JP4628587B2 - Softener composition - Google Patents

Description

【０００９】
［式中、Ｒ¹及びＲ²は同一又は異なって、ヘテロ原子を含む置換基を有していてもよい、炭素数２〜２２の直鎖もしくは分岐鎖のアルキレン基、アルケニレン基又はアリーレン基を示す。Ｘは−Ｏ−又は−ＮＨ−基を示す。Ｍは前記の意味を示す。］
【００１０】
【化４】

【００１１】
［式中、Ｒ¹、Ｒ²、Ｘ及びＭは前記の意味を示し、Ｒ³及びＲ⁴は同一又は異なって、ヘテロ原子を含む置換基を有していてもよい、炭素数２〜２２の直鎖もしくは分岐鎖のアルキレン基、アルケニレン基又はアリーレン基を示す。］
一般式（１）及び（２）中、Ｒ¹は、好ましくは炭素数２〜１２の直鎖もしくは分岐鎖のアルキレン基又はアルケニレン基であり、Ｒ²及びＲ⁴は、好ましくは炭素数２〜８の直鎖もしくは分岐鎖のアルキレン基又はアルケニレン基、あるいはフェニレン基であり、Ｒ³は、好ましくは炭素数２〜８の直鎖もしくは分岐鎖のアルキレン基又はアルケニレン基であり、より好ましくはエチレン基である。Ｒ¹〜Ｒ⁴において、ヘテロ原子を含む置換基としては、エステル基、エーテル基等が挙げられる。
【００１２】
Ｍ中、金属は、アルカリ金属、アルカリ土類金属、遷移金属を含むが、アルカリ金属、アルカリ土類金属が好ましく、ナトリウム、カリウムがより好ましい。アルカノールアンモニウムは、モノ、ジ又はトリアルカノールアンモニウムを含み、総炭素数１〜９のアルカノールアンモニアが好ましく、更に好ましくは、モノエタノールアンモニウム、ジエタノールアンモニウム、トリエタノールアンモニウムである。塩基性アミノ酸としては、アルギニン、ヒスチジン、リジン等が挙げられる
カルボキシ基等を有するオルガノポリシロキサンは、水酸基及び／又はアミノ基を含有するオルガノポリシロキサン（以下、前駆体オルガノポリシロキサンという）と、酸無水物又は酸塩化物とを反応させることで合成することができるが、酸無水物が好ましく用いられ、このような酸無水物は、無水フタル酸、無水マレイン酸、無水コハク酸、無水グルタル酸、無水アジピン酸の中から選ばれる１種以上を単独あるいは混合状態で用いることが好ましい。
【００１３】
前駆体オルガノポリシロキサンの水酸基、アミノ基の部分構造は特に限定されないが、一般式（３）又は（４）で表されるものが好ましい。
【００１４】
【化５】

【００１５】
また、前駆体オルガノポリシロキサンのポリシロキサン鎖としては、［Ｒ₂ＳｉＯ］単位（ここで、Ｒはメチル基等の炭素数１〜４の低級アルキル基、フェニル基又はビニル基を示す。）が直鎖状又は分岐鎖状に結合している構造を有するものが挙げられ、これらは架橋していても、架橋していなくてもよい。この前駆体オルガノポリシロキサンの中では、粘度３０〜１０万ｍＰａ・ｓのものが好ましい。
【００１６】
前駆体オルガノポリシロキサンと、酸無水物との反応の際に、反応溶媒は、何も用いないか、あるいは酸無水物と反応しないものであれば特に制限はなく、例えば、２−ブタノン等のケトン類、ヘプタンやシクロヘキサン等の飽和炭化水素類、トルエン等の芳香族炭化水素類、１，４−ジオキサンやジエチレングリコールジエチルエーテルやアニソール等のエーテル類、ジメチルホルムアミド等のアミド類、酢酸エチルや安息香酸メチル等のエステル類、１，２−ジクロロエタンやクロロベンゼン等のハロゲン化炭化水素類、スルホラン等のスルホン類、ジメチルスルホキシド等のスルホキシド類等が挙げられる。
【００１７】
反応温度は、酸無水物の開環反応を早め、前駆体オルガノポリシロキサンと酸無水物とを混合し易くし、またポリシロキサン鎖の断裂等の副反応が起こりにくく、また変色などを引き起こさない観点から、３０℃〜１５０℃が好ましく、５０℃〜１１０℃がさらに好ましい。
【００１８】
反応時間は、充分な反応を行い、またポリシロキサン鎖の断裂や変色等の好ましくない副反応を引き起こさない観点から、２〜２３時間が適当である。反応雰囲気は、乾燥窒素などの不活性気体雰囲気が好ましい。
【００１９】
前駆体オルガノポリシロキサンと酸無水物との割合は、求められる性質に依存して決められるが、生成物にカルボキシ基等を含有させる特徴を出し、反応しないで残留する酸無水物量を抑え、その後の変質や使用時の副反応を引き起こさない観点から、前駆体オルガノポリシロキサンの水酸基とアミノ基との合計当量モル数に対して０．３倍〜１．２倍当量モルの酸無水物が仕込まれることが好ましく、０．６倍〜１．１倍当量モル用いることが特に好ましい。ここで、酸無水物１モルは、反応性から１当量モルとする。特に式（４）においてＸがＮＨである基を有する、前駆体オルガノポリシロキサンを用い、これに酸無水物を反応させる場合には、全てのアミノ基の０．７倍当量モル以上用いることが好ましい。
【００２０】
［（Ｂ）成分：柔軟基剤］
本発明に用いる（Ｂ）成分の柔軟基剤は、分子中にエステル基及び／又はアミド基と、１つ以上の炭素数１０〜３６、好ましくは１０〜２２のアルキル基又はアルケニル基とを有する３級アミン又はその塩もしくはその４級化物である。柔軟基剤としては、特に下記一般式（５）で表される化合物（以下化合物（５）という）、化合物（５）と酸剤との塩、又は化合物（５）と４級化剤との４級化物が繊維製品の風合いの点から好ましい。
【００２１】
【化６】

【００２２】
［式中、Ｒ⁵及びＲ⁷は、それぞれ独立に、炭素数１０〜２２、好ましくは１２〜１８のアルキル基又はアルケニル基を示し、Ｙ及びＺは、それぞれ独立に、−ＣＯＯ−、−ＣＯＮＲ¹⁰−、−ＯＣＯ−又は−ＮＲ¹⁰ＣＯ−であり、少なくともいずれか一方は−ＣＯＯ−又は−ＯＣＯ−である。ここでＲ¹⁰は水素原子、炭素数１〜３のアルキル基又はヒドロキシアルキル基、好ましくは水素原子を示す。また、Ｒ⁶及びＲ⁸は、それぞれ独立に、炭素数１〜５のアルキレン基であり、Ｒ⁹は炭素数１〜３のアルキル基もしくはヒドロキシアルキル基又は式Ｒ⁵−（Ｗ）_n−Ｒ⁶−（Ｒ⁵及びＲ⁶は前記の意味を示し、Ｗは−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−又は−ＮＨＣＯ−であり、ｎは０又は１である。）で表される基である。］
なお塩の場合、用いる酸は、塩酸、硫酸、リン酸、炭素数１〜１２の脂肪酸又は炭素数１〜３のアルキル硫酸が好ましい。また４級化物とする場合にこの３級アミンに作用させる４級化剤には、硫酸ジエチル、硫酸ジメチル、塩化メチル、塩化エチル、臭化メチル、ｐ−トルエンスルホン酸メチル、ベンゼンスルホン酸メチル、メタンスルホン酸メチルが好ましい。
【００２３】
化合物（５）のうち、下記式（５−１）又は（５−２）で表される化合物が特に好ましく、これらの塩であれば塩酸、硫酸又はリン酸との塩が好ましく、４級化物であれば硫酸ジメチル、塩化メチルで４級化されたものが好ましい。
【００２４】
【化７】

【００２５】
［式中、Ｒ¹¹、Ｒ¹²は同一又は異なって、炭素数１２〜１８のアルキル基又はアルケニル基を示し、Ｒ⁹は前記の意味を示す。］
本発明では、繊維製品の風合いの点から化合物（５）に加えて一般式（６）で表される化合物（以下化合物（６）という）を併用することが望ましい。
【００２６】
【化８】

【００２７】
［式中、Ｒ¹³は炭素数１２〜２２、好ましくは１４〜１８のアルキル基又はアルケニル基を示し、Ｂは−ＣＯＯ−、−ＣＯＮＲ¹⁷−、−ＯＣＯ−又は−ＮＲ¹⁷ＣＯ−であり、好ましくは−ＣＯＯ−又は−ＣＯＮＲ¹⁷−である。ここで、Ｒ¹⁷は水素原子、炭素数１〜３のアルキル基又はヒドロキシアルキル基、好ましくは水素原子を示す。また、Ｒ¹⁴は炭素数１〜５のアルキレン基であり、Ｒ¹⁵及びＲ¹⁶は同一又は異なって、炭素数１〜３のアルキル基又はヒドロキシアルキル基を示す。］
化合物（６）は、塩又は４級化物の状態であってもよく、用いる酸は塩酸、硫酸、リン酸、炭素数１〜１２の脂肪酸又は炭素数１〜３のアルキル硫酸が好ましく、４級化剤は、ハロゲン化アルキル（アルキル基の炭素数１〜３）、ジアルキル硫酸（アルキル基の炭素数１〜３）が好ましい。
【００２８】
本発明の柔軟剤組成物は、柔軟効果の点から、柔軟基剤として、化合物（５）、その塩又はその４級化物と、化合物（６）、その塩又はその４級化物を、（５）：（６）＝７０：３０〜９９：１、特に８０：２０〜９５：５の重量比率で含有することが特に好ましい。
【００２９】
［柔軟剤組成物］
本発明の柔軟剤組成物は、（Ａ）成分であるオルガノポリシロキサンを好ましくは０．０５〜３０重量％、さらに好ましくは０．１〜２０重量％、特に好ましくは０．２〜１０重量％含有する。また（Ｂ）成分である柔軟基剤を好ましくは２〜５０重量％、さらに好ましくは３〜４０重量％、特に好ましくは５〜３５重量％含有する。
【００３０】
本発明の柔軟剤組成物には、これらオルガノポリシロキサンと柔軟基剤とが水で稀釈された水溶液の形態が好ましい。使用する水には蒸留水又はイオン交換水が好ましい。水は組成物中に４０〜９０重量％、さらに好ましくは５０〜８５重量％、特に好ましくは６０〜８５重量％配合される。
【００３１】
さらに、貯蔵安定性の点から、２０℃における本発明の組成物のｐＨは２〜５、特に２．５〜４に調整されることが好ましい。
【００３２】
本発明では貯蔵安定性の点からオルガノポリシロキサンと柔軟基剤に加えてさらに非イオン界面活性剤及び／又は陰イオン界面活性剤を配合することが好ましい。
【００３３】
非イオン界面活性剤としては炭素数８〜２０のアルキル基又はアルケニル基を有するポリオキシエチレンアルキルエーテルが好ましく、特に下記一般式（７）で表される非イオン界面活性剤が好ましい。
【００３４】
Ｒ¹⁸−Ｔ−［（Ｒ¹⁹Ｏ）_p−Ｈ］_q （７）
［式中、Ｒ¹⁸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、Ｒ¹⁹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は平均値で２〜１００、好ましくは５〜８０、特に好ましくは２０〜６０の数を示す。Ｔは−Ｏ−、−ＣＯＮ＜又は−Ｎ＜であり、Ｔが−Ｏ−の場合はｑは１であり、Ｔが−ＣＯＮ＜又は−Ｎ＜の場合はｑは２である。なお、複数個のＲ¹⁹は同一でも異なっていてもよい。］
一般式（７）で表される化合物の具体例として以下の化合物を挙げることができる。
【００３５】
Ｒ¹⁸−Ｏ−（Ｃ₂Ｈ₄Ｏ）_r−Ｈ
［式中、Ｒ¹⁸は前記の意味を示す。ｒは８〜１００、好ましくは２０〜６０の数である。］
Ｒ¹⁸−Ｏ−（Ｃ₂Ｈ₄Ｏ）_s（Ｃ₃Ｈ₆Ｏ）_t−Ｈ
［式中、Ｒ¹⁸は前記の意味を示す。ｓ及びｔはそれぞれ独立に２〜４０、好ましくは５〜４０の数であり、エチレンオキシドとプロピレンオキシドはランダムあるいはブロック付加体であってもよい。］
【００３６】
【化９】

【００３７】
［式中、Ｒ¹⁸は前記の意味を示す。ｕ及びｖの合計は５〜１００、好ましくは５〜８０である。］
本発明の柔軟剤組成物中の上記非イオン界面活性剤の配合量は、安定性の点から０．５〜１０重量％、特に１〜８重量％が好ましい。
【００３８】
本発明では繊維製品の風合いを向上させる目的で陰イオン界面活性剤、中でも脂肪酸又はその塩類を配合することが好ましく、具体的にはカプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、あるいはこれらの混合物であり、特にラウリン酸、ステアリン酸、オレイン酸から選ばれる１種以上が好ましい。また、ヤシ油、パーム油、パーム核油、牛脂から誘導されるアルキル組成を有する脂肪酸も好ましい。本発明の柔軟剤組成物中の上記脂肪酸又はその塩の配合量は、０．０１〜５重量％、特に０．５〜３重量％が好ましい。
【００３９】
本発明では、貯蔵安定性の点から、炭素数８〜２２の飽和又は不飽和脂肪酸と多価アルコールとのエステル化合物を組成物中０．１〜１０重量％、特に０．５〜５重量％配合することが好ましい。エステル化合物としては、トリグリセライド、ジグリセライド、モノグリセライド、ペンタエリスリトールのモノ、ジ、トリエステル、ソルビタンエステルが好ましい。
【００４０】
本発明では、無機塩、例えば塩化カルシウム等を０〜１０００ｐｐｍ、好ましくは１０〜５００ｐｐｍ添加することが貯蔵安定性の点で望ましい。但し、脂肪酸塩類等の界面活性剤にはナトリウム塩やカリウム塩が含まれているが、このような界面活性剤の使用によって組成物に混入する無機塩は上記制限を受けるものではない。
【００４１】
さらに本発明では、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及びポリオキシエチレンフェニルエーテルから選ばれる溶媒成分を配合することが貯蔵安定性の点から好ましい。これら溶媒成分は、組成物中に０〜２０重量％、特に０．５〜１０重量％配合することが好ましい。
【００４２】
本発明の柔軟剤組成物には、従来繊維処理剤に配合されるオルガノポリシロキサン類を併用しても良く、香料（特に好ましくは特開平８−１１３８７号公報記載の成分（ｃ）及び（ｄ）にて示された香気成分の組み合わせ）あるいは色素等の成分を配合しても差し支えない。
【００４３】
本発明の組成物において、アニオン性基を有するオルガノポリシロキサンと柔軟基剤との混合方法は特に限定されないが、該ポリシロキサンをソープフリーエマルジョン又は非イオン界面活性剤を共存させたエマルジョンにし、その後、エマルジョンを柔軟基剤の水溶液（あるいは水分散液）と混合する手法が好ましい。必要に応じて高圧剪断や超音波照射を施して粒子を微細にすることもできる。その他の成分は、いずれの過程において組成物に加えられても構わない。
【００４４】
本発明の組成物のｐＨを調節するためには、酸としては塩酸、硫酸、リン酸、アルカリとしては、水酸化ナトリウム、水酸化カリウム、から選ばれる一種以上を用いるのが好ましい。ｐＨの調整は、組成物を製造するどのタイミングで行っても構わない。
【００４５】
［繊維の処理方法］
本発明の柔軟剤組成物を用いた繊維の処理方法は特に限定されないが、次の手法が例示される。すなわち、洗濯後、通常のすすぎを経た繊維と共に張られた水に対して、本発明の柔軟剤組成物を添加し、１分間以上攪拌して繊維に馴染ませ、遠心脱水や手絞り等の操作で脱水後、温風乾燥機で乾燥するか吊り下げて干す。
【００４６】
【実施例】
例中の部及び％は、特記しない限り重量基準である。また以下の合成例において、アミノ基、カルボキシ基及び水酸基は以下の方法で定量した。
【００４７】
＜アミノ基の定量＞
クロロホルム・メタノール混合溶媒（容量比１：１）の中で、過塩素酸の酢酸溶液を用いて電位差滴定によって分析した。
【００４８】
＜カルボキシ基の定量＞
クロロホルム・メタノール混合溶媒（容量比１：１）の中で、フェノールフタレインを指示薬とし、水酸化カリウムのエタノール溶液を用いて滴定した。
【００４９】
＜水酸基の定量＞
クロロホルム溶媒中、無水酢酸のピリジン溶液で処理し、水を加えて過剰の無水酢酸を酢酸に変え、フェノールフタレインを指示薬として、生成した酢酸を水酸化カリウムで逆滴定した。得られた値からカルボキシ基の滴定値を差し引いて、残存している水酸基量に換算した。
【００５０】
合成例１（連結基にアミド結合を含むもの）
ＫＦ−８００２（信越化学工業（株）製、アミノ基含有ポリジメチルシロキサン）２００部と無水コハク酸（和光純薬工業製）１２．０部とを混合して、窒素雰囲気下、８５〜８８℃で４時間攪拌し、カルボキシ基を有するポリジメチルシロキサンを薄黄色の糊状物として得た。
【００５１】
このポリジメチルシロキサンは、元のアミノ基の９２％が消失していた。また、カルボキシ基の定量の結果は、２２．５ｍｇ水酸化カリウム当量／ｇサンプルであった。液膜法で赤外線吸収スペクトルを測定した結果、１７０８ｃｍ^-1にカルボキシ基の吸収が、１６４１ｃｍ^-1にアミド基の吸収が観測された。
【００５２】
合成例２（連結基にエステル結合を含むもの）
ＫＦ−６００３（信越化学工業（株）製、水酸基含有ポリジメチルシロキサン）２００部と無水コハク酸（和光純薬工業製）７．１４部とを混合して、窒素雰囲気下、９０〜９５℃で９時間攪拌し、カルボキシ基を有するポリジメチルシロキサンを無色の糊状物として得た。
【００５３】
このポリジメチルシロキサンは、元の水酸基の９３％が消失しており、カルボキシ基の定量の結果は、１８．８ｍｇ水酸化カリウム当量／ｇサンプルであった。液膜法で赤外線吸収スペクトルを測定した結果、１７１６ｃｍ^-1にカルボキシ基の吸収が、１７３０ｃｍ^-1にエステル基の吸収が観測された。
【００５４】
実施例１〜８及び比較例１〜５
下記成分を用い、表１に記載の組成を有する柔軟剤組成物を調製した。得られた柔軟剤組成物について、下記方法で、木綿、ポリエステル及びウールに対する柔軟性能を評価した。結果を表１に示す。
【００５５】
＜配合成分＞
・オルガノポリシロキサン成分
ｓ−１：合成例１で得たオルガノポリシロキサン
ｓ−２：合成例２で得たオルガノポリシロキサン
ｓ−３：Ｘ２２−１６２Ａ（信越化学工業（株）製、カルボキシ変性ポリジメチルシロキサン）
ｓ−４：ＳＭ８７０５（東レ・ダウコーニングシリコーン（株）製、ポリジメチルシロキサン）
ｓ−５：ＳＭ８７０２Ｃ（東レ・ダウコーニングシリコーン（株）製、アミノ変性ポリジメチルシロキサン）
ｓ−６：特開平１１−２２９２７３号公報の製造例２の（ii）の記載に則して合成したＮ−プロピオニルエチレンイミン−ジメチルシロキサン共重合体
・柔軟基剤
【００５６】
【化１０】

【００５７】
・その他成分
ｂ−１：ラウリルアルコールにエチレンオキシドを平均２０モル付加させたもの
ｂ−２：ソフタノール３００（炭素数１２〜１４の２級アルコールにエチレンオキシドを平均３０モル付加させたもの、日本触媒（株）製）
ｂ−３：エソミンＴ７０（アルキルアミンのエチレンオキシド付加物、ライオンアクゾ（株）製）
ｃ：ルナックＳ−５０（ステアリン酸、花王（株）製）
ｈ−１：色素（アシッドブルー９）
ｈ−２：香料［ヘキシルシンナミックアルデヒド（１８）、ネロリンヤラヤラ（４）、トリシクロデセニルアセテート（４）、ベンジルアセテート（１０）、ムスクケトン（５）、アニシルアセトン（２）、サンダルマイソールコア（２）、アルデヒドＣ１４ピーチ（１）、リナロール（１８）、ジヒドロキシミルセノール（８）、ボルネオール（４）、セドロール（４）、ムゴール（５）、ベンジルアルコール（５）、ジプロピレングリコール（１０）の混合物：カッコ内は香料中の重量％］。
【００５８】
＜柔軟性能評価法＞
・木綿に対する性能
(1) 洗濯処理
ワイシャツ（木綿１００％）６枚（衣料の全重量１．５ｋｇ）を市販の弱アルカリ性洗剤（花王（株）製「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％、水道水３０Ｌ使用、水温２０℃、１０分間）。その後洗浄液を排出し、３０秒間脱水後、３０Ｌの水道水を注水して５分間すすぎを行い、排水後３０秒間脱水を行った。再び３０Ｌの水道水を注水して５分間すすぎを行い、排水後１分間脱水を行った。
【００５９】
(2) 柔軟処理
前記洗濯処理した後に続いて、３０Ｌの水道水を注水した後、表１の柔軟剤組成物を７ｍＬ添加し５分間攪拌した。その後、排水して脱水し、湿度６０％、２５℃の恒温室で１２時間乾燥した。
【００６０】
(3) 柔軟性能の評価
塩化ジメチルジステアリルアンモニウム（花王（株）製コータミンＤ８６Ｐから２−プロパノールを除いたもの）５％からなる柔軟剤２０ｍＬを用いて前記と同じく柔軟処理したワイシャツを基準ワイシャツとした。
【００６１】
実施例あるいは比較例の柔軟剤組成物で処理をしたワイシャツを、前記基準ワイシャツと比較し、１０人のパネラー（３０代男性１０人）により判定した。判定基準は下記であり、１０人の平均点の小数第１位を四捨五入して表１に記載した。
【００６２】
柔らかさの判定基準
＋２：基準より非常に柔らかい
＋１；基準よりやや柔らかい
０；基準と同等である
−１：基準よりやや硬い
−２：基準より非常に硬い
弾力性の判定基準
＋２：基準より非常に弾力性がある
＋１；基準よりやや弾力性がある
０；基準と同等の弾力性がある
−１：基準の方がやや弾力性がある
−２：基準の方が非常に弾力性がある
・ポリエステル及びウールに対する性能
(1) 洗濯処理
市販のポリエステルデシン１ｋｇ、ウールセーター１ｋｇをそれぞれ、市販の家庭用軽質洗剤エマール（花王（株）製）と水道水を用いて、市販全自動洗濯機（ナショナル製やさしい愛妻号）で３回繰り返し洗濯し、１分間脱水した。
【００６３】
(2) 柔軟処理
前記洗濯処理した後に続いて、３０Ｌの水道水を注水した後、表１の柔軟剤組成物を７ｍＬ添加し５分間攪拌した。その後、排水して脱水し、湿度６０％、２５℃の恒温室で２４時間乾燥した。
【００６４】
(3) 柔軟性能の評価
塩化ジメチルジステアリルアンモニウム（花王（株）製コータミンＤ８６Ｐから２−プロパノールを除いたもの）５％からなる柔軟剤２０ｍＬを用いて前記と同じく柔軟処理したポリエステルデシン、あるいはウールセーターを各々の場合の基準とした。
【００６５】
実施例あるいは比較例の柔軟剤組成物で処理をしたポリエステルデシン、あるいはウールセーターを、それぞれ前記基準ポリエステルデシン、あるいはウールセーターと比較し、１０人のパネラー（３０代女性１０人）により判定した。判定基準は下記であり、１０人の平均点の小数第１位を四捨五入して表１に記載した。
【００６６】
柔らかさの判定基準
＋２：基準より非常に柔らかい
＋１；基準よりやや柔らかい
０；基準と同等である
−１：基準の方がやや柔らかい
−２：基準の方が非常に柔らかい
弾力性の判定基準
＋２：基準より非常に弾力性がある
＋１；基準よりやや弾力性がある
０；基準と同等の弾力性がある
−１：基準の方がやや弾力性がある
−２：基準の方が非常に弾力性がある
【００６７】
【表１】

【００６８】
【発明の効果】
本発明の柔軟剤組成物は、柔軟性に優れ、また少量のシリコーン含有量でも繊維製品に優れた風合いを付与することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a softener composition capable of imparting a preferable softness, slipperiness, and elastic texture to textile products (clothing, bedding, bedding, towels, etc.).
[0002]
[Prior art and problems to be solved by the invention]
Conventional fabric softeners have a high flexibility-imparting effect on cotton, but can be applied to synthetic fibers such as acrylic, polyester and polyamide, and hydrophobic natural fibers such as wool and cashmere. On the other hand, the effect of imparting flexibility is not sufficient, and further, slipperiness and elasticity that affect the texture are not sufficient. As a method for solving this problem and imparting slipperiness and elasticity to textile products, it has been proposed to add organopolysiloxane (for example, JP-A-5-508889, JP-A-5-509342). Publication). However, in these cases, the organopolysiloxane is liquid at room temperature and normal pressure, and is present as a liquid on the fiber after the softening treatment, so that the slipperiness is improved, but there is a problem that a sticky feeling remains, and Since the effect of imparting elasticity is low, a preferable texture could not be imparted. Good texture in textiles, especially clothing, is an important factor that leads to good comfort and good appearance, and there is a need for a softening agent that can improve the texture as well as impart flexibility.
[0003]
In response to this demand, Japanese Patent Application Laid-Open No. 11-229273 proposes that the texture can be improved satisfactorily by blending solid silicone that is not liquid but highly elastic.
[0004]
As described above, when using liquid silicone or elastic solid silicone, the texture has been improved accordingly. In this case, as a matter of course, the blended silicone remains on the fiber to improve the texture. However, based on the amount of blended silicone, the silicone actually remaining on the fiber When the amount was expressed as a percentage, it was almost less than 50%. That is, since the adsorptivity of the blended silicones to the fibers is low, more than half of the blended silicones are wasted, and the texture improving effect is not sufficiently exhibited. This poor adsorptivity was undesirable when considering the economic effect of the actual effect per raw material price used.
[0005]
An object of the present invention is to provide a softener composition containing highly adsorbable silicone, in which most of the blended silicone acts to improve the texture, in other words, exhibits a similar effect to the conventional amount in a smaller amount than the conventional one. It is.
[0006]
[Means for Solving the Problems]
The present invention relates to an organopolysiloxane (component (A)) having one or more anionic groups in the molecule, an ester group and / or an amide group in the molecule, and one or more alkyl groups having 10 to 36 carbon atoms. Alternatively, a softener composition containing a tertiary amine having an alkenyl group or a salt thereof or a quaternized product thereof (component (B)) is provided.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
[Component (A): Organopolysiloxane]
The organopolysiloxane of component (A) used in the present invention is an organopolysiloxane having at least one anionic group in the molecule. The anionic group is at least the formula -COOM (where M is a hydrogen atom, metal, ammonium, alkyl or alkenyl ammonium having 1 to 22 carbon atoms, alkyl or alkenyl substituted pyridinium having 1 to 22 carbon atoms, 1 carbon atom) To 22 alkanol ammonium or a basic amino acid)), or a salt thereof (hereinafter referred to as a carboxy group or the like), and other anionic groups include —OSO ₃ M, —SO. ₃ M, -OPO ₃ M ₂ , -PO ₃ M ₂ (all of which M has the above meaning). The structure of the organic group having a carboxy group or the like is not limited, but the carboxy group itself, an alkyl carboxy group, a polyoxyethylene alkyl carboxy group, preferably between the carboxy group and the silicon atom in terms of high affinity with the fiber. And those having a divalent group containing at least an ester bond or an amide bond. The carboxy group and the like are preferably those linked to a silicon atom in a structure represented by at least one of the general formulas (1) and (2).
[0008]
[Chemical 3]

[0009]
[Wherein, R ¹ and R ² are the same or different and each represents an optionally substituted linear or branched alkylene group, alkenylene group or arylene group having 2 to 22 carbon atoms, which may have a substituent containing a hetero atom. Show. X represents —O— or —NH— group. M represents the above meaning. ]
[0010]
[Formula 4]

[0011]
[Wherein R ¹ , R ² , X and M represent the above-mentioned meanings, and R ³ and R ⁴ may be the same or different and may have a substituent containing a hetero atom, which has 2 to 22 carbon atoms. A linear or branched alkylene group, alkenylene group or arylene group. ]
In the general formulas (1) and (2), R ¹ is preferably a linear or branched alkylene group or alkenylene group having 2 to 12 carbon atoms, and R ² and R ⁴ are preferably 2 to 2 carbon atoms. 8 is a linear or branched alkylene group or alkenylene group or phenylene group, and R ³ is preferably a linear or branched alkylene group or alkenylene group having 2 to 8 carbon atoms, more preferably ethylene. It is a group. In R ^{1 to} R ⁴ , examples of the substituent containing a hetero atom include an ester group and an ether group.
[0012]
In M, the metal includes an alkali metal, an alkaline earth metal, and a transition metal, but an alkali metal and an alkaline earth metal are preferable, and sodium and potassium are more preferable. The alkanol ammonium includes mono-, di- or trialkanol ammonium and is preferably alkanol ammonia having 1 to 9 carbon atoms, more preferably monoethanol ammonium, diethanol ammonium or triethanol ammonium. Examples of basic amino acids include arginine, histidine, lysine, and other organopolysiloxanes having a carboxy group, such as an organopolysiloxane containing a hydroxyl group and / or an amino group (hereinafter referred to as a precursor organopolysiloxane), an acid Although it can be synthesized by reacting with an anhydride or acid chloride, an acid anhydride is preferably used, and such an acid anhydride includes phthalic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride. It is preferable to use one or more selected from adipic anhydride alone or in a mixed state.
[0013]
The partial structure of the hydroxyl group and amino group of the precursor organopolysiloxane is not particularly limited, but those represented by the general formula (3) or (4) are preferable.
[0014]
[Chemical formula 5]

[0015]
The polysiloxane chain of the precursor organopolysiloxane includes [R ₂ SiO] units (where R represents a lower alkyl group having 1 to 4 carbon atoms such as a methyl group, a phenyl group, or a vinyl group). Examples thereof include those having a structure bonded in a straight chain or branched chain, and these may or may not be cross-linked. Among these precursor organopolysiloxanes, those having a viscosity of 300 to 100,000 mPa · s are preferable.
[0016]
In the reaction between the precursor organopolysiloxane and the acid anhydride, the reaction solvent is not particularly limited as long as it does not use anything or does not react with the acid anhydride. For example, 2-butanone or the like Ketones, saturated hydrocarbons such as heptane and cyclohexane, aromatic hydrocarbons such as toluene, ethers such as 1,4-dioxane, diethylene glycol diethyl ether and anisole, amides such as dimethylformamide, ethyl acetate and benzoic acid Examples thereof include esters such as methyl, halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, sulfones such as sulfolane, and sulfoxides such as dimethyl sulfoxide.
[0017]
The reaction temperature accelerates the ring-opening reaction of the acid anhydride, facilitates mixing of the precursor organopolysiloxane and the acid anhydride, does not easily cause side reactions such as polysiloxane chain breakage, and does not cause discoloration. From the viewpoint, 30 ° C to 150 ° C is preferable, and 50 ° C to 110 ° C is more preferable.
[0018]
The reaction time is suitably 2 to 23 hours from the viewpoint of performing a sufficient reaction and not causing undesirable side reactions such as polysiloxane chain breakage or discoloration. The reaction atmosphere is preferably an inert gas atmosphere such as dry nitrogen.
[0019]
The ratio between the precursor organopolysiloxane and the acid anhydride is determined depending on the required properties, but the product is characterized by containing a carboxy group and the like, and the amount of acid anhydride remaining without reacting is suppressed. From the standpoint of not causing side effects during use or deterioration, 0.3 to 1.2 times equivalent mole of acid anhydride is charged relative to the total number of moles of hydroxyl groups and amino groups of the precursor organopolysiloxane. It is preferable to use 0.6 to 1.1 times equivalent mole. Here, 1 mol of acid anhydride is defined as 1 equivalent mol in view of reactivity. In particular, when a precursor organopolysiloxane having a group in which X is NH in the formula (4) is used and an acid anhydride is reacted with this, it is necessary to use 0.7 times equivalent mole or more of all amino groups. preferable.
[0020]
[(B) component: flexible base]
The soft base of the component (B) used in the present invention has an ester group and / or an amide group in the molecule and one or more alkyl groups or alkenyl groups having 10 to 36 carbon atoms, preferably 10 to 22 carbon atoms. A tertiary amine or a salt thereof or a quaternized product thereof. As the flexible base, in particular, a compound represented by the following general formula (5) (hereinafter referred to as compound (5)), a salt of compound (5) and an acid agent, or a compound (5) and a quaternizing agent. Quaternized products are preferred from the viewpoint of the texture of the textile product.
[0021]
[Chemical 6]

[0022]
[Wherein, R ⁵ and R ⁷ each independently represents an alkyl or alkenyl group having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and Y and Z each independently represent —COO— or —CONR ^10- , -OCO- or -NR ¹⁰ CO-, and at least one of them is -COO- or -OCO-. R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably a hydrogen atom. R ⁶ and R ⁸ are each independently an alkylene group having 1 to 5 carbon atoms, and R ⁹ is an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, or a formula R ⁵ — (W) _n —R. ^{A group represented by 6-} (R ⁵ and R ⁶ are as defined above, W is —COO—, —OCO—, —CONH— or —NHCO—, and n is 0 or 1). is there. ]
In the case of a salt, the acid used is preferably hydrochloric acid, sulfuric acid, phosphoric acid, a fatty acid having 1 to 12 carbon atoms or an alkyl sulfuric acid having 1 to 3 carbon atoms. The quaternizing agent that acts on the tertiary amine in the case of a quaternized product includes diethyl sulfate, dimethyl sulfate, methyl chloride, ethyl chloride, methyl bromide, methyl p-toluenesulfonate, methyl benzenesulfonate, Methyl methanesulfonate is preferred.
[0023]
Of the compounds (5), compounds represented by the following formula (5-1) or (5-2) are particularly preferred, and salts thereof with hydrochloric acid, sulfuric acid or phosphoric acid are preferred, and quaternized products. In this case, quaternized with dimethyl sulfate or methyl chloride is preferable.
[0024]
[Chemical 7]

[0025]
[Wherein, R ¹¹ and R ¹² are the same or different and each represents an alkyl group or an alkenyl group having 12 to 18 carbon atoms, and R ⁹ represents the above meaning. ]
In the present invention, it is desirable to use a compound represented by general formula (6) (hereinafter referred to as compound (6)) in addition to compound (5) from the viewpoint of the texture of the textile product.
[0026]
[Chemical 8]

[0027]
[Wherein R ¹³ represents an alkyl group or alkenyl group having 12 to 22 carbon atoms, preferably 14 to 18 carbon atoms, B represents —COO—, —CONR ¹⁷ —, —OCO— or —NR ¹⁷ CO—, Preferred is —COO— or —CONR ¹⁷ —. Here, R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably a hydrogen atom. R ¹⁴ is an alkylene group having 1 to 5 carbon atoms, and R ¹⁵ and R ¹⁶ are the same or different and represent an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. ]
Compound (6) may be in the form of a salt or quaternized compound, and the acid used is preferably hydrochloric acid, sulfuric acid, phosphoric acid, a fatty acid having 1 to 12 carbon atoms or an alkyl sulfuric acid having 1 to 3 carbon atoms, and is preferably quaternary. The agent is preferably a halogenated alkyl (alkyl group having 1 to 3 carbon atoms) or a dialkyl sulfate (alkyl group having 1 to 3 carbon atoms).
[0028]
From the viewpoint of the softening effect, the softening agent composition of the present invention comprises compound (5), a salt thereof or a quaternized product thereof, and a compound (6), a salt thereof or a quaternized product thereof as a softening base (5 ): (6) = 70: 30 to 99: 1, particularly preferably 80:20 to 95: 5.
[0029]
[Softener composition]
The softener composition of the present invention is preferably 0.05 to 30% by weight, more preferably 0.1 to 20% by weight, particularly preferably 0.2 to 10% by weight of the organopolysiloxane as the component (A). contains. The soft base as component (B) is preferably contained in an amount of 2 to 50% by weight, more preferably 3 to 40% by weight, particularly preferably 5 to 35% by weight.
[0030]
The softener composition of the present invention is preferably in the form of an aqueous solution in which these organopolysiloxane and softening base are diluted with water. The water used is preferably distilled water or ion exchange water. Water is blended in the composition in an amount of 40 to 90% by weight, more preferably 50 to 85% by weight, and particularly preferably 60 to 85% by weight.
[0031]
Further, from the viewpoint of storage stability, the pH of the composition of the present invention at 20 ° C. is preferably adjusted to 2 to 5, particularly 2.5 to 4.
[0032]
In the present invention, it is preferable to blend a nonionic surfactant and / or an anionic surfactant in addition to the organopolysiloxane and the soft base from the viewpoint of storage stability.
[0033]
As the nonionic surfactant, a polyoxyethylene alkyl ether having an alkyl group or an alkenyl group having 8 to 20 carbon atoms is preferable, and a nonionic surfactant represented by the following general formula (7) is particularly preferable.
[0034]
^{R 18 -T - [(R 19} O) p -H] q (7)
[Wherein, R ¹⁸ is an alkyl or alkenyl group having 10 to ¹⁸ carbon atoms, preferably 12 to ¹⁸ carbon atoms, and R ¹⁹ is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. p is an average value of 2 to 100, preferably 5 to 80, particularly preferably 20 to 60. T is -O-, -CON <or -N <, q is 1 when T is -O-, and q is 2 when T is -CON <or -N <. A plurality of R ¹⁹ may be the same or different. ]
Specific examples of the compound represented by the general formula (7) include the following compounds.
[0035]
R ¹⁸ —O— (C ₂ H ₄ O) _r —H
[Wherein R ¹⁸ has the above-mentioned meaning. r is a number from 8 to 100, preferably from 20 to 60. ]
R ¹⁸ —O— (C ₂ H ₄ O) _s (C ₃ H ₆ O) _t —H
[Wherein R ¹⁸ has the above-mentioned meaning. s and t are each independently a number of 2 to 40, preferably 5 to 40, and ethylene oxide and propylene oxide may be random or block adducts. ]
[0036]
[Chemical 9]

[0037]
[Wherein R ¹⁸ has the above-mentioned meaning. The sum of u and v is 5 to 100, preferably 5 to 80. ]
The blending amount of the nonionic surfactant in the softener composition of the present invention is preferably 0.5 to 10% by weight, particularly 1 to 8% by weight from the viewpoint of stability.
[0038]
In the present invention, an anionic surfactant, particularly a fatty acid or a salt thereof, is preferably blended for the purpose of improving the texture of the textile product. Specifically, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearin It is an acid, oleic acid, or a mixture thereof, and particularly preferably at least one selected from lauric acid, stearic acid, and oleic acid. Also preferred are fatty acids having an alkyl composition derived from coconut oil, palm oil, palm kernel oil, and beef tallow. The blending amount of the fatty acid or salt thereof in the softener composition of the present invention is preferably 0.01 to 5% by weight, particularly preferably 0.5 to 3% by weight.
[0039]
In the present invention, from the viewpoint of storage stability, an ester compound of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol is contained in the composition in an amount of 0.1 to 10% by weight, particularly 0.5 to 5% by weight. It is preferable to mix. As the ester compound, triglyceride, diglyceride, monoglyceride, and mono, di, triester and sorbitan ester of pentaerythritol are preferable.
[0040]
In the present invention, it is desirable in terms of storage stability that an inorganic salt such as calcium chloride is added in an amount of 0 to 1000 ppm, preferably 10 to 500 ppm. However, although surfactants such as fatty acid salts include sodium salts and potassium salts, the inorganic salts mixed into the composition by using such surfactants are not limited to the above.
[0041]
Furthermore, in this invention, it is preferable from the point of storage stability to mix | blend the solvent component chosen from ethanol, isopropanol, glycerol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and polyoxyethylene phenyl ether. These solvent components are preferably blended in the composition in an amount of 0 to 20% by weight, particularly 0.5 to 10% by weight.
[0042]
In the softener composition of the present invention, organopolysiloxanes that are conventionally blended in fiber treatment agents may be used in combination, and perfumes (particularly preferably components (c) and (d) described in JP-A-8-11387. Or a combination of components such as pigments.
[0043]
In the composition of the present invention, the mixing method of the organopolysiloxane having an anionic group and the soft base is not particularly limited, but the polysiloxane is made into a soap-free emulsion or an emulsion coexisting with a nonionic surfactant, and thereafter A method of mixing the emulsion with an aqueous solution (or aqueous dispersion) of a soft base is preferable. If necessary, the particles can be made fine by applying high-pressure shearing or ultrasonic irradiation. Other components may be added to the composition in any process.
[0044]
In order to adjust the pH of the composition of the present invention, it is preferable to use at least one selected from hydrochloric acid, sulfuric acid, phosphoric acid, and alkali as sodium hydroxide and potassium hydroxide as the acid. The pH may be adjusted at any timing for producing the composition.
[0045]
[Fiber treatment method]
Although the processing method of the fiber using the softening agent composition of this invention is not specifically limited, The following method is illustrated. That is, after washing, the softener composition of the present invention is added to water stretched together with fibers that have undergone normal rinsing, and the mixture is agitated for 1 minute or longer to adjust to the fibers, and operations such as centrifugal dehydration and hand drawing are performed. After dehydration, dry with a hot air dryer or hang it to dry.
[0046]
【Example】
Parts and% in the examples are based on weight unless otherwise specified. In the following synthesis examples, amino groups, carboxy groups and hydroxyl groups were quantified by the following method.
[0047]
<Quantification of amino group>
Analysis was carried out by potentiometric titration using an acetic acid solution of perchloric acid in a chloroform / methanol mixed solvent (volume ratio 1: 1).
[0048]
<Quantification of carboxy group>
In a chloroform / methanol mixed solvent (volume ratio 1: 1), phenolphthalein was used as an indicator, and titration was performed using an ethanol solution of potassium hydroxide.
[0049]
<Quantification of hydroxyl group>
The mixture was treated with a pyridine solution of acetic anhydride in a chloroform solvent, water was added to change excess acetic anhydride to acetic acid, and the resulting acetic acid was back titrated with potassium hydroxide using phenolphthalein as an indicator. The carboxy group titration value was subtracted from the obtained value to convert the amount of hydroxyl groups remaining.
[0050]
Synthesis Example 1 (Containing group containing an amide bond)
200 parts of KF-8002 (manufactured by Shin-Etsu Chemical Co., Ltd., amino group-containing polydimethylsiloxane) and 12.0 parts of succinic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed, and 85 to 88 ° C. in a nitrogen atmosphere. Was stirred for 4 hours to obtain polydimethylsiloxane having a carboxy group as a pale yellow paste.
[0051]
In this polydimethylsiloxane, 92% of the original amino groups had disappeared. Further, the result of quantification of the carboxy group was 22.5 mg potassium hydroxide equivalent / g sample. A result of measuring the infrared absorption spectrum in the liquid film method, the absorption of a carboxyl group in the 1708 cm ^-1 is the absorption of an amide group was observed at 1641cm ^-1.
[0052]
Synthesis Example 2 (Containing an ester bond in the linking group)
200 parts of KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group-containing polydimethylsiloxane) and 7.14 parts of succinic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and the mixture was 90 to 95 ° C. in a nitrogen atmosphere. The mixture was stirred for 9 hours to obtain a polydimethylsiloxane having a carboxy group as a colorless paste.
[0053]
In this polydimethylsiloxane, 93% of the original hydroxyl groups had disappeared, and the result of quantitative determination of the carboxy group was 18.8 mg potassium hydroxide equivalent / g sample. A result of measuring the infrared absorption spectrum in the liquid film method, the absorption of a carboxyl group in the 1716 cm ^-1 is absorption of the ester group was observed at 1730 cm ^-1.
[0054]
Examples 1-8 and Comparative Examples 1-5
A softener composition having the composition shown in Table 1 was prepared using the following components. About the obtained softening agent composition, the softening performance with respect to cotton, polyester, and wool was evaluated by the following method. The results are shown in Table 1.
[0055]
<Compounding ingredients>
Organopolysiloxane component s-1: Organopolysiloxane s-2 obtained in Synthesis Example 1 Organopolysiloxane s-3 obtained in Synthesis Example 2 X22-162A (Shin-Etsu Chemical Co., Ltd., carboxy-modified poly Dimethylsiloxane)
s-4: SM8705 (manufactured by Dow Corning Toray Silicone Co., Ltd., polydimethylsiloxane)
s-5: SM8702C (Toray Dow Corning Silicone Co., Ltd., amino-modified polydimethylsiloxane)
s-6: N-propionylethyleneimine-dimethylsiloxane copolymer / soft base synthesized according to the description in Production Example 2 (ii) of JP-A-11-229273
Embedded image

[0057]
-Other components b-1: An average of 20 mol of ethylene oxide added to lauryl alcohol b-2: Softanol 300 (an average of 30 mol of ethylene oxide added to a secondary alcohol having 12 to 14 carbon atoms, Nippon Shokubai Co., Ltd.) ) Made)
b-3: Esomine T70 (ethylene oxide adduct of alkylamine, manufactured by Lion Akzo Co., Ltd.)
c: LUNAC S-50 (stearic acid, manufactured by Kao Corporation)
h-1: Dye (Acid Blue 9)
h-2: Perfume [Hexylcinnamic aldehyde (18), Neroline Yarayara (4), Tricyclodecenyl acetate (4), Benzyl acetate (10), Musk ketone (5), Anisylacetone (2), Sandalmysol core (2), aldehyde C14 peach (1), linalool (18), dihydroxymyrsenol (8), borneol (4), cedrol (4), mugor (5), benzyl alcohol (5), dipropylene glycol (10 ) Mixture: The weight in the parenthesis is in parentheses].
[0058]
<Flexible performance evaluation method>
・ Performance against cotton
(1) Washing shirts (100% cotton 100%) (total weight of clothing 1.5kg) were washed with a washing machine using a commercially available weak alkaline detergent ("ATTACK" manufactured by Kao Corporation) (Toshiba 2 Tank type washing machine VH-360S1, detergent concentration 0.0667%, use of 30 L of tap water, water temperature 20 ° C., 10 minutes). Thereafter, the cleaning liquid was discharged, dehydrated for 30 seconds, poured 30 L of tap water, rinsed for 5 minutes, and dehydrated for 30 seconds after drainage. 30 L of tap water was poured again for rinsing for 5 minutes, and dewatering was performed for 1 minute after drainage.
[0059]
(2) Softening treatment After the washing treatment, 30 L of tap water was poured, and then 7 mL of the softening agent composition shown in Table 1 was added and stirred for 5 minutes. Then, it drained and dehydrated, and it dried for 12 hours in the constant temperature room of 60% of humidity and 25 degreeC.
[0060]
(3) Evaluation of flexibility performance dimethyl distearyl ammonium chloride (Coatamine D86P manufactured by Kao Co., Ltd., excluding 2-propanol) 5% of a softening agent consisting of 20 mL of a softening agent as described above was used as a reference shirt. did.
[0061]
The shirt treated with the softening agent composition of the example or the comparative example was compared with the reference shirt and judged by 10 panelists (10 men in their 30s). The judgment criteria are as follows, and are listed in Table 1 by rounding off the first decimal place of the average score of 10 people.
[0062]
Softness criterion +2: Very softer than the standard +1; Slightly softer than the standard 0; Equivalent to the standard -1: Slightly harder than the standard -2: Elasticity criterion very harder than the standard +2: Very much higher than the standard Elasticity +1; slightly elastic than the standard 0; elasticity equivalent to the standard -1: the standard is slightly more elastic -2: the standard is much more elastic Performance against polyester and wool
(1) Laundry treatment 1 kg of commercially available polyester desine and 1 kg of wool sweater, respectively, using a commercially available light detergent for home use Emar (manufactured by Kao Corporation) and tap water. And then washed three times and dehydrated for 1 minute.
[0063]
(2) Softening treatment After the washing treatment, 30 L of tap water was poured, and then 7 mL of the softening agent composition shown in Table 1 was added and stirred for 5 minutes. Then, it drained and dehydrated, and it dried for 24 hours in the constant temperature room of 60% of humidity and 25 degreeC.
[0064]
(3) Evaluation of softness performance Polyester decine or wool softened in the same manner as described above using 20 ml of softening agent consisting of 5% of dimethyldistearylammonium chloride (Coatamine D86P manufactured by Kao Corporation excluding 2-propanol) The sweater was the standard for each case.
[0065]
The polyester decyne or the wool sweater treated with the softening agent composition of the example or the comparative example was compared with the reference polyester decyne or the wool sweater, respectively, and judged by 10 panelists (10 women in their 30s). The judgment criteria are as follows, and are listed in Table 1 by rounding off the first decimal place of the average score of 10 people.
[0066]
Criteria for softness +2: Very softer than the standard +1; slightly softer than the standard 0; equivalent to the standard −1: Slightly softer than the standard -2: Judgment standard of elasticity +2 softer than the standard : Very elastic than the standard +1; slightly elastic than the standard 0; elasticity equivalent to the standard -1: the standard is slightly more elastic -2: the standard is much more elastic [0067]
[Table 1]

[0068]
【The invention's effect】
The softener composition of the present invention is excellent in flexibility and can impart an excellent texture to the textile even with a small amount of silicone content.

Claims (3)

Organopolysiloxane having at least one anionic group in the molecule, wherein the anionic group is linked to a silicon atom in a structure represented by at least one of general formulas (1) and (2) A tertiary having 0.05 to 3% by weight of polysiloxane (component (A)) , an ester group and / or an amide group and one or more alkyl groups or alkenyl groups having 10 to 36 carbon atoms in the molecule. A softener composition containing 2 to 50% by weight of an amine or a salt thereof or a quaternized product thereof (component (B)).

[Wherein, R ¹ and R ² are the same or different and each represents an optionally substituted linear or branched alkylene group, alkenylene group or arylene group having 2 to 22 carbon atoms, which may have a substituent containing a hetero atom. Show. X represents an -O- or -NH- group. M represents a hydrogen atom, a metal, ammonium, an alkyl or alkenyl ammonium having 1 to 22 carbon atoms, an alkyl or alkenyl substituted pyridinium having 1 to 22 carbon atoms, an alkanol ammonium having 1 to 22 carbon atoms, or a basic amino acid. ]

[Wherein R ¹ , R ² , X and M represent the above-mentioned meanings, and R ³ and R ⁴ are the same or different and may have a substituent containing a hetero atom, and have 2 to 22 carbon atoms. A linear or branched alkylene group, alkenylene group or arylene group. ] Further, a nonionic surfactant and / or anionic surfactants softener composition of claim 1 Symbol placement contains. The softener composition according to claim 1 or 2 , wherein the component (A) is obtained by reacting an organopolysiloxane having a hydroxyl group and / or an amino group with an acid anhydride or acid chloride.