温２０℃）を注水した。注水後、表１に示す柔軟剤組成物２０ｍＬを添加し５分間攪拌した。その後３分間脱水し自然乾燥した。
【００５５】
（２）柔軟処理タオルＢの調製
市販の木綿タオル（白色、綿１００％）２ｋｇを市販の衣料用洗剤（花王（株）アタック）を用いて洗濯機で洗浄した（東芝製２槽式洗濯機ＶＨ−３６０Ｓ１、洗剤濃度０．０６６７質量％、水道水３０Ｌ（水温２０℃）使用、水温２０℃、１０分間）。その後洗浄液を排出し、３分間脱水後、３０Ｌの水道水（水温２０℃）を注水した。５分間攪拌後、濯ぎ液を排出し、３分間脱水後、水道水３０Ｌ（水温２０℃）を注水した。次に表１に示す柔軟剤組成物２０ｍＬを添加し５分間攪拌した。その後３分間脱水し自然乾燥した。
【００５６】
（３）柔軟性評価
上記処理した衣料の柔軟性を１０人のパネラー（３０代男性１０人）により下記の基準で判定し、平均点を求めた。平均点が０．５以上を◎、０以上０．５未満を○、０未満−０．５以上を△、−０．５未満−１．０以上を×として判定し表１、及び表２に示した。
柔軟処理タオルＡに比べて、柔軟処理タオルＢが柔らかく仕上がった…−１
柔軟処理タオルＡに比べて、柔軟処理タオルＢのやわらかさは同等であった…０
柔軟処理タオルＡの方が、柔軟処理タオルＢよりも柔らかく仕上がった…＋１
【００５７】
【表１】

【００５８】
配合例１〜４
上記成分を用いて表２に示す液体柔軟剤組成物を調製した。３００ｍＬビーカーに、液体柔軟剤組成物の出来上がり質量が２００ｇになるのに必要な量の９５％相当量の、予め次亜塩素酸ナトリウムを３ｍｇ／ｋｇ添加したイオン交換水を入れ、ウォーターバスで６０℃に昇温した。一つの羽根の長さが２ｃｍの攪拌羽根が４５℃の角度で３枚ついたタービン型の攪拌羽根で攪拌羽根で攪拌しながら（３００ｒ／ｍｉｎ）、所要量の（ｃ）成分〜（ｄ）成分を添加した。そのまま５分攪拌後、次に６０℃で溶融させた（ａ）成分を添加した。そのまま５分攪拌した。次に（ｈ）成分を添加し５分攪拌後、３５％塩酸水溶液、４８％水酸化ナトリウム水溶液で目標のｐＨに調整し、必要に応じて香料成分を添加した。（ｅ）成分、（ｉ）成分は場合によっては（ａ）成分とプレミックスして添加してもよい。その後は、実施例１等と同様の操作を行った。得られた液体柔軟剤組成物を実施例１等の方法で評価した柔軟性は、配合例１は◎、配合例２〜４は○であった。
【００５９】
【表２】

【００６０】
【発明の効果】
本発明によれば、通常の洗濯工程のように比較的洗剤残留量の低いすすぎ水で処理した場合はもちろん、節水コースのように通常の工程よりも洗剤残留量が多いすすぎ水で処理した場合でも優れた柔軟付与効果を示す液体柔軟剤組成物が得られる。更に、（ｃ）成分を含有する場合は、透明で水で希釈された場合でも増粘しない液体柔軟剤組成物が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid softener composition.
[0002]
[Prior art]
Conventionally, a quaternary ammonium salt or a tertiary amine acid salt having a long-chain alkyl group (usually having an alkyl group having 16 to 18 carbon atoms) is used for the softening agent. These softeners have a good softening effect on various fibers in a small amount. Moreover, since these are insoluble in water, they exist in a dispersed state in the composition, and the appearance of the composition is usually cloudy.
[0003]
From the aesthetic point of view, transparent or translucent softeners have been developed, and Patent Document 1 discloses a composition using a softener having an unsaturated alkyl group and a non-aqueous solvent. Patent Document 2 discloses a technique using a specific softener compound having an alkenyl group and a solvent having a specific ClogP value. However, the softener compound having an unsaturated group has a problem that the odor of the softened clothing becomes worse. Patent Document 3 discloses a soft base composition having an ester bond and an unsaturated group in an alkyl chain, or a microemulsion-type softener composition excellent in residual fragrance containing a dialkyl ammonium compound, an oil, and a solvent. Has been. Patent Document 4 discloses a transparent and stable liquid softener composition using a specific aromatic compound. Patent Document 5 discloses a transparent softener composition that is highly dispersible in water by containing an electrolyte at a high level.
[0004]
It has also been proposed to use quaternary ammonium salts and tertiary amines having different alkyl chain lengths in the softener composition. For example, Patent Document 6 includes a tertiary amine having one or more alkyl groups having 10 to 22 carbon atoms and a quaternary ammonium salt having 2 to 3 carbon atoms having 8 to 12 carbon atoms. A softener composition that can be used together to suppress the smell of clothing derived from sweat is disclosed. Patent Document 7 discloses a quaternary ammonium salt having an alkyl group having 16 to 22 carbon atoms, and a quaternary ammonium salt having an alkyl group having 6 to 16 carbon atoms and an alkyl group having 1 to 12 carbon atoms. A post-treatment composition for laundry is disclosed.
[0005]
[Patent Document 1]
JP-A-7-229061
[Patent Document 2]
Japanese National Patent Publication No. 11-507095
[Patent Document 3]
International Publication No. 01/04254 Pamphlet
[Patent Document 4]
Japanese Patent Laid-Open No. 7-3650
[Patent Document 5]
JP-T-2001-524616
[Patent Document 6]
JP 2001-303440 A
[Patent Document 7]
Japanese translation of PCT publication No. 10-512015
[0006]
[Problems to be solved by the invention]
Nowadays, there are an increasing number of washing machines considering energy saving, such as providing a so-called water-saving course that simplifies the rinsing process. In a normal washing course, after the laundry is washed with a detergent, for example, a softener is introduced when the second rinse is performed. However, since the rinsing process is shortened in the water-saving course, the residual amount of the detergent in the rinsing water into which the softening agent is added tends not to be sufficiently reduced as compared with the normal washing course. When used in such a method, a softening agent composition using a conventional softening base (for example, an alkyl group having 16 or 18 carbon atoms) does not exhibit the original softening effect and lowers the softness. . Further, it is difficult to say that the softening agent composition described in the above-mentioned patent document discloses a composition optimized for such a method. Furthermore, the transparent liquid softening agent composition also thickens in the process of being poured into rinsing water and diluted with water, and as a result, dispersibility may be lowered. In Patent Document 5, dispersibility is improved. However, blending of a high concentration electrolyte is not preferable in view of influence on equipment.
[0007]
The subject of the present invention is not only when processing with rinse water with a relatively low residual amount of detergent as in a normal washing process, but also when processing with rinse water with a larger amount of residual detergent than in the normal process such as a water-saving course However, it is to provide a liquid softener composition exhibiting an excellent softening effect and a liquid softener composition that is transparent and does not thicken in the process of being diluted with water.
[0008]
[Means for Solving the Problems]
The present invention is one or more kinds selected from tertiary amines having at least two hydrocarbon groups having 10 to 14 carbon atoms or salts thereof and quaternary ammonium salts having two hydrocarbon groups having 10 to 14 carbon atoms. Compound (a) [hereinafter referred to as component (a)], a tertiary amine having a hydrocarbon group having 16 to 22 carbon atoms or a salt thereof, and a quaternary ammonium salt having a hydrocarbon group having 16 to 22 carbon atoms 1 or more selected compounds (b) [hereinafter referred to as component (b)], and the mass ratio (b) / (a) of compound (a) to compound (b) is 2/9 or less. The present invention relates to a liquid softener composition.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
<(A) component>
The component (a) is preferably such that the hydrocarbon group having 10 to 14 carbon atoms is a group selected from an alkyl group having 10 to 14 carbon atoms and an alkanoyl group having 10 to 14 carbon atoms.
[0010]
The component (a) is preferably one or more compounds selected from the tertiary amine represented by the general formula (1) or a salt thereof and the quaternary ammonium salt represented by the general formula (2).
[0011]
[Chemical 2]

[0012]
[In the formula, R ¹ , R ² , R ⁶ And R ⁷ Are each independently an alkyl group having 10 to 14 carbon atoms or an alkanoyl group, and R ^Four , R ^Five , R ^Ten And R ¹¹ Are each independently an alkylene group having 1 to 6 carbon atoms, R ^Three , R ⁸ And R ⁹ Each independently represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group or R ^{12 '} -E-Y- (where R ^{12 '} Is an alkyl group having 6 to 14 carbon atoms or an alkanoyl group, Y is an alkylene group having 1 to 6 carbon atoms), A, B, C, D and E are each independently R ¹ , R ² , R ⁶ , R ⁷ And R ^{12 '} Is an alkyl group, it is a group selected from —OCO— and —NHCO—, and R ¹ , R ² , R ⁶ , R ⁷ And R ^{12 '} When is an alkanoyl group, it is a group selected from —O— and —NH—. a and b are each independently a number of 0 or 1; X ^- Is an anionic group. ]
[0013]
In the present invention, as the component (a), at least one compound selected from the following compounds (1-1) to (1-3) and the following compounds (2-1) to (2-4) is preferable. It is.
[0014]
[Chemical 3]

[0015]
[In the formula, R ¹² Is an alkyl group having 9 to 13 carbon atoms, R ¹³ , R ¹⁴ Each independently represents a methyl group, an ethyl group, a hydroxyethyl group, or R ¹² -COO- (CH ₂ ) _a -, R ¹⁵ Is an alkyl group having 10 to 14 carbon atoms, a and b are each independently a number of 2 or 3, X ^- Is an anionic group. ]
[0016]
Usually, the component (a) is lauric acid, myristic acid (or its lower alkyl ester), lauryl alcohol, myristyl alcohol, which is obtained from oils and fats such as palm oil, palm kernel oil, sunflower oil, soybean oil and the like through a purification process such as distillation. Manufactured as a raw material.
[0017]
As a preferred production method of the component (a), the above compound (1-1) can be obtained by dehydration esterification reaction of a fatty acid and methyldiethanol, and the compound (1-1) is further converted to methyl chloride or dimethyl. The compound (2-1) can be obtained by alkylating with an alkylating agent such as sulfuric acid or diethyl sulfuric acid. Moreover, the compound of (1-1) can be obtained by esterifying a fatty acid and triethanolamine, and the compound of (2-1) can be obtained by alkylating. Moreover, the compound of (1-2) can be obtained by esterification and amidation reaction of a fatty acid and N-hydroxyethyl-N-aminopropyl-N-methylamine, and by alkylating (2-2) Can be obtained. Moreover, the compound of (1-3) can be obtained by amidation reaction of a fatty acid and N, N-diaminopropyl-N-methylamine, and the compound of (2-3) can be obtained by alkylation. it can. Moreover, it can also esterify or amidate by transesterification using the methyl esterification thing of a fatty acid instead of a fatty acid. Preferred are compounds of general formulas (1-2), (1-3), (2-1), and (2-2), and most preferred are those of general formulas (2-1) and (2-2). A compound.
[0018]
In the present invention, from the viewpoint of flexibility when treated with rinsing water with a large amount of residual detergent, together with component (a), a hydrocarbon group having 10 to 14 carbon atoms, particularly an alkyl group having 10 to 14 carbon atoms and carbon number. A tertiary amine having one group selected from 10 to 14 alkyl groups and an alkanoyl group or a salt thereof, and a hydrocarbon group having 10 to 14 carbon atoms, particularly an alkyl group having 10 to 14 carbon atoms and 10 to 14 carbon atoms; One or more compounds selected from quaternary ammonium salts having one group selected from an alkyl group alkanoyl group [hereinafter referred to as (a _m ))] Can be used in combination.
[0019]
(A _m ) Component is a compound selected from the following general formulas (1-4) to (1-6) and general formulas (2-5) to (2-8) [hereinafter, (a _m ) Component] is preferred, and R ¹³ When the group is a hydroxyethyl group, (a _m ) Component / (a) component is preferably 1/99 to 1/1, more preferably 3/97 to 40/60, and particularly preferably 5/95 to 30/70 in terms of mass ratio. Also R ¹³ When the group is a methyl group or an ethyl group, (a _m ) Component / (a) component is preferably 0.5 / 99.5 to 1/1, more preferably 1/99 to 30/70, still more preferably 1/99 to 20/80, and particularly preferably 2 / 98-15 / 85. R ¹³ The group is R ¹² -COO- (CH ₂ ) _a -In the case of a group (a _m ) Component / (a) component is preferably 1/99 to 1/1, more preferably 3/97 to 40/60, and particularly preferably 5/95 to 30/70 in terms of mass ratio.
[0020]
[Formula 4]

[0021]
[In the formula, R ¹² , A, b, X ^- Has the same meaning as described above. R ¹⁶ , R ¹⁷ Are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, R ¹⁸ Represents an alkyl group having 16 to 22 carbon atoms. ]
[0022]
When the component (a) of the present invention is a tertiary amine, a salt neutralized with an inorganic or organic acid is preferred. When used as a salt, it is also possible to use an amino group neutralized with an acid agent before blending into the softener composition. After blending the component (a) in the softener composition, the amino group You may neutralize with an acid agent. The acid for neutralization is preferably an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, glycolic acid, citric acid, a sulfonic acid or carboxylic acid having an aromatic group in the molecule, or an alkyl sulfuric acid having 1 to 3 carbon atoms. In particular, hydrochloric acid, sulfuric acid, glycolic acid, citric acid, p-toluenesulfonic acid, cumenesulfonic acid, and metaxylenesulfonic acid are preferable. These acid agents used for neutralization may be used alone or in combination.
[0023]
In the present invention, like the component (a), by using a soft base having two hydrocarbon groups having a specific number of carbon atoms (preferably an alkyl group or an alkanoyl group), the detergent is more than usual. Even when used by adding to existing rinsing water, flexibility is improved. This is because the component (a) of the present invention does not insolubilize in water even if it forms a complex with a detergent component, particularly an anionic surfactant, and the anionic surfactant is used as a part of the flexible component. it is conceivable that.
[0024]
<(B) component>
The component (b) is a long-chain compound that is usually used as a softening base of a softening agent composition. In the present invention, such a compound (b) is composed of the compound (a) and the compound (b). Even if the mass ratio (b) / (a) is a very small amount of 2/9 or less, a good softening effect is obtained, and even when rinsing is simplified as in a water-saving course, the softening effect is maintained. After satisfying this mass ratio, the component (b) can be contained in the composition in the range of 0 to 5 mass%, and further 0 to 2 mass%.
[0025]
As the component (b), for example, one or more amine compounds selected from the following general formulas (3-1), (3-3), and (3-4), or a salt thereof with an inorganic acid or an organic acid , One or more quaternary ammonium compounds selected from general formulas (3-2) and (3-5) to (3-8).
[0026]
[Chemical formula 5]

[0027]
[In the formula, R ^18a , R ^19a , R ^21a , R ^22a Are each independently an alkyl group or alkanoyl group having 16 to 22 carbon atoms; ^4a , R ^5a , R ^10a , R ^11a Are each independently an alkylene group having 1 to 6 carbon atoms, R ^20a , R ^23a , R ^24a Are each independently an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, or R ^25a -E-Y- (where R ^25a Is an alkyl group having 16 to 22 carbon atoms or an alkanoyl group, and Y is an alkylene group having 1 to 6 carbon atoms. R ^26a , R ^27a Are each independently an alkyl group having 15 to 21 carbon atoms. R ^28a Is an alkyl group having 1 to 3 carbon atoms and R ^29a , R ^30a Are each independently an alkyl group having 16 to 21 carbon atoms, and A, B, C, D and E are each independently R ^18a , R ^19a , R ^21a , R ^22a And R ^25a Is an alkyl group, it is a group selected from —OCO— and —NHCO—, and R ^18a , R ^19a , R ^21a , R ^22a And R ^25a When is an alkanoyl group, it is a group selected from —O— and —NH—. a and b are each independently a number of 0 or 1. X ^- Is an anionic group. ]
[0028]
As above-mentioned, the composition of this invention does not need to contain (b) component, and (b) / (a) mass ratio should just be 2/9 or less. The mass ratio (b) / (a) is preferably 1/10 or less, more preferably 1/20 or less, particularly preferably 1/100 or less, and most preferably 1/550 or less.
[0029]
Since the amount of the component (b) is small and the component (a) is the main component, the composition of the present invention has an excellent softening effect even when it is treated with rinsing water in which the residual amount of detergent is larger than that in a normal process. In the process of being diluted with water, the liquid softening agent composition does not thicken and has excellent dispersibility.
[0030]
<Liquid softener composition>
The liquid softener composition of the present invention preferably contains a solvent (c) having a ClogP of 0.5 to 3 (hereinafter referred to as (c) component) together with the components (a) and (b). . By using the component (c), a transparent composition that does not thicken even when diluted with water can be obtained. Here, the term “transparent” means that the light transmittance at 660 nm is 30% or more, preferably 50% or more, more preferably 70% or more when the optical path length is 1 cm.
[0031]
Component (c) has a ClogP of 0.5 to 3, preferably 0.5 to 2.5, more preferably 0.7 to 2.2, and particularly preferably 0.9 to 2.0. Here, logP is a coefficient indicating the affinity of an organic compound for water and 1-octanol. 1-octanol / water partition coefficient P is a distribution equilibrium when a trace amount of compound is dissolved as a solute in a two-liquid solvent of 1-octanol and water, and is a ratio of the equilibrium concentration of the compound in each solvent. It is common to show them in the form of their logarithm logP relative to the base 10. Log P values of many compounds are reported, and many values are listed in a database available from Daylight Chemical Information Systems, Inc. (Daylight CIS), and can be referred to. When there is no measured log P value, it is most convenient to calculate with the program “CLOGP” available from Daylight CIS. This program outputs the value of “calculated log P (Clog P)” calculated by the Hansch, Leo fragment approach together with the measured log P value, if any. The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bond (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammens, JB Taylor and CA Ramsden, Eds., P.295, Pergamon Press, 1990). Since this ClogP value is currently the most general and reliable estimate, it can be used in place of the actual logP value when selecting a compound. In the present invention, the ClogP value calculated by the program CLOGP v4.01 is used.
[0032]
As the organic solvent having such ClogP, compounds represented by the following general formula (4), general formula (5) and general formula (6) are suitable.
[0033]
R ^{twenty five} -OH (4)
[In the formula, R ^{twenty five} Is a hydrocarbon group having 4 to 8 carbon atoms, preferably an alkyl group, an aryl group, or an arylalkyl group. ]
R ²⁶ -(O-R ²⁷ ) G-O-R ²⁸ (5)
[In the formula, R ²⁶ , R ²⁸ Each independently represents a hydrogen atom, R ²⁹ CO-, a hydrocarbon group having 1 to 7 carbon atoms, preferably a hydrogen atom, an alkyl group having 3 to 7 carbon atoms, an aryl group or an arylalkyl group having 6 to 8 carbon atoms in total, R ²⁶ , R ²⁸ Except when both are hydrogen atoms. R ²⁷ Is an alkylene group having 2 to 9 carbon atoms which may have a branched chain. g is a number of 1-5. Where R ²⁹ Is an alkyl group having 1 to 3 carbon atoms. ]
R ³⁰ -O-CH ₂ CH (O-R ³¹ ) CH ₂ -O-R ³² (6)
[In the formula, R ³⁰ Is an alkyl group having 3 to 8 carbon atoms, and R ³¹ , R ³² Are each independently an alkyl group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom or a hydroxy group. ]
[0034]
More specifically preferred compounds include n-butanol, isobutanol, 2-butanol, n-hexanol, cyclohexanol, phenol, benzyl alcohol, phenethyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, diethylene glycol monobenzyl ether, Diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether, 2-ethylhexane-1,3-diol, nonane-1,6-diol, 2-methyloctane-1,8-diol, 2 -Butoxyethanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, 2- (2-methyl) propoxyethanol, diethylene glycol Cole mono-2-methylpropyl ether, 2-propoxy-1-propanol, dipropylene glycol monopropyl ether, 2-butoxy-1-propanol, dipropylene glycol monobutyl ether, 2-t-butoxy-1-propanol, 2- Phenoxy-1-propanol, 2-ethoxypropyl-1-acetate, 2-propoxypropyl-1-acetate, 1,2-diacetoxypropane, 3-dimethyl-3-methoxy-1-propanol, 1,3-dimethyl Examples include butyl glyceryl ether, pentyl glyceryl ether, and hexyl glyceryl ether.
[0035]
Among these, n-hexanol, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, diethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether, nonane-1,6 -Diol, 2-propoxy-1-propanol, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether are preferred, and the most preferred component (c) is 2-phenoxyethanol, from the viewpoint of transparency of the composition and storage stability. And at least one selected from diethylene glycol monophenyl ether and triethylene glycol monophenyl ether.
[0036]
<Liquid softener composition>
The softener composition of the present invention preferably contains 1 to 40% by mass, more preferably 3 to 30% by mass, still more preferably 15 to 30% by mass, and most preferably 20 to 30% by mass of the component (a). .
[0037]
When the component (c) is used, the mass ratio of the component (a) to the component (c) is 1/5 to 5/1, further 1/3 to 3/1, and further 1/3 to 2/1. In particular, 1/2 to 2/1 is preferable.
[0038]
The softener composition of the present invention is in the form of an aqueous solution obtained by diluting the component (a), the component (b), and the component (c) blended as necessary with water. The water used is distilled water, ion Exchange water or ion exchange water added with hypochlorite in an amount of 1 to 5 mg / kg is preferred.
[0039]
Furthermore, in the present invention, it is preferable to adjust the pH of the composition at 20 ° C. to 2 to 8.5, more preferably 2 to 7.5, and particularly 2 to 5 from the viewpoint of storage stability and odor.
[0040]
In the present invention, an appropriate inorganic or organic electrolyte can be included as the component (d) in order to adjust the viscosity or transparency of the composition. However, the electrolyte contained in a high concentration does not corrode the manufacturing equipment material of this composition (generally, stainless steel is often used) or corrodes the stainless steel material of a washing tub that has become common in recent years. Since it causes, it is not preferable to contain a large amount. As content, it is 0-2 mass%, Preferably it is 0-0.5 mass%, More preferably, it is 0-0.4 mass%. As the inorganic electrolyte, one or more selected from sodium chloride, magnesium chloride, potassium chloride, sodium sulfate, and magnesium sulfate are preferable. Examples of the organic electrolyte include p-toluenesulfonate, cumenesulfonate, m-xylenesulfonate, methyl sulfate, ethyl sulfate, triethanolamine salt, N-methyl-N, N, N-tri (2 -Hydroxyethyl) ammonium salt, N-methyl-N, N-di (2-hydroxyethyl) amine salt, N, N-dimethyl-N, N-di (2-hydroxyethyl) ammonium salt are preferred.
[0041]
For the purpose of improving the flexibility of the composition, as the component (e), a linear alkyl group or alkenyl group having 10 to 36 carbon atoms, preferably 12 to 16 carbon atoms, or 20 to 28 carbon atoms in the molecule. A branched alkyl group or alkenyl group, more preferably a linear alkyl group or alkenyl group having 12 to 14 carbon atoms, or a branched alkyl group or alkenyl group having 20 to 24 carbon atoms and —SO _Three M group and / or -OSO _Three It is preferable to contain an anionic surfactant having an M group [M: counter ion]. Specifically, alkylbenzene sulfonic acid, alkyl (or alkenyl) sulfate, polyoxyethylene alkyl (or alkenyl) ether sulfate, olefin sulfonic acid, alkane sulfonic acid, α-, wherein the alkyl group or alkenyl group has the above carbon number. Sulfo fatty acids, α-sulfo fatty acid esters and salts thereof are preferred. Among these, in particular, an alkyl (or alkenyl) sulfate ester, an alkyl group (or alkenyl group) has an average added mole number of ethylene oxide (hereinafter referred to as EO) of 1 to 6, preferably 1 to 4, particularly preferably. Is preferably 1 to 3 selected from polyoxyethylene alkyl (or alkenyl) ether sulfates and salts thereof. Most preferably, one or more selected from alkyl (or alkenyl) sulfates and salts thereof are blended. As the salt, sodium salt, potassium salt, ammonium salt and alkanolamine salt are preferable from the viewpoint of storage stability. The molar ratio of component (a) / component (e) is 99/1 to 50/50, more preferably 98/2 to 60/40, more preferably 95/5 to 65/35, and particularly preferably 95/5 to 70/30. .
[0042]
As another method for improving the flexibility of the composition, (f) a fatty acid or salt having 6 to 18 carbon atoms, an alkyl (carbon number 1 to 4) esterified product of a fatty acid having 6 to 18 carbon atoms, carbon number Contains an esterified product (average esterification degree: 0.5 to 3) of a fatty acid having 6 to 18 carbon atoms, a fatty alcohol having 6 to 18 carbon atoms or a polyhydric alcohol having 2 to 10 carbon atoms and a fatty acid having 8 to 18 carbon atoms can do. The content is preferably such that it does not make it difficult to make the composition transparent or deteriorate the storage stability. Specifically, in the composition, it is preferably 5% by mass or less, more preferably 3% by mass or less. Particularly preferably, it is 1% by mass or less.
[0043]
For the purpose of adjusting the transparency of the composition and / or improving the fragrance, a solvent other than the component (c) may be used. The solvent that can be used other than the component (c) (hereinafter referred to as the component (g)) is a solvent selected from ethanol, isopropanol, ethylene glycol, glycerin, propylene glycol, and sorbitol, particularly ethanol, ethylene glycol, and glycerin. Is preferred. When these (g) components are ethylene glycol, glycerin and sorbitol, 0 to 20% by mass, particularly 0.5 to 10% by mass can be blended in the composition. In the case of ethanol or isopropanol, 0 to 8% by mass, preferably 0.1 to 4% by mass, particularly preferably 0.1 or more and less than 3% by mass, most preferably 0.1 to 2% by mass in the composition. 5% by mass.
[0044]
For the purpose of improving the storage stability of the composition, an alkylene oxide addition type nonionic surfactant is preferably contained as the component (h). The nonionic surfactant is preferably a compound obtained by adding an average of 8 to 40 moles of alkylene oxide to an alcohol, amine, or fatty acid having 8 to 18 carbon atoms, an oil or fat, or a partial hydrolyzate of oil or fat, or an 8 to 18 carbon atom. It is preferable to contain a nonionic surfactant obtained by adding an average of 8 to 40 moles of alkylene oxide to a condensate of the above fatty acid and a polyhydric alcohol having 3 to 8 carbon atoms.
[0045]
For the purpose of suppressing color change and odor change during storage of the composition, it is preferable to contain an antioxidant and a chelating agent as component (i). As the antioxidant, 2,6-t-butyl-4-methylphenol and 2,6-t-butyl-4-ethylphenol are preferable, and as the chelating agent, represented by ethylenediaminetetraacetate, diethylenetriaminepentaacetate and the like. Inorganic phosphorus compounds represented by aminocarboxylic acids, tripolyphosphates, pyrophosphates, 1-hydroxyethane-1,1-diphosphonates, polyphosphonic acids, and organic phosphoric acids represented by phytic acid. These may be blended as acids or salts. These antioxidants are preferably blended in an amount of 1-1000 mg / kg of component (a) with respect to component (a). Moreover, it is preferable that a metal sequestering agent is mix | blended in the range of 1-1000 mg / kg in the softening agent composition of this invention.
[0046]
In the softener composition of the present invention, components such as silicone, a fragrance composition, and a pigment that are usually blended in a fiber treatment agent may be blended.
[0047]
When a textile product is softened using the liquid softener composition of the present invention, a treatment medium containing the composition of the present invention and water is prepared, and the mass ratio of the compound (a) and the textile product in the medium is prepared. However, it is preferable to use it so that it may become textiles / compound (a) = 3000 / 1-50 / 1, and also 2000 / 1-200 / 1.
[0048]
【Example】
Synthesis of Synthesis Example 1 (a-1)
Dehydration condensation reaction of mixed fatty acid mixed with lauric acid / myristic acid at 50/50 (mass ratio) and N-methyl-N, N-diethanolamine at a molar ratio of fatty acid / amine = 1.9 / 1 by a conventional method. As a result, N, N-dialkanoyloxyethyl-N-methylamine was obtained. Next, this compound was alkylated with methyl chloride by a usual method to obtain N, N-dialkanoyloxyethyl-N, N-dimethylammonium chloride (a-1). (In addition, the reaction solvent used ethanol, and ethanol content was 10 mass% in the synthetic | combination product.) (A-1) is (a _m ) / (A) mass ratio was 7/93, and the unreacted fatty acid content was 4%. Moreover, content of the compound applicable to the (a) component in (a-1) was 80 mass%.
[0049]
Synthesis of Synthesis Example 2 (a-2)
N, N-dialkyl-N, N-dimethylamine was obtained by a conventional method using a mixed alcohol obtained by mixing lauryl alcohol / myristyl alcohol at 50/50 (mass ratio) and methylamine. This compound was then alkylated with methyl chloride to give N, N-dialkyl-N, N-dimethylammonium chloride. (The reaction solvent used was ethanol, and the ethanol content in the synthesized product was 8% by mass.) (A-2) _m ) / (A) mass ratio was 2/98. Moreover, content of the compound applicable to the (a) component in (a-2) was 89 mass%.
[0050]
Synthesis of Synthesis Example 3 (a-3)
A mixed fatty acid obtained by mixing lauric acid / myristic acid at 50/50 (mass ratio) and triethanolamine are subjected to dehydration condensation by a usual method at a mixed fatty acid / amine = 1.9 / 1 molar ratio. -Dialkanoyloxyethyl-N- (2-hydroxyethyl) amine was obtained. Next, this compound is alkylated with dimethyl sulfate by a conventional method to obtain N, N-dialkanoyloxyethyl-N- (2-hydroxyethyl) -N-methylammonium methyl sulfate (a-3). It was. (Note that ethanol was used as the reaction solvent, and the ethanol content in the synthesized product was 7% by mass) (a-3) _m ) / (A) mass ratio was 17/83, and the unreacted fatty acid content was 5 mass%. Moreover, content of the compound applicable to the (a) component in (a-3) was 70 mass%.
[0051]
Synthesis of Comparative Synthesis Example (b-1)
N, N-dialkanoyloxyethyl-N- (2-hydroxyethyl) amine is obtained by dehydrating condensation reaction of beef tallow composition fatty acid and triethanolamine at a molar ratio of fatty acid / amine = 1.9 / 1 by an ordinary method. Obtained. Next, this compound is alkylated with dimethyl sulfate by a conventional method to obtain N, N-dialkanoyloxyethyl-N- (2-hydroxyethyl) -N-methylammonium methyl sulfate (b-1). It was. (Note that ethanol was used as the reaction solvent, and the ethanol content in the synthesized product was 7% by mass) (b-1) (b _m ) / (B) mass ratio is 16/84 [where (b _m ) Is an N-monoalkanoyloxyethyl compound, (b) is an N, N-dialkanoyloxyethyl compound], and the unreacted fatty acid was 5% by mass. The content of N, N-dialkanoyloxyethyl compound in (b-1) was 70% by mass.
[0052]
The components used in Examples and Formulation Examples are shown below.
(A-1): N, N-dialkanoyloxyethyl-N, N-dimethylammonium chloride obtained in Synthesis Example 1
(A-2): N, N-dialkyl-N, N-dimethylammonium chloride obtained in Synthesis Example 2
(B-1): N, N-dialkanoyloxyethyl-N- (2-hydroxyethyl) -N-methylammonium methyl sulfate obtained in Comparative Synthesis Example
(C-1): Diethylene glycol monophenyl ether (ClogP = 1.25)
(C-2): Triethylene glycol monophenyl ether (ClogP = 1.32)
(C-3): 2-phenoxyethanol (ClogP = 1.19)
(C′-1): Hexylene glycol (ClogP = −0.02)
(C′-2): 2,2,4-trimethyl-1,3-pentanediol (ClogP = 1.0)
(D-1): Magnesium chloride
(E-1): Lauryl sulfate sodium salt
(E-2): 2-decyl-tetradecyl sulfur + acid ester sodium salt
(H-1): EO adduct of lauryl alcohol (average EO addition mole number 20 mol)
(I-1): Ethylenediaminetetraacetic acid tetrasodium salt
[0053]
Examples 1-7 and Comparative Examples 1-4
<Method for Preparing Liquid Softener Composition>
Liquid softener compositions shown in Table 1 were prepared using the above components. In a 300 mL beaker, 95% of the amount necessary for the finished mass of the liquid softening agent composition to be 200 g, ion-exchanged water added with 3 mg / kg of sodium hypochlorite in advance is added, and the water is added in a water bath. The temperature was raised to ° C. While stirring with a stirring blade (300 r / min) with a turbine-type stirring blade having three blades each having a length of 2 cm at an angle of 45 ° C., the required amount of component (c) [(c ′ ) Components] to (d) were added. After stirring for 5 minutes, the component (a) (or component (b)) melted at 60 ° C. was added. The mixture was stirred for 5 minutes. Next, the target pH was adjusted with a 35% hydrochloric acid aqueous solution and a 48% sodium hydroxide aqueous solution, and a fragrance component was added as necessary. In some cases, the component (c ′) may be added after being premixed with the component (a). Thereafter, 60 ° C. ion-exchanged water (3 mg / kg of sodium hypochlorite was added in advance) in an amount necessary to obtain a finished mass was added. Thereafter, the mixture was stirred for 10 minutes, the beaker was transferred to a water bath containing 5 ° C. water, and cooled to 20 ° C. while stirring. The pH shown in Table 1 is the pH after cooling (20 ° C.).
[0054]
<Flexibility evaluation of cotton towel>
(1) Preparation of soft towel A
2 kg of a commercially available cotton towel (white, 100% cotton) was washed with a washing machine using a commercially available detergent for clothing (Kao Corp. Attack) (Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0667) % By mass, using 30 L of tap water (water temperature 20 ° C., water temperature 20 ° C., 10 minutes). Thereafter, the washing liquid was discharged, and after dehydration for 3 minutes, 30 L of tap water (water temperature 20 ° C.) was poured. After the water injection, 20 mL of the softener composition shown in Table 1 was added and stirred for 5 minutes. Thereafter, it was dehydrated for 3 minutes and air dried.
[0055]
(2) Preparation of soft towel B
2 kg of a commercially available cotton towel (white, 100% cotton) was washed with a washing machine using a commercially available detergent for clothing (Kao Corp. Attack) (Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0667) % By mass, using 30 L of tap water (water temperature 20 ° C., water temperature 20 ° C., 10 minutes). Thereafter, the washing liquid was discharged, and after dehydration for 3 minutes, 30 L of tap water (water temperature 20 ° C.) was poured. After stirring for 5 minutes, the rinsing liquid was discharged, and after dehydration for 3 minutes, 30 L of tap water (water temperature 20 ° C.) was poured. Next, 20 mL of the softening agent composition shown in Table 1 was added and stirred for 5 minutes. Thereafter, it was dehydrated for 3 minutes and air dried.
[0056]
(3) Flexibility evaluation
The flexibility of the treated garments was determined by 10 panelists (10 men in their 30s) according to the following criteria, and the average score was determined. Table 1 and Table 2 where the average score is 0.5 or more is evaluated as ◎, 0 or more and less than 0.5 as ○, less than 0 -0.5 or more as Δ, and less than -0.5 -1.0 or more as ×. It was shown to.
Soft finish towel B was softer than soft finish towel A ...- 1
The softness of the soft towel B was the same as that of the soft towel A ... 0
Soft towel A was softer than soft towel B ... + 1
[0057]
[Table 1]

[0058]
Formulation Examples 1-4
The liquid softening agent composition shown in Table 2 was prepared using the said component. In a 300 mL beaker, 95% of the amount necessary for the finished mass of the liquid softening agent composition to be 200 g, ion-exchanged water added with 3 mg / kg of sodium hypochlorite in advance is added, and the water is added in a water bath. The temperature was raised to ° C. While stirring with a stirring blade (300 r / min) with a turbine-type stirring blade having three blades each having a length of 2 cm at an angle of 45 ° C., the required amount of component (c) to (d) Ingredients were added. After stirring for 5 minutes, the component (a) melted at 60 ° C. was added. The mixture was stirred for 5 minutes. Next, the component (h) was added, stirred for 5 minutes, adjusted to the target pH with a 35% hydrochloric acid aqueous solution and a 48% sodium hydroxide aqueous solution, and a fragrance component was added as necessary. The component (e) and the component (i) may be premixed with the component (a) depending on circumstances. Thereafter, the same operation as in Example 1 was performed. The softness | flexibility which evaluated the obtained liquid softening agent composition by methods, such as Example 1, was (double-circle) in the compounding example 1, and (circle) in the compounding examples 2-4.
[0059]
[Table 2]

[0060]
【The invention's effect】
According to the present invention, when treated with rinsing water having a relatively low residual amount of detergent as in a normal washing process, as well as when treating with rinsing water having a larger amount of residual detergent than in a normal process such as a water-saving course However, a liquid softener composition exhibiting an excellent softening effect can be obtained. Further, when the component (c) is contained, a liquid softener composition that is transparent and does not thicken even when diluted with water is obtained.

Claims (9)

One or more compounds selected from quaternary ammonium salts having two hydrocarbon groups of carbon number 10 to 14 (a) [hereinafter compound (a) as] a,
One or more compounds selected from quaternary ammonium salts having one hydrocarbon group of 10 to 14 carbon atoms (a _m) [hereinafter compound (a _m) of! And,
Quaternary least one compound selected from an ammonium salt having a hydrocarbon group having a carbon number of 16 to 22 and (b)
A solvent (c) having a ClogP of 0.5 to 3,
The liquid softening agent composition containing the compound (a) and the compound (b) and having a mass ratio (b) / (a) of 2/9 or less.   The liquid softener composition according to claim 1, wherein the hydrocarbon group having 10 to 14 carbon atoms of the compound (a) is a group selected from an alkyl group having 10 to 14 carbon atoms and an alkanoyl group having 10 to 14 carbon atoms. Compound (a) is, under following general formula (2) is a compound selected from quaternary ammonium salts represented by claim 1 or 2 liquid softener composition.

[ Wherein, R ⁶ and R ⁷ are each independently an alkyl group having 10 to 14 carbon atoms or an alkanoyl group, and R ¹⁰ and R ¹¹ are each independently an alkylene group having 1 to 6 carbon atoms. Each of R ⁸ and R ⁹ is independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group or R ^{12 ′} -E—Y— (where R ^{12 ′} is an alkyl group having 6 to 14 carbon atoms) C , D and E are each independently —OCO when R ⁶ , R ⁷ and R ^{12 ′} are alkyl groups, and Y is an alkylene group having 1 to 6 carbon atoms. A group selected from — and —NHCO—, and when R ⁶ , R ⁷ and R ^{12 ′} are an alkanoyl group, it is a group selected from —O— and —NH—. a and b are each independently a number of 0 or 1; X ^- is an anionic group. ] One general formula (2) in the R ^6, R ⁷ and R ^{12 'that} put each independently claim 3 liquids softener composition according alkyl group or an alkanoyl group having 12 carbon atoms.   The liquid softening agent composition of any one of Claims 1-4 which contains a compound (a) 1-40 mass% in total. The compound (a) is at least one compound selected from the following compounds (2-1) to (2-4), and the mass ratio of the compound (a _m ) / the compound (a) is 1/99 to 1 The liquid softener composition according to any one of claims 1 to 5 , which is / 1 .

[Wherein, R ¹² is an alkyl group having 9 to 13 carbon atoms, R ¹³ and R ¹⁴ are each independently a methyl group, an ethyl group, a hydroxyethyl group, or R ¹² —COO— (CH ₂ ) _a —. , R ¹⁵ is an alkyl group having 10 to 14 carbon atoms, a and b are each independently 2 or 3, and X ⁻ is an anionic group. ] The liquid softener composition according to any one of claims 1 to 6, wherein the mass ratio of the compound (a) to the solvent (c) is (a) / (c) = 1/5 to 5/1. It is transparent, The liquid softening agent composition in any one of Claims 1-7 .   A method for softening a textile product using a treatment medium containing the liquid softener composition according to any one of claims 1 to 8 and water, wherein the compound (a) in the medium and the mass of the textile product The method for softening a textile product, wherein the ratio is textile product / compound (a) = 3000/1 to 50/1.