JP4176317B2 - Liquid detergent composition - Google Patents

Description

【０００５】
〔式中、ｌ＝１００〜６００であり、ｍ，ｎはｌ：ｍ＝１００：１〜１０：１、且つｍ：ｎ＝１：１０〜１０：１となる数である。Ｒは炭素数１〜４のアルキル基、ヒドロキシ基又はアルコキシ基であり、Ｒ¹は炭素数１〜４のアルキル基であり、それぞれ異なってもよい。Ａは下記（イ）で表される基又は（イ）及び（ロ）で表される基であり、後者の場合、Ａ中の（ロ）の割合は５０モル％以下である。
【０００６】
【化４】

【０００７】
（ここで、ａ＝２〜６、ｂ＝２〜６、Ｒ²は水素原子又は炭素数１〜４のアルキル基、ｐ＝１〜６、ｑ＝１〜２０、ｒ＝０〜２０、Ｒ³は炭素数１〜１８のアルキル基）、Ｂは-(ＣＨ₂)_a-Ｏ-(Ｃ₂Ｈ₄Ｏ)_s-(Ｃ₃Ｈ₆Ｏ)_t-Ｒ^2'又はＲ²（ここで、Ｒ^2'は炭素数１〜１０のアルキル基、ｓ＝１〜２０、ｔ＝０〜２０）を示す。尚、式（Ｉ）中に-Ｃ₂Ｈ₄Ｏ-及び-Ｃ₃Ｈ₆Ｏ-が存在する場合は、ブロック付加でもランダム付加でも良い。〕
【０００８】
【発明の実施の形態】
＜（ａ）成分＞
本発明の液体洗浄剤組成物は、（ａ）成分である前記式（Ｉ）で表されるシリコーン誘導体を、０．０５〜１５重量％、更に０．０５〜１０重量％、特に０．１〜５重量％含有するのが、衣類に対する柔軟化効果の点で好ましい。前記式（Ｉ）のシリコーン誘導体としては、柔軟化効果の点でｌ＝１００〜４００、ｌ：ｍ＝６０：１〜１０：１、ｍ：ｎ＝１：５〜５：１、Ｒ及びＲ¹はメチル基、Ａは（イ）、又は（イ）及び（ロ）の混合〔ここで（イ）／（ロ）＝５／１〜１／１（モル比）、ａ＝２〜４、Ｒ²は水素原子、ｐ＝１〜３、ｑ＝１〜１５、ｒ＝０〜１０、Ｒ³は炭素数６〜１６のアルキル基〕、Ｂは-(ＣＨ₂)_a-Ｏ-(Ｃ₂Ｈ₄Ｏ)_s-(Ｃ₃Ｈ₆Ｏ)_t-Ｒ^1'又はＲ¹（ここでＲ^1'はメチル基、ｓ＝５〜２０、ｔ＝０〜１０）のものが好ましい。尚、一般式（Ｉ）中に-Ｃ₂Ｈ₄Ｏ-及び-Ｃ₃Ｈ₆Ｏ-が存在する場合は、ブロック付加でもランダム付加でも良いが、配合安定性の点で、ブロック付加が好ましい。
【０００９】
前記式（Ｉ）のシリコーン誘導体は、特公昭５６−２９６９１号の請求項１記載の方法等により得ることができる。
【００１０】
＜（ｂ）成分＞
本発明の（ｂ）成分としては、分子中にエステル基及び／又はアミド基を１個以上有するものが好ましく、特に下記一般式（II）で表される化合物及び／又は下記一般式（III）若しくはその塩で表される化合物が好ましい。
【００１１】
【化５】

【００１２】
〔式中Ｒ⁴は炭素数８〜３６、好ましくは１０〜２４、特に好ましくは１２〜２０のアルキル基又はアルケニル基であり、Ｒ⁵は炭素数１〜５、好ましくは１〜３のアルキレン基であり、Ｘは−ＣＯＯ−、−ＣＯＮＲ⁹−、−ＯＣＯ−、−ＮＲ⁹ＣＯ−から選ばれる基である。ここでＲ⁹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であり、好ましくは水素原子である。Ｒ⁶、Ｒ⁷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Ｒ⁴−Ｘ−Ｒ⁵−、Ｒ⁸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を示し、Ｙ^-は無機又は有機の陰イオン、好ましくはハロゲンイオン、硫酸イオン、リン酸イオン、炭素数１〜３のアルキル硫酸エステルイオン、炭素数１〜１２の脂肪酸イオンであり、特に好ましくはハロゲンイオン、硫酸イオン、炭素数１〜３のアルキル硫酸エステルイオンである。〕。
【００１３】
前記式（II）で表される化合物及び／又は前記一般式（III）で表される化合物は、特開平０５−２３０００１号の段落０００８〜００２０に記載の方法等により得ることができる。
【００１４】
本発明の液体洗浄剤組成物は、（ｂ）成分、好ましくは前記式（II）及び／又は（III）で表される化合物を、０．０５〜１５重量％、更に０．０５〜１０重量％、特に０．１〜５重量％含有するのが、衣類に対する柔軟化効果の点で好ましい。
【００１５】
本発明の（ａ）成分と（ｂ）成分の総量は、好ましくは組成物中に０．１〜３０重量％、より好ましくは０．１〜２０重量％、特に好ましくは０．２〜１０重量％であり、（ａ）成分／（ｂ）成分の重量比は、１／５〜５／１、更に１／３〜３／１、より更に１／２〜２／１、特に１／１．２〜１．２／１、より特に約１／１であることが衣類、特に木綿製品に対する柔軟化効果の点で好ましい。
【００１６】
＜その他の成分＞
本発明では、従来、液体洗浄剤組成物に配合することが知られている界面活性剤を使用することができる。なお洗浄性を高める上で界面活性剤は、陰イオン界面活性剤、非イオン界面活性剤を主界面活性剤として使用することが好ましい。更に柔軟性を高めるために陽イオン界面活性剤と併用する場合は、非イオン界面活性剤を主界面活性剤とすることが好ましい。
【００１７】
陰イオン界面活性剤としては、炭素数１０〜１８のアルキル鎖を持つ直鎖アルキルベンゼンスルホン酸塩、アルキル硫酸エステル塩、ポリオキシアルキレンアルキルエーテル硫酸エステル塩、アルファスルホ脂肪酸アルキル（例えばメチル）エステル塩等のアルカリ金属塩が好ましく、牛脂やヤシ由来の脂肪酸塩を少量配合してもよい。
【００１８】
陰イオン界面活性剤の対イオンとしてはナトリウム、カリウム等のアルカリ金属以外に、マグネシウム等のアルカリ土類金属及び／又はモノ、ジ、トリエタノールアミン等のアルカノールアミン等を使用するが、特にアルカノールアミンを用いることで液安定性が向上することから好適である。その場合、組成物中の陰イオン界面活性剤の含有量は５〜５０重量％、特に１０〜５０重量％が好ましい。
【００１９】
非イオン界面活性剤としては、下記（１）〜（４）のようなものが使用できる。
（１）平均炭素数が８〜２０の直鎖１級アルコールまたは直鎖２級アルコール由来のアルキル基又は分岐アルコール由来のアルキル基又はアルケニル基を有し、エチレンオキサイド（以下、ＥＯと表記する）を平均で１〜２０モルを付加したポリオキシエチレンアルキル又はアルケニルエーテル。
（２）平均炭素数が８〜２０のアルキル基又はアルケニル基を有し、ＥＯを平均で１〜１５モル及びプロピレンオキサイド（以下、ＰＯと表記する）を平均で１〜５モル付加したポリオキシアルキレンアルキル又はアルケニルエーテル。この場合、ＥＯ及びＰＯはランダム付加でもブロック付加でもいずれでもよい。
（３）次の一般式（IV）で表されるアルキル多糖界面活性剤。
Ｒ¹⁰−(ＯＲ¹¹)_iＧ_j （IV）
〔式中、Ｒ¹⁰は直鎖又は分岐鎖の炭素数８〜１８のアルキル基、アルケニル基、又はアルキルフェニル基、Ｒ¹¹は炭素数２〜４のアルキレン基、Ｇは炭素数５又は６の還元糖に由来する残基、ｉは平均値０〜６の数、ｊは平均値１〜１０の数を示す。〕
（４）脂肪酸アルカノールアミド、ポリヒドロキシ脂肪酸アミド。
【００２０】
特に、油性汚れ洗浄力の点で、（１）または（２）のポリオキシアルキレンアルキルエーテルが好ましい。また、組成物中の非イオン界面活性剤の含有量は５〜５０重量％、特に１０〜５０重量％が好ましい。
【００２１】
また、更に衣類などへの柔軟性向上させるためには、モノ長鎖アルキル４級アンモニウム塩等の陽イオン界面活性剤を、組成物中０．５〜１０重量％、特に１〜５重量％含有することが好ましい。柔軟性向上効果の点で、長鎖アルキル基が炭素数１２〜２２、特に１４〜２０のアルキル基である長鎖アルキルトリメチルアンモニウム塩が好ましい。陽イオン界面活性剤の対イオンとしては、ハロゲンイオン、ＣＨ₃ＳＯ₄ ^-、Ｃ₂Ｈ₅ＳＯ₄ ^-、ＣＨ₃ＣＯＯ^-又はＨＣＯＯ^-が好ましい。更に柔軟性を高めるため、陽イオン界面活性剤を陰イオン界面活性剤に対して、陽イオン界面活性剤／陰イオン界面活性剤＝３／１〜１／２、更に２／１〜１／２、特に１．２／１〜１／１．２のモル比で配合することが好ましい。
【００２２】
その他界面活性剤として、液の安定性及び泥汚れ洗浄性の点で、両性界面活性剤を配合してもよい。両性界面活性剤としてアルキルカルボベタイン、アルキルスルホベタイン、アルキルアミドヒドロキシスルホベタイン、アルキルアミドアミン型ベタイン及びアルキルイミダゾリン型ベタインなどが配合できる。両性界面活性剤は、組成物中１〜２０重量％含有されるのが好ましい。
【００２３】
更に本発明の洗浄剤組成物には、次の成分を配合することができる。アルカリ金属の水酸化物、ケイ酸塩、炭酸ナトリウム等の炭酸塩、及びアルカノールアミン等のアルカリ剤０．０１〜１０重量％；エタノール等のアルコール類、エチレングリコール及びプロピレングリコール等のグリコール類、パラトルエンスルホン酸、安息香酸塩（防腐剤としての効果もある）並びに尿素等の減粘剤及び可溶化剤０．０１〜３０重量％；ポリオキシアルキレンベンジルエーテル、ポリオキシアルキレンフェニルエーテル等の相調整剤及び洗浄力向上剤０．０１〜１０重量％；ニトリロ三酢酸塩、エチレンジアミン四酢酸塩、イミノ二酢酸塩、ジエチレントリアミン五酢酸塩、グリコールエーテルジアミン四酢酸塩、ヒドロキシエチルイミノ二酢酸塩及びトリエチレンテトラミン六酢酸塩等のアミノポリ酢酸塩、マロン酸、コハク酸、ジグリコール酸、リンゴ酸、酒石酸及びクエン酸等の塩等の金属イオン捕捉剤０．１〜２０重量％；ポリアクリル酸、ポリマレイン酸、カルボキシメチルセルロース、平均分子量５０００以上のポリエチレングリコール、無水マレイン酸−アクリル酸共重合体、無水マレイン酸−ジイソブチレン共重合体、無水マレイン酸−メチルビニルエーテル共重合体、無水マレイン酸−イソブチレン共重合体、無水マレイン酸―酢酸ビニル共重合体、ナフタレンスルホン酸塩ホルマリン縮合物、及び特開昭５９−６２６１４号公報の請求項１〜２１（１頁３欄５行〜３頁４欄１４行）記載のポリマー等の再汚染防止剤及び分散剤０．０１〜１０重量％；ポリビニルピロリドン等の色移り防止剤０．０１〜１０重量％；過炭酸ナトリウム又は過硼酸ナトリウム等の漂白剤０．０１〜１０重量％；テトラアセチルエチレンジアミン、特開平６−３１６７００号の一般式（Ｉ−２）、（Ｉ−３）、（Ｉ−４）、（Ｉ−５）、（Ｉ−６）、（Ｉ−７）で示される漂白活性化剤等の漂白活性化剤０．０１〜１０重量％；アミラーゼ、プロテアーゼ、リパーゼ及びセルラーゼ等の酵素０．００１〜２重量％；塩化カルシウム、硫酸カルシウム、ギ酸、ホウ酸（ホウ素化合物）等の酵素安定化剤０．００１〜２重量％；チノパールＣＢＳ（チバガイギー社製）やホワイテックスＳＡ(住友化学社製)等の蛍光染料０．００１〜１重量％；シリカ、（ａ）成分以外のシリコーン等の消泡剤０．０１〜２重量％；ブチルヒドロキシトルエン、ジスチレン化クレゾール、亜硫酸ナトリウム及び亜硫酸水素ナトリウム等の酸化防止剤０．０１〜２重量％；青味付け剤；香料；抗菌防腐剤等が挙げられる。
【００２４】
本発明の液体洗浄剤組成物は上記（ａ）、（ｂ）成分と任意成分と残部の水とからなる。本発明の液体洗浄剤組成物のｐＨは７．５〜９（２５℃）が好ましく、ｐＨはアルカリ剤又は酸剤により調整することが好ましい。アルカリ剤としては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、メチルモノエタノールアミン、ジメチルエタノールアミン、３−アミノプロパノール等のアルカノールアミン類、水酸化ナトリウム、水酸化カリウム等、珪酸ナトリウム、炭酸ナトリウム等の無機塩類を使用することができ、特にモノエタノールアミン、水酸化ナトリウム、水酸化カリウムから選ばれる１種以上が好ましい。酸剤としては、硫酸、塩酸、リン酸、炭素数１〜１２の脂肪酸、炭素数１〜３のアルキル硫酸から選ばれる１種以上が好ましい。
【００２５】
【実施例】
表１に示す液体洗浄剤組成物を調製し、得られた組成物を用いて下記の柔軟化効果、及びカラーケア（色あせ防止）効果についての評価を行った。その結果を表１に示す。
【００２６】
〔柔軟化効果の評価〕
（１−１）前処理布の調製
自動二槽式洗濯機（東芝銀河３．６ ＶＨ−３６０Ｓ１）を準備し、洗濯槽に４０Ｌの水道水を入れ、これに合計２．０ｋｇになるように木綿タオル、木綿メリアス未着用肌着を混ぜて入れた。更にコンパクト型粉末洗剤（アタック、花王（株））を標準使用量に従い投入し、１０分洗濯、１分脱水、８分流水すすぎし（１５Ｌ／分の水量）、乾燥機で乾燥させた。この洗濯サイクルを５回繰り返し、前処理布とした。
【００２７】
（１−２）評価法
上記洗濯機の洗濯槽に３０Ｌの水道水を入れ、柔軟性評価用前処理布のうち木綿タオル２枚、木綿メリアス未着用肌着３枚を入れる。更に表１の液体洗浄剤組成物を２０ｍＬ入れ１０分間普通洗浄した。次に１分間脱水し、３０Ｌの水道水で５分間×２回ためすすぎした。最後に１分間脱水し、屋内で自然乾燥させ、２０℃／６５％ＲＨの恒温恒湿室に一日間静置した。
【００２８】
（１−３）柔軟化効果判定基準
木綿タオル２枚、木綿メリアス未着用肌着３枚の計５枚についてそれぞれ未洗浄品と手触りを比較することにより下記のごとく評点した。

以上の評点は熟練したパネラー５人により行われ、判定した衣類計５枚の平均合計点で柔軟化効果を比較した。
【００２９】
〔色あせ防止効果の評価〕
（２−１）試験布
試験布としては、木綿ブロード２０２３布を染料Cibacron Blue F-GFN（チバガイギー社製）５％水溶液で染色した布を６ｃｍ×６ｃｍに裁断したものを数枚用意し、試験布とした。
【００３０】
（２−２）洗浄条件
二槽式洗濯機（東芝銀河３．６ ＶＨ−３６０Ｓ１）を準備し、洗濯槽に４０Ｌの２０℃水道水を入れ、これに１．４ｋｇの綿製の未着用肌着及び０．６ｋｇの綿／ポリエステル混紡の未着用肌着ワイシャツを入れる。また、３０ｃｍ×３０ｃｍの綿布に評価用の試験布を５枚縫い付けたものを１枚用意し洗濯槽に入れ、更に表１の液体洗浄剤組成物を２６．６７ｍＬ入れ、１０分間普通洗浄する。その後１分脱水し、４分間ためすすぎを２回繰り返す。その後５分間脱水し、室内で自然乾燥させる。この工程を１工程とし、５回累積洗浄を行った。
【００３１】
（２−３）測色方法
測色は、色差計（日本電色工業株式会社：ND(F)-300A）を用いて試験布のＬ値、ａ値及びｂ値を測色し、５枚の試験布の各平均値から、次式によりΔＥ値を求めた。ΔＥ値が小さいほど、累積洗浄による変褪色が少ないことを意味する。
ΔＥ＝｛(ΔＬ)²＋(Δａ)²＋(Δｂ)²｝^1/2
ΔＬ；〔洗浄後の試験布のＬ値(平均値)〕−〔洗浄前の試験布のＬ値(平均値)〕
Δａ；〔洗浄後の試験布のａ値(平均値)〕−〔洗浄前の試験布のａ値(平均値)〕
Δｂ；〔洗浄後の試験布のｂ値(平均値)〕−〔洗浄前の試験布のｂ値(平均値)〕
【００３２】
【表１】

【００３３】
表１に用いた成分を下記に示す。
・化合物ａ−１：一般式（Ｉ）中の構造が以下の化合物。
〔Ｒ：CH₃、Ｒ⁵：CH₃、Ａ：（イ）-(CH₂)₃-NH-CO-CH₂-O-(C₂H₄O)₅-C₁₂H₂₅及び、（ロ）-(CH₂)₃-NH₂の混合、（イ）／（ロ）＝７／３（モル比）、Ｂ：-(CH₂)₃-O-(C₂H₄O)₁₀-CH₃、ｌ＝３００、ｍ＝７、ｎ＝４〕
・化合物ａ−２：一般式（Ｉ）中の構造が以下の化合物。
〔Ｒ：CH₃、Ｒ⁵：CH₃、Ａ：（イ）-(CH₂)₃-NH-CO-CH₂-O-(C₂H₄O)₅-C₁₂H₂₅、Ｂ：-CH₃、ｌ＝３００、ｍ＝７、ｎ＝４〕
・化合物ａ−３：一般式（Ｉ）中の構造が以下の化合物。
〔Ｒ：CH₃、Ｒ⁵：CH₃、Ａ：（イ）-(CH₂)₃-NH-CO-CH₂-O-(C₂H₄O)₅-C₁₂H₂₅及び、（ニ）-(CH₂)₃-NH-CO-CH₂-O-(C₂H₄O)₅-C₁₄H₂₉の混合、（イ）／（ニ）＝７／３（モル比）、Ｂ：-(CH₂)₃-O-(C₂H₄O)₁₀-CH₃、ｌ＝２００、ｍ＝１４、ｎ＝８〕・化合物ｂ−１：一般式（II）中の構造が以下の化合物。
〔Ｒ⁴：炭素数１７及び１５が混合したアルキル基（炭素数１７／炭素数１５＝６０／４０）、Ｒ⁵はエチレン基、Ｘは−ＣＯＯ−基、Ｒ⁶はＲ⁴−Ｘ−Ｒ⁵−基、Ｒ⁷、Ｒ⁸はメチル基、Ｙ^-は塩化物イオン〕
・化合物ｂ−２：一般式（III）中の構造が以下の化合物。
〔Ｒ⁴：炭素数１７及び１５が混合したアルキル基（炭素数１７／炭素数１５＝６０／４０）、Ｒ⁵はエチレン基、Ｘは−ＣＯＯ−基、Ｒ⁶はＲ⁴−ＣＯＮＨ−Ｃ₃Ｈ₆−基、Ｒ⁷はメチル基〕
・化合物ｂ−３：一般式（III）中の構造が以下の化合物。
〔Ｒ⁴：炭素数１７及び１５が混合したアルキル基（炭素数１７／炭素数１５＝６０／４０）、Ｒ⁵はプロピレン基、Ｘは−ＣＯＮＨ−基、Ｒ⁶はヒドロキシエチル基、Ｒ⁷はメチル基〕
・非イオン界面活性剤１：炭素数１０〜１４の直鎖第１級アルコールにＥＯを平均８モル、ＰＯを平均２モルランダム付加させたもの
・非イオン界面活性剤２：炭素数１０〜１４の直鎖第１級アルコールにＥＯを平均７モル、ＰＯを平均２モル、ＥＯを平均３モルの順にブロック付加させたもの・非イオン界面活性剤３：炭素数１０〜１４の直鎖第２級アルコールにＥＯを平均７モル付加させたもの
・非イオン界面活性剤４：炭素数１０〜１４の直鎖第１級アルコールにＥＯを平均１２モル付加させたもの
・陽イオン界面活性剤：炭素数１６〜１８のモノアルキルトリメチルアンモニウムクロリド（炭素数１６と１８の比率は３／７）
・ＬＡＳ−Ｓ剤：炭素数１０〜１４の直鎖アルキルベンゼンスルホン酸
・ＥＳ：ポリオキシエチレンアルキルエーテル硫酸エステルナトリウム（アルキル炭素数１２、ＥＯ平均付加モル数３）
・脂肪酸：炭素数１２〜１４のヤシ油系脂肪酸
・高分子化合物：無水マレイン酸ジイソブチレン共重合体、平均分子量５０００・ポリエチレングリコールフェニルエーテル：ポリオキシエチレンモノフェニルエーテル（ＥＯ平均付加モル数３）
・酵素：デュラザイム１６．０Ｌ（プロテアーゼ、ノボザイム社製）
・蛍光染料：チノパールＣＢＳ−Ｘ（チバスペシャリティケミカルス株式会社製）
【００３４】
【発明の効果】
本発明の液体洗浄剤組成物は、木綿衣料に対する柔軟化効果に優れ、更にカラーケア効果に優れる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid detergent composition that has an excellent softening effect on cotton garments and also has an excellent color care effect.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, liquid detergents have a soft image on clothes, and therefore liquid detergents having a softening effect on clothes have been developed for some time. JP-A-60-215099 and JP-A-9-67594 describe that a detergent containing an amino-modified silicone or a derivative thereof has an excellent softening effect or an excellent felt shrinkage preventing effect. Has been. Japanese Patent Application Laid-Open No. 10-60480 describes that a detergent containing an amino-modified silicone derivative and a specific nonionic surfactant has an appropriate detergency and is excellent in texture and dimensional stability. ing. However, the softening effect of garments, particularly cotton fiber products, by these techniques is insufficient, and the development of a liquid detergent imparting a further excellent softening effect is desired. In addition to the above-mentioned softening effect, it is desirable that the cleaning composition is excellent in color care effect for preventing the fading of clothes due to repeated washing, but the above-mentioned technique is not mentioned about improvement of the color care effect.
[0003]
[Means for Solving the Problems]
The present invention includes (a) a silicone derivative represented by the following general formula (I) (hereinafter referred to as component (a)), (b) a quaternary ammonium salt having one or more hydrocarbon groups having 8 to 36 carbon atoms, and The present invention relates to a liquid detergent composition containing at least one selected from tertiary amines having at least one hydrocarbon group having 8 to 36 carbon atoms or acid salts thereof (hereinafter referred to as component (b)).
[0004]
[Chemical 3]

[0005]
[Wherein, l = 100 to 600, and m and n are numbers such that l: m = 100: 1 to 10: 1 and m: n = 1: 10 to 10: 1. R is an alkyl group having 1 to 4 carbon atoms, a hydroxy group or an alkoxy group, and R ¹ is an alkyl group having 1 to 4 carbon atoms, which may be different from each other. A is a group represented by the following (A) or a group represented by (A) and (B). In the latter case, the ratio of (B) in A is 50 mol% or less.
[0006]
[Formula 4]

[0007]
(Where, a = 2~6, b = 2~6 , R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p = 1~6, q = 1~20 , r = 0~20, R ³ is an alkyl group having 1 to 18 carbon atoms), B is — (CH ₂ ) _a —O— (C ₂ H ₄ O) _s — (C ₃ H ₆ O) _t —R ^{2 ′} or R ² (where , R ^{2 ′} represents an alkyl group having 1 to 10 carbon atoms, s = 1 to 20, t = 0 to 20). When -C ₂ H ₄ O- and -C ₃ H ₆ O- are present in the formula (I), block addition or random addition may be used. ]
[0008]
DETAILED DESCRIPTION OF THE INVENTION
<(A) component>
In the liquid detergent composition of the present invention, the silicone derivative represented by the formula (I) as the component (a) is 0.05 to 15% by weight, more preferably 0.05 to 10% by weight, particularly 0.1%. The content of ˜5% by weight is preferable in terms of the effect of softening clothes. Examples of the silicone derivative of the formula (I) include l = 100 to 400, l: m = 60: 1 to 10: 1, m: n = 1: 5 to 5: 1, R and R in terms of a softening effect. ¹ is a methyl group, A is (a), or a mixture of (a) and (b) [where (a) / (b) = 5/1 to 1/1 (molar ratio), a = 2 to 4, R ² is a hydrogen atom, p = 1 to 3, q = 1 to 15, r = 0 to 10, R ³ is an alkyl group having 6 to 16 carbon atoms, and B is — (CH ₂ ) _a —O— (C ₂ H ₄ O) _s — (C ₃ H ₆ O) _t —R ^{1 ′} or R ¹ (where R ^{1 ′} is a methyl group, s = 5 to 20, t = 0 to 10) is preferable. When -C ₂ H ₄ O- and -C ₃ H ₆ O- are present in the general formula (I), block addition or random addition may be used, but block addition is preferable from the viewpoint of blending stability. .
[0009]
The silicone derivative of the formula (I) can be obtained by the method described in claim 1 of JP-B-56-29691.
[0010]
<(B) component>
As the component (b) of the present invention, those having at least one ester group and / or amide group in the molecule are preferable. Particularly, the compound represented by the following general formula (II) and / or the following general formula (III) Or the compound represented with the salt is preferable.
[0011]
[Chemical formula 5]

[0012]
[Wherein R ⁴ is an alkyl or alkenyl group having 8 to 36 carbon atoms, preferably 10 to 24, particularly preferably 12 to 20 carbon atoms, and R ⁵ is an alkylene group having 1 to ⁵ carbon atoms, preferably 1 to 3 carbon atoms. And X is a group selected from —COO—, —CONR ⁹ —, —OCO—, and —NR ⁹ CO—. Here, R ⁹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably a hydrogen atom. R ⁶ and R ⁷ each independently represents an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, or R ⁴ —X—R ⁵ —, R ⁸ represents an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms; ^- is an inorganic or organic anion, preferably a halogen ion, sulfate ion, phosphate ion, alkyl sulfate ion having 1 to 3 carbon atoms, fatty acid ion having 1 to 12 carbon atoms, particularly preferably a halogen ion, sulfate An ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms. ].
[0013]
The compound represented by the formula (II) and / or the compound represented by the general formula (III) can be obtained by the method described in paragraphs 0008 to 0020 of JP-A No. 05-230001.
[0014]
In the liquid detergent composition of the present invention, the component (b), preferably the compound represented by the formula (II) and / or (III) is 0.05 to 15% by weight, more preferably 0.05 to 10% by weight. %, Particularly 0.1 to 5% by weight is preferable from the viewpoint of a softening effect on clothes.
[0015]
The total amount of the component (a) and the component (b) of the present invention is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, particularly preferably 0.2 to 10% by weight in the composition. The weight ratio of component (a) / component (b) is 1/5 to 5/1, further 1/3 to 3/1, more preferably 1/2 to 2/1, particularly 1/1. A ratio of 2 to 1.2 / 1, more particularly about 1/1 is preferable in terms of a softening effect on clothes, particularly cotton products.
[0016]
<Other ingredients>
In the present invention, a surfactant that is conventionally known to be blended in a liquid detergent composition can be used. In order to improve detergency, it is preferable to use an anionic surfactant or a nonionic surfactant as the main surfactant. Furthermore, when using together with a cationic surfactant in order to improve a softness | flexibility, it is preferable to use a nonionic surfactant as a main surfactant.
[0017]
Examples of the anionic surfactant include linear alkyl benzene sulfonate having alkyl chain having 10 to 18 carbon atoms, alkyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate ester salt, alpha sulfo fatty acid alkyl (for example, methyl) ester salt, etc. Alkali metal salts are preferred, and a small amount of fatty acid salts derived from beef tallow or palm may be blended.
[0018]
In addition to alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and / or alkanolamines such as mono-, di-, and triethanolamine are used as counter ions for anionic surfactants. Is preferable because the liquid stability is improved. In that case, the content of the anionic surfactant in the composition is preferably 5 to 50% by weight, more preferably 10 to 50% by weight.
[0019]
As the nonionic surfactant, the following (1) to (4) can be used.
(1) It has an alkyl group derived from a linear primary alcohol or linear secondary alcohol having an average carbon number of 8 to 20, or an alkyl group or alkenyl group derived from a branched alcohol, and ethylene oxide (hereinafter referred to as EO). Polyoxyethylene alkyl or alkenyl ether added with 1 to 20 moles on average.
(2) Polyoxygen having an alkyl group or alkenyl group having an average carbon number of 8 to 20, and adding 1 to 15 mol of EO on average and 1 to 5 mol of propylene oxide (hereinafter referred to as PO) on average Alkylene alkyl or alkenyl ether. In this case, EO and PO may be either random addition or block addition.
(3) An alkyl polysaccharide surfactant represented by the following general formula (IV):
R ¹⁰ − (OR ¹¹ ) _i G _j (IV)
[Wherein R ¹⁰ is a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group, or an alkylphenyl group, R ¹¹ is an alkylene group having 2 to 4 carbon atoms, and G is a group having 5 or 6 carbon atoms. Residues derived from reducing sugars, i is an average value of 0-6, and j is an average value of 1-10. ]
(4) Fatty acid alkanolamide, polyhydroxy fatty acid amide.
[0020]
In particular, the polyoxyalkylene alkyl ether of (1) or (2) is preferable from the viewpoint of oily soil detergency. The content of the nonionic surfactant in the composition is preferably 5 to 50% by weight, particularly preferably 10 to 50% by weight.
[0021]
In addition, in order to further improve the flexibility of clothing, etc., a cationic surfactant such as a mono long chain alkyl quaternary ammonium salt is contained in the composition in an amount of 0.5 to 10% by weight, particularly 1 to 5% by weight. It is preferable to do. From the viewpoint of improving flexibility, a long-chain alkyltrimethylammonium salt in which the long-chain alkyl group is an alkyl group having 12 to 22 carbon atoms, particularly 14 to 20 carbon atoms is preferable. The counter ion of the cationic surfactant is preferably a halogen ion, CH ₃ SO ₄ ⁻ , C ₂ H ₅ SO ₄ ⁻ , CH ₃ COO ⁻ or HCOO ⁻ . In order to further increase the flexibility, the cationic surfactant is anionic surfactant with respect to the cationic surfactant / anionic surfactant = 3/1 to 1/2, and further 2/1 to 1/2. In particular, it is preferable to blend at a molar ratio of 1.2 / 1 to 1 / 1.2.
[0022]
In addition, as the surfactant, an amphoteric surfactant may be blended from the viewpoint of the stability of the liquid and the ability to clean mud dirt. As the amphoteric surfactant, alkylcarbobetaine, alkylsulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine type betaine, alkylimidazoline type betaine and the like can be blended. The amphoteric surfactant is preferably contained in the composition in an amount of 1 to 20% by weight.
[0023]
Furthermore, the following components can be mix | blended with the cleaning composition of this invention. Alkali metal hydroxides, silicates, carbonates such as sodium carbonate, and alkali agents such as alkanolamines 0.01 to 10% by weight; alcohols such as ethanol, glycols such as ethylene glycol and propylene glycol, para Toluenesulfonic acid, benzoate (also has an effect as a preservative) and urea and other thinning agents and solubilizers 0.01 to 30% by weight; phase adjustment of polyoxyalkylene benzyl ether, polyoxyalkylene phenyl ether, etc. Agent and detergency improver 0.01 to 10% by weight; nitrilotriacetate, ethylenediaminetetraacetate, iminodiacetate, diethylenetriaminepentaacetate, glycol etherdiaminetetraacetate, hydroxyethyliminodiacetate and triethylene Aminopolyacetates such as tetramine hexaacetate, malonic acid 0.1-20% by weight of metal ion scavenger such as succinic acid, diglycolic acid, malic acid, tartaric acid and citric acid; polyacrylic acid, polymaleic acid, carboxymethylcellulose, polyethylene glycol having an average molecular weight of 5000 or more, anhydrous Maleic acid-acrylic acid copolymer, maleic anhydride-diisobutylene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-isobutylene copolymer, maleic anhydride-vinyl acetate copolymer, naphthalene sulfone Acid salt formalin condensate, and a recontamination preventive and dispersing agent such as a polymer described in claims 1 to 21 (page 1, column 3, line 5 to page 3, column 4, line 14) of JP-A-59-62614. 01 to 10% by weight; 0.01 to 10% by weight of a color transfer inhibitor such as polyvinylpyrrolidone; sodium percarbonate or Bleaching agent such as sodium borate 0.01 to 10% by weight; tetraacetylethylenediamine, general formulas (I-2), (I-3), (I-4), (I-5) of JP-A-6-316700 , (I-6), bleach activators such as bleach activators represented by (I-7) 0.01 to 10% by weight; enzymes such as amylase, protease, lipase and cellulase 0.001 to 2% by weight ; 0.001 to 2% by weight of enzyme stabilizer such as calcium chloride, calcium sulfate, formic acid, boric acid (boron compound); 0.001 to 1% by weight; silica, antifoaming agent such as silicone other than component (a) 0.01 to 2% by weight; butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium hydrogensulfite Antioxidant 0.01 to 2 wt%, such as helium, bluing agents; perfumes; antimicrobial preservative, and the like.
[0024]
The liquid detergent composition of the present invention comprises the above components (a) and (b), optional components and the remaining water. The pH of the liquid detergent composition of the present invention is preferably 7.5 to 9 (25 ° C.), and the pH is preferably adjusted with an alkali agent or an acid agent. Alkaline agents include monoethanolamine, diethanolamine, triethanolamine, methylmonoethanolamine, dimethylethanolamine, alkanolamines such as 3-aminopropanol, sodium hydroxide, potassium hydroxide, sodium silicate, sodium carbonate, etc. Inorganic salts can be used, and at least one selected from monoethanolamine, sodium hydroxide, and potassium hydroxide is particularly preferable. As an acid agent, 1 or more types chosen from a sulfuric acid, hydrochloric acid, phosphoric acid, a C1-C12 fatty acid, and a C1-C3 alkyl sulfuric acid are preferable.
[0025]
【Example】
The liquid cleaning composition shown in Table 1 was prepared, and the following softening effect and color care (fading prevention) effect were evaluated using the obtained composition. The results are shown in Table 1.
[0026]
[Evaluation of softening effect]
(1-1) Preparation of pre-treatment cloth An automatic two-tank washing machine (Toshiba Galaxy 3.6 VH-360S1) is prepared, and 40 L of tap water is put into the washing tub so that the total amount becomes 2.0 kg. Cotton towels and cotton underwear were worn and mixed. Further, a compact type powder detergent (Attack, Kao Co., Ltd.) was added according to the standard usage amount, washed for 10 minutes, dehydrated for 1 minute, rinsed with running water for 8 minutes (15 L / min water amount), and dried with a dryer. This washing cycle was repeated 5 times to obtain a pretreated fabric.
[0027]
(1-2) Evaluation Method 30 L of tap water is put into the washing tub of the washing machine, and two cotton towels and three cotton underwears are put on the pretreatment cloth for flexibility evaluation. Further, 20 mL of the liquid detergent composition shown in Table 1 was added and washed normally for 10 minutes. Next, it was dehydrated for 1 minute and rinsed twice with 30 L of tap water for 5 minutes. Finally, it was dehydrated for 1 minute, naturally dried indoors, and left in a constant temperature and humidity room of 20 ° C./65% RH for one day.
[0028]
(1-3) Criteria for determination of softening effect The total score of 2 cotton towels and 3 underwears of cotton melias was evaluated as follows by comparing the unwashed product with the touch.

The above scores were made by five skilled panelists, and the softening effect was compared with the average total score of the five clothing totals judged.
[0029]
[Evaluation of anti-fading effect]
(2-1) Test cloth As a test cloth, several sheets of cotton broad 2023 cloth, which was dyed with a dye Cibacron Blue F-GFN (manufactured by Ciba Geigy) 5% aqueous solution and cut into 6 cm × 6 cm, were prepared and tested. Cloth.
[0030]
(2-2) Washing conditions A two-tank washing machine (Toshiba Galaxy 3.6 VH-360S1) is prepared, 40 L of 20 ° C. tap water is placed in the washing tub, and 1.4 kg of cotton unweared underwear And a 0.6 kg cotton / polyester blended underwear shirt. Also prepared is a piece of 30 cm × 30 cm cotton cloth with 5 test cloths for evaluation, put in a washing tub, and then add 26.67 mL of the liquid detergent composition shown in Table 1 for 10 minutes. . Then dehydrate for 1 minute and repeat rinse twice for 4 minutes. Then dehydrate for 5 minutes and let it air dry indoors. This process was regarded as one process, and cumulative cleaning was performed 5 times.
[0031]
(2-3) Color measurement method Color measurement is performed by measuring the L value, a value and b value of the test cloth using a color difference meter (Nippon Denshoku Industries Co., Ltd .: ND (F) -300A). From each average value of the test cloth, ΔE value was obtained by the following formula. A smaller ΔE value means less discoloration due to cumulative cleaning.
ΔE = {(ΔL) ² + (Δa) ² + (Δb) ² } ^1/2
ΔL; [L value (average value) of test cloth after washing]-[L value (average value) of test cloth before washing]
Δa; [a value (average value) of test cloth after washing]-[a value (average value) of test cloth before washing]
Δb; [b value (average value) of test cloth after washing]-[b value (average value) of test cloth before washing]
[0032]
[Table 1]

[0033]
The components used in Table 1 are shown below.
Compound a-1: A compound having the following structure in the general formula (I):
[R: CH ₃ , R ⁵ : CH ₃ , A: (I)-(CH ₂ ) ₃ —NH—CO—CH ₂ —O— (C ₂ H ₄ O) ₅ —C ₁₂ H ₂₅ ) — (CH ₂ ) ₃ —NH ₂ , (I) / (B) = 7/3 (molar ratio), B: — (CH ₂ ) ₃ —O— (C ₂ H ₄ O) ₁₀ —CH ₃ , l = 300, m = 7, n = 4]
Compound a-2: A compound having the following structure in the general formula (I):
^{_{[R: CH 3, R 5:}} CH 3, A :( _{b) - (CH 2) 3 -NH} -CO-CH 2 -O- (C 2 H 4 O) 5 -C 12 H 25, B: - CH ₃ , l = 300, m = 7, n = 4]
Compound a-3: A compound having the following structure in the general formula (I):
[R: CH ₃ , R ⁵ : CH ₃ , A: (I)-(CH ₂ ) ₃ —NH—CO—CH ₂ —O— (C ₂ H ₄ O) ₅ —C ₁₂ H ₂₅ ) — (CH ₂ ) ₃ —NH—CO—CH ₂ —O— (C ₂ H ₄ O) ₅ —C ₁₄ H ₂₉ , (b) / (d) = 7/3 (molar ratio), B :-( CH ₂ ) ₃ —O— (C ₂ H ₄ O) ₁₀ —CH ₃ , l = 200, m = 14, n = 8]. Compound b-1: The structure in the general formula (II) is as follows: Compound.
[R ⁴ : alkyl group in which carbon numbers 17 and 15 are mixed (carbon number 17 / carbon number 15 = 60/40), R ⁵ is an ethylene group, X is a —COO— group, and R ⁶ is R ⁴ —X—R. ⁵ -group, R ⁷ and R ⁸ are methyl groups, Y ⁻ is chloride ion)
Compound b-2: A compound having the following structure in the general formula (III):
[R ^4: an alkyl group of a mixture of several 17 and 15 carbon atoms (15 = 60/40 Number 17 / carbon atoms), R ⁵ is an ethylene group, X is -COO- group, R ⁶ is R ⁴ -CONH-C ₃ H ₆ -group, R ⁷ is methyl group]
Compound b-3: A compound having the following structure in the general formula (III):
[R ^4: an alkyl group of a mixture of several 17 and 15 carbon atoms (number 17 / carbon atoms 15 = 60/40 carbon), R ⁵ is a propylene group, X is -CONH- group, R ⁶ is hydroxyethyl group, R ⁷ Is a methyl group]
・ Nonionic surfactant 1: Random addition of 8 mol of EO and 2 mol of PO on average to a linear primary alcohol having 10 to 14 carbon atoms ・ Nonionic surfactant 2: 10 to 14 carbon atoms Non-ionic surfactant 3: straight chain second having 10 to 14 carbon atoms in which EO is averagely 7 mol, PO is average 2 mol and EO is average 3 mol Non-ionic surfactant with an average of 7 moles of EO added to a secondary alcohol: Non-ionic surfactant with an average of 12 moles of EO added to a linear primary alcohol having 10 to 14 carbon atoms. Cationic surfactant: Carbon Monoalkyltrimethylammonium chloride having 16 to 18 carbon atoms (ratio of carbon numbers 16 and 18 is 3/7)
-LAS-S agent: linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms-ES: sodium polyoxyethylene alkyl ether sulfate ester (12 alkyl carbons, 3 EO average addition moles)
Fatty acid: C12-14 coconut oil fatty acid Polymer compound: maleic anhydride diisobutylene copolymer, average molecular weight 5000 Polyethylene glycol phenyl ether: polyoxyethylene monophenyl ether (EO average addition mole number 3)
Enzyme: Durazyme 16.0L (protease, manufactured by Novozyme)
・ Fluorescent dye: Chino Pearl CBS-X (manufactured by Ciba Specialty Chemicals Co., Ltd.)
[0034]
【The invention's effect】
The liquid detergent composition of the present invention is excellent in the softening effect on cotton clothing and further in the color care effect.

Claims (2)

(A) a silicone derivative represented by the following general formula (I), (b) a tertiary amine represented by the following general formula ( III ) or at least one selected from its acid salt, and having a pH of 7.5 ~ 9 (25 ° C) liquid detergent composition.

[Wherein, l = 100 to 600, and m and n are numbers such that l: m = 100: 1 to 10: 1 and m: n = 1: 10 to 10: 1. R is an alkyl group having 1 to 4 carbon atoms, a hydroxy group or an alkoxy group, and R ¹ is an alkyl group having 1 to 4 carbon atoms, which may be different from each other. A is a group represented by the following (A) or a group represented by (A) and (B). In the latter case, the ratio of (B) in A is 50 mol% or less.

(Where, a = 2~6, b = 2~6 , R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p = 1~6, q = 1~20 , r = 0~20, R ³ is an alkyl group having 1 to 18 carbon atoms), B is — (CH ₂ ) _a —O— (C ₂ H ₄ O) _s — (C ₃ H ₆ O) _t —R ^{2 ′} or R ² (where , R ^{2 ′} represents an alkyl group having 1 to 10 carbon atoms, s = 1 to 20, t = 0 to 20). When -C ₂ H ₄ O- and -C ₃ H ₆ O- are present in the formula (I), block addition or random addition may be used. ]

[Wherein R ⁴ is an alkyl or alkenyl group having 12 to 20 carbon atoms, R ⁵ is an alkylene group having 1 to 3 carbon atoms, and X is —CONR ⁹ —. Here, R ⁹ is a hydrogen atom. R ⁶ and R ⁷ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. ]   The liquid detergent composition according to claim 1, wherein the weight ratio of (a) / (b) is 1/5 to 5/1.