JP4087147B2 - Liquid detergent composition - Google Patents

Description

【００２７】
〔式中、Ｒ₁、Ｒ₂、Ｒ₃は、同一又は異なって、水素原子、炭素数１〜４のアルキル基又はフェニル基を示す。Ｒ₄は、水素原子、炭素数１〜２２の直鎖若しくは分岐鎖のアルキル基若しくはアルケニル基、又は炭素数６〜２２のアリール基、炭素数７〜２２のアルキルアリール基若しくはアリールアルキル基を示す。ｎ個のＡＯは、同一又は異なって、アルキレンオキシ基を示す。ｎは、３〜２００の数を示す。ｐは、０又は１を示す。Ｘは、炭素数１〜１２のアルキレン基、炭素数６〜１２のアリーレン基又は下記一般式（４）
【００２８】
【化２】

【００２９】
で表わされる２価の基を示す。（式中、Ｒ₅は、水素原子、炭素数１〜２２の直鎖若しくは分岐鎖のアルキル基若しくはアルケニル基、又は炭素数６〜２２のアリール基、炭素数７〜２２のアルキルアリール基若しくはアリールアルキル基を示す。ｍ個のＡＯは、同一又は異なって、アルキレンオキシ基を示す。ｑは、１〜１０の数を示す。ｍは、０〜２００の数を示す。）〕
【００３０】
一般式（３）中、Ｒ₁、Ｒ₂、Ｒ₃は、同一又は異なって、水素原子又はメチル基が好ましい。
【００３１】
一般式（３）のＲ₄と一般式（４）中のＲ₅は、同一又は異なって、水素原子、又は炭素数１〜８のアルキル基若しくはフェニル基が好ましく、炭素数１〜３のアルキル基が更に好ましく、メチル基が特に好ましい。例えばメチル、エチル、プロピル、イソプロピル、ブチル、ｔ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル基等が挙げられる。
【００３２】
一般式（３）中のＸは、炭素数１〜８のアルキレン基が好ましく、炭素数１〜３のアルキレン基が更に好ましく、例えばメチレン、エチレン、プロピレン、トリメチレン基が挙げられ、メチレン基が特に好ましい。
【００３３】
一般式（３）、（４）中のＡＯは、同一又は異なって、炭素数２〜４のアルキレンオキシ基が好ましく、ブロック、ランダム、交互何れの重合体であってもよい。ｍ、ｎは、同一又は異なって、好ましくは、３〜１００であり、更に好ましくは３〜５０である。ｍ＋ｎは、好ましくは３〜２００、更に好ましくは６〜１００である。ＡＯが、炭素数２のオキシエチレン基の単独重合体である場合、前述のＲ₄、Ｒ₅は、同一又は異なって、水素原子以外が好ましい。特に、一般式（３）、（４）の(ＡＯ)_n、(ＡＯ)_mは、同一又は異なって、下記一般式（５）で表わされるブロック重合体又はランダム重合体、特にブロック重合体が好ましく、ブロック重合体の場合は、反応性不飽和基Ｒ₁Ｒ₂Ｃ＝Ｃ(Ｒ₃)により近い位置にエチレンオキシ基が結合していることが好ましい。
【００３４】
−[(Ｃ₂Ｈ₄Ｏ)_r／(Ｃ₃Ｈ₆Ｏ)_s]− （５）
（式中、ｒは、３〜１３０、ｓは、１〜５０の数を示す。）
ここで、一般式（５）のｒは、好ましくは３〜５０、ｓは、好ましくは１〜３０である。
【００３５】
一般式（３）のｐは、１が好ましく、一般式（４）のｑは、１〜５が好ましく、１が更に好ましい。
【００３６】
一般式（３）で表される化合物は、例えばｐ＝０の場合、アリルアルコールにアルカリ条件下、アルキレンオキシドを付加重合することで得られる。ｐ＝１の場合、例えば、アリルアルコールに、グリシドールを付加し、次にアルカリ条件下、アルキレンオキシドを付加重合することで得られる。Ｒ₄、Ｒ₅が水素原子以外の基である場合、アミン類の共存下に、アルキル化剤を反応させるいわゆるウイリアムソン反応によってエーテル結合を有する化合物を合成することができる。
【００３７】
（ｂ）成分の重量平均分子量は、粘度の過度な上昇を防ぐ目的から、好ましくは１００万以下、さらに好ましくは１０００から５０万、特に好ましくは５０００〜３０万である。この重量平均分子量は、後述する測定法により求めた。
【００３８】
本発明の液体洗浄剤組成物において、（ａ）成分と（ｂ）成分の質量比は、（ａ）成分の分散安定性から、（ｂ）／（ａ）＝１／８０〜１／４が好ましく、１／６０〜１／５が更に好ましく、１／４０〜１／８が特に好ましい。
【００３９】
［液体分散媒］
本発明の液体洗浄剤組成物中、液体分散媒の比率は、３０〜６９質量％が好ましく、４０〜６９質量％が更に好ましい。近似的に液体分散媒の比率は、液体洗浄剤組成物中の非イオン性界面活性剤、水酸基含有水溶性有機溶剤及び水の合計配合量の比率とみなすことができる。液体分散媒量は、通常、遠心分離によって、固形分を沈降させ、場合によりろ過することで求めることができる。
【００４０】
液体分散媒は、液体と該液体に溶解した成分とから構成され、界面活性剤を必須成分とし、水及び水溶性有機溶剤を含有することが好ましい。この液体分散媒は水を含んでいても良いが、洗浄剤組成物のコンパクト化のために、液体分散媒中の水の比率は、好ましくは４０質量％以下であり、さらに好ましくは３〜２０質量％であり、特に好ましくは３〜１５質量％、最も好ましくは３〜１２質量％である。下限は、製造のし易さから、好ましくは０．１質量％以上であり、さらに好ましくは１質量％以上である。
【００４１】
液体分散媒中、界面活性剤の比率は１０〜９０質量％が好ましく、３０〜８０質量％が更に好ましく、５０〜７０質量％が特に好ましい。なお、全界面活性剤（後述の液体分散媒に不溶のものを含む）の液体洗浄剤組成物中の比率は、３〜６５質量％が好ましく、更に１５〜６０質量％、特に２０〜５０質量％が好ましい。界面活性剤としては非イオン性界面活性剤が好ましく、アニオン性界面活性剤、カチオン性界面活性剤、双性界面活性剤も製品の安定性を阻害しない範囲で、非イオン性界面活性剤と共に液体分散媒に溶解して使用することが出来る。
【００４２】
本発明の液体洗浄剤において、全界面活性剤と（ｂ）成分の質量比は、液体洗浄剤組成物の安定性から、（ｂ）成分／全界面活性剤＝１／８０〜１／４．１が好ましく、１／６０〜１／４．５が更に好ましく、１／３０〜１／５が特に好ましい。
【００４３】
本発明において、液体分散媒を構成し得る成分を以下に示す。
【００４４】
（１）非イオン性界面活性剤
非イオン性界面活性剤を洗浄剤組成物に配合して用いることは従来から行われており、洗浄力と安定性に優れる点で好適である。非イオン性界面活性剤の全界面活性剤中の比率は７０〜１００質量％が好ましく、更に９０〜１００質量％、特に１００質量％が好ましい。
【００４５】
非イオン性界面活性剤として、例えば日本国特許庁公報「周知・慣用技術集（衣料用粉末洗剤）の３章の１」記載の公知の非イオン性界面活性剤を用いることができる。
【００４６】
本発明の液体洗浄剤組成物には、特にポリエチレンオキシド及び／又はポリプロピレンオキシド型の非イオン性界面活性剤を使用することが好ましく、とりわけ炭素数８〜１８を有する直鎖もしくは分岐鎖の第１級又は第２級アルコールにエチレンオキシド（以下、ＥＯと表記する）を平均５〜２０モル付加したポリオキシエチレンアルキルエーテル並びに前記アルコールにＥＯを平均５〜１５モル及びプロピレンオキシド（以下、ＰＯと表記する）を平均１〜５モル付加したポリオキシエチレンポリオキシプロピレンアルキルエーテル（但し、ＥＯとＰＯは、ランダム状に付加していてもブロック状に付加していてもよい。）から選択される１種以上を使用することが好ましい。
【００４７】
その他の非イオン性界面活性剤として、ポリオキシエチレンアルキルフェニルエーテル類、Ｎ−ポリオキシエチレンアルキルアミン、蔗糖脂肪酸エステル類、脂肪酸グリセリンモノエステル類、高級脂肪酸アルカノールアミド類、ポリオキシエチレン高級脂肪酸アルカノールアミド類、アミンオキサイド類、アルキルグリコシド類、アルキルグリセリルエーテル類及びＮ−アルキルグルコンアミド類等も使用することができる。
【００４８】
（２）アニオン性界面活性剤
本発明の液体洗浄剤組成物には、例えば日本国特許庁公報「周知・慣用技術集（衣料用粉末洗剤）の３章の１」記載の公知のアニオン性界面活性剤を使用することができる。特にスルホン酸塩型、硫酸塩型、リン酸塩型及び／又はカルボン酸塩型のアニオン性界面活性剤が好適に配合される。
【００４９】
具体的には、平均炭素数８〜２２の直鎖又は分岐鎖のアルキル基又はアルケニル基を有する、アルキル又はアルケニルベンゼンスルホン酸塩、アルキル又はアルケニル硫酸エステル塩、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塩（平均ＥＯ付加モル数０．５〜６モル）、モノアルキル又はアルケニルリン酸塩及び脂肪酸塩から選ばれる１種以上のアニオン性界面活性剤が好ましい。
【００５０】
これらのアニオン性界面活性剤の対イオンとして、ナトリウム、カリウム、マグネシウム、カルシウム、エタノールアミン類等のアミンがプロトン化された陽イオン、第４級アンモニウム塩及びそれらの混合物等が挙げられる。アニオン性界面活性剤を配合する場合は、酸型で配合し、別途アルカリ（例えばエタノールアミン等）を添加するような方法を用いてもよい。
【００５１】
（３）カチオン性界面活性剤
本発明の液体洗浄剤組成物には、例えば日本国特許庁公報「周知・慣用技術集（衣料用粉末洗剤）の３章の１」記載の公知のカチオン性界面活性剤を使用することができ、例えばベンザルコニウム型等の４級アンモニウム塩が好適に配合される。
【００５２】
（４）双性界面活性剤
本発明の液体洗浄剤組成物には、例えば日本国特許庁公報「周知・慣用技術集（衣料用粉末洗剤）の３章の１」記載の公知の双性界面活性剤を使用することができ、例えばアルキルベタイン型双性界面活性剤等が好適に配合される。
【００５３】
（５）水酸基含有水溶性有機溶剤
水酸基含有水溶性有機溶剤は、製品の粘度調節、非イオン性界面活性剤のゲル化防止、洗濯水への溶解性調節を行う目的で本発明の液体洗浄剤組成物中に配合される。更には（ｂ）成分を製造する際、重合溶剤の一部として用い、（ｂ）成分の分子量を調整する役割を担わせることもできる。
【００５４】
水酸基含有水溶性有機溶剤は特に限定されないが、一般式（６）及び／又は（７）及び／又は（８）及び／又は（９）にて表記されるものが好ましい。
ＨＯ[ＣＨ₂ＣＨ₂Ｏ]_a[ＣＨ_2-b(ＣＨ₃)_bＣＨ_2-c(ＣＨ₃)_cＯ]_dＨ （６）
ＨＯ[ＣＨ₂ＣＨ₂Ｏ]_a[ＣＨ_2-b(ＣＨ₃)_bＣＨ_2-c(ＣＨ₃)_cＯ]_d−Ｐｈ （７）
ＣＨ_3-e(ＯＨ)_eＣＨ_2-f(ＯＨ)_fＣＨ_3-g(ＯＨ)_g （８）
ＣＨ_3-h(ＯＨ)_hＣＨ_2-i(ＯＨ)_iＣＨ_2-j(ＯＨ)_jＣＨ_3-k(ＯＨ)_k （９）
（式中、ａは平均値として１〜１２０、ｄは平均値として０〜３０の数を示す。但し、ａ＞ｄである。ｂ，ｃ，ｅ，ｆ，ｇ，ｈ，ｉ，ｊ，ｋは、それぞれ０又は１の整数を表す。但し、ｂ＋ｃ＝１、ｅ＋ｆ＋ｇ＝２又は３、ｈ＋ｉ＋ｊ＋ｋ＝２である。Ｐｈはフェニル基である。）
【００５５】
液体分散媒中、水酸基含有水溶性有機溶剤の比率は７〜６０質量％が好ましく、７〜５０質量％が更に好ましく、１５〜４０質量％が特に好ましい。全液体洗浄剤組成物中、２．１〜４１．４質量％が好ましく、２．８〜３４．５質量％が更に好ましく、６〜２７．６質量％が特に好ましい。
【００５６】
具体的には、ブタンジオール、ペンタンジオール、ヘキサンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の多価アルコール類、多価アルコール類のモノ−、ジ−又はトリ−アルキルエーテル、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、エチレンオキサイド／プロピレンオキサイド共重合体等のグリコール類、グリコール類のモノアルキルエーテル、モノアリールエーテル特にモノフェニルエーテル等が挙げられる。これら水酸基含有水溶性有機溶剤は１種又は２種以上の混合物として配合される。
【００５７】
（５）その他の有機溶剤
その他、有機溶剤として、アルキルアミン、脂肪族アミン、脂肪族又は芳香族カルボン酸のアミド又はアルキルエステル類、低級アルキルエステル、ケトン、アルデヒド、グリセリド等が配合される。液体分散媒中、その他の有機溶剤の比率は、洗浄力及び洗浄剤組成物のコンパクト化の点から、０〜５０質量％が好ましく、更に０〜２０質量％、特に０〜１０質量％が好ましい。
【００５８】
（６）水
水は、製品の粘度調節、非イオン性界面活性剤のゲル化防止、洗濯水への溶解性調節を行う目的で配合する。（ａ）成分の無機ビルダー粒子に吸着されている水の量以外に、本発明の液体洗浄剤組成物に配合される水の量は、液体洗浄剤組成物中、１〜３０質量％が好ましく、１〜１５質量％が更に好ましく、２〜１２質量％が特に好ましい。
【００５９】
本発明の液体洗浄剤組成物において、液体分散媒と（ａ）成分の質量比は、（ａ）成分の分散安定性から、液体分散媒／（ａ）成分＝１／３〜３／１が好ましく、１／２〜２／１が更に好ましい。
【００６０】
［その他の成分］
本発明の液体洗浄剤組成物は、その他の成分として、液体分散媒に不溶な界面活性剤、無機ビルダー、有機ビルダー、漂白剤、一般の洗浄剤添加物を含有することができる。これらは２種以上を併用しても良い。これらは、（ａ）成分と同様に、本洗浄剤組成物中に分散配合することができる。その際、（ａ）成分を解砕する前に混合して（ａ）成分と共に解砕分散しても良いし、（ａ）成分を解砕後、混合しても良い。以下に、その他の成分の具体例を示す。
【００６１】
その他−１：液体分散媒に不溶な界面活性剤
本発明の液体洗浄剤組成物は、好ましくは液体分散媒に界面活性剤を含有しているが、これとは別に、液体分散媒に不溶性である界面活性剤が固体分散質として分散配合されていても良い。
【００６２】
その他−２：無機ビルダー
公知のケイ酸塩、メタケイ酸塩等の洗剤用ビルダーを任意に配合することが出来る。これらはアルカリ金属塩であることが好ましい。例えばトリポリ燐酸塩、ピロ燐酸塩等の燐酸塩、アミノトリ（メチレンホスホン酸）、１−ヒドロキシエチリデン−１，１−ジホスホン酸、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）又はそれらの塩も用いることができる。
【００６３】
その他−３：有機ビルダー
本発明の液体洗浄剤組成物は、液体分散媒に溶解する又は／及び溶解しない公知の有機ビルダーも含有することが出来る。具体的には、クエン酸、こはく酸、マロン酸等の多価カルボン酸、アスパラギン酸、グルタミン酸等のアミノ酸、ニトリロ三酢酸、エチレンジアミン四酢酸等のアミノポリ酢酸、ポリアクリル酸、アクリル酸／マレイン酸共重合体等の高分子多価カルボン酸が挙げられ、これらはアルカリ金属塩、アンモニウム塩、置換アンモニウム塩等の塩の形態が好ましい。有機ビルダーの比率は液体洗浄剤組成物中０．５〜１５．０質量％が好ましく、更に１．０〜１０．０質量％が好ましく、特に２．０〜７．０質量％が好ましい。
【００６４】
その他−４：漂白剤
本発明の液体洗浄剤組成物は、漂白剤を含有することも好ましい。漂白剤は、無機過酸素漂白剤、又は無機過酸素漂白剤と漂白活性化剤を組み合わせて用いることができる。
【００６５】
無機過酸素漂白剤として、アルカリ金属の過ホウ酸塩、過炭酸塩、過ケイ酸塩、過リン酸塩が挙げられ、特に過ホウ酸ナトリウム、過炭酸ナトリウム等が好ましい。また製品の分散安定性を高める上で、特開平１１−２７９５９３号公報第２頁第２欄１３〜４４行に挙げられるような、カルボン酸系ポリマー及び／又は多価カルボン酸により被覆されている過炭酸塩を用いることができる。
【００６６】
無機過酸素漂白剤と漂白活性化剤とを組み合わせて用いる場合、漂白活性化剤は通常過酸を形成する反応性アシル基を１つ以上有する有機化合物であり、無機過酸素漂白剤単独で使用するよりも、漂白作用がより有効となる。漂白活性化剤の構造は特に限定されないが、一般式(１０)で表されるものが好ましい。
【００６７】
【化３】

【００６８】
[式中、Ｒ⁶は炭素数１〜１５の直鎖又は分岐鎖のアルキル基を示し、ＸはＣＯＯＭ又はＳＯ₃Ｍ（ここで、Ｍは水素原子、アルカリ金属原子又はアルカリ土類金属原子）を示す。]。
【００６９】
一般式(１０)で表される漂白活性化剤は、一般式(１０)において、Ｒ⁶が炭素数７〜１１の直鎖又は分岐鎖のアルキル基であり、ＸがＣＯＯＨ又はＳＯ₃Ｎaであるものが好ましい。このような漂白活性化剤として、ラウロイルオキシベンゼンスルホン酸ナトリウム、デカノイルオキシベンゼンスルホン酸ナトリウム、オクタノイルオキシベンゼンスルホン酸ナトリウム、ラウロイルオキシ安息香酸、デカノイルオキシ安息香酸、オクタノイルオキシ安息香酸等を挙げることが出来る。
【００７０】
その他一般の洗浄剤に用いられるポリエチレングリコール、カルボキシメチルセルロース等のポリマー、ポリビニルピロリドン等の色移り防止剤、プロテアーゼ、セルラーゼ、リパーゼ等の酵素、塩化カルシウム、ギ酸、ホウ酸等の酵素安定化剤、シリコーン等の消泡剤、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、亜硫酸水素ナトリウム等の酸化防止剤、香料成分、染料、蛍光染料、顔料等を必要に応じて含んでも良い。
【００７１】
［製造方法］
本発明の液体洗浄剤組成物の製造には、（ａ）成分を含む固体成分を湿式粉砕して微細化固体分散質スラリーを得る工程を含む。この場合、全成分を攪拌混合してスラリー化し、湿式粉砕するか、又は（ａ）成分と他の成分の一部との混合物を湿式粉砕し、その後残りの成分を追加することが好ましい。さらに好ましくは、（ａ）成分と（ｂ）成分を、好ましくは溶剤中で、接触させた後、溶剤を留去し、次に液体分散媒と混合し、湿式粉砕する液体洗浄剤組成物の製法である。溶剤として、エタノール、メタノール等の低級アルコール系溶剤、又はヘキサン、ヘプタン、ドデカン、シクロヘキサン、メチルシクロヘキサン、イソオクタン、水添トリイソブチレン等の脂肪族炭化水素、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素等が例示される。
【００７２】
あるいは、固体分散質を予め乾式粉砕等にて微細化し、液体分散媒と混合後、攪拌又は湿式粉砕して製造することも好ましい。乾式粉砕等により、予め十分に小粒径となった固体分散質を用いる場合、フロージェットミキサー等の分散機を用いることで、簡便に液体洗浄剤組成物を得ることもできる。
【００７３】
湿式粉砕法としては、ストーンミル、コロイドミル、ケーディーミル、スラッシャーミル、ハイスピードディスパーサー、メディアミル、ロールミル、ニーダー、エクストルーダー、液体ジェット相互作用室を有する粉砕機（例えばマイクロフライディックス社製マイクロフライダイザー）、超音波分散器などが挙げられるが、とりわけメディアを用いる湿式粉砕、例えばサンドミル、サンドグラインダー、湿式振動ミル、アトライター等を用いる方法が粉砕効率の点から好適である。メディアとしてチタニア、ジルコニア等、公知の材質を適用することができる。
【００７４】
サンドミルを用いる粉砕による場合、メディアの直径として０．１〜１．０ｍｍのものが特に適する。原料となる固体ビルダーの粒度が特に大きい場合には、あらかじめ大きな直径、例えば直径２ｍｍのメディアを用いて粉砕を行った後、これに続いてより直径の小さいメディアを用いることにより、効果的な微粉砕が行える場合もある。
【００７５】
湿式粉砕時、固体分散質の粉砕効率を高めるため、好ましくは固体分散質混合物／液体分散媒（質量比）＝３０／７０〜６０／４０とする。
【００７６】
湿式粉砕の時間は、安定分散に十分な平均粒径となった時を終点とするが、３分以上が好ましい。更に好ましくは５分以上である。
【００７７】
湿式粉砕時、系の粘度を低く保ち、粉砕効率を高めるために、液体分散媒を数回に分けて追加することが出来る。
【００７８】
湿式粉砕後の微細化固体分散質の平均粒径は、１０μｍ以下が良く、好ましくは０．０１〜５μｍ、さらに好ましくは０．０５〜２μｍ、特に好ましくは０．１〜１．０μｍ、最も好ましくは０．１〜０．７μｍである。
【００７９】
（液体洗浄剤組成物）
本発明の液体洗浄剤組成物に配合される（ｂ）成分は、配合物中での固体分散質の化学的安定性を充分に有する分散剤として作用するが、それと共に洗浄時に汚れの分散剤、すなわち洗浄対象から剥離した汚れが再び洗浄対象に付着するのを防止する再汚染防止剤としても作用する。これは、液体洗浄剤組成物中では、この（ｂ）成分のカルボキシル基又はその塩（イ）が分散質に吸着し、アルキレンオキシ基を構成単位とするポリマー鎖（ロ）が液体成分に溶解状態をとることで、立体効果によって、分散質の凝集・ネットワーク化を防ぎ、良好な分散状態を維持することで低粘度を作り出すと考えられる。一方洗浄水中では、この共重合体は汚れ成分に吸着し、汚れ表面をアニオン性とすることによるイオン性反発効果で汚れ成分を水中に分散し、洗浄対象物の再汚染を防止すると考えられる。本発明の液体洗浄剤組成物は、安定な分散系が得られるため、その低粘度化を可能とする。
【００８０】
本発明の液体洗浄剤組成物は、作業性を向上するために、３０００ｍＰａ・ｓ以下であることが好ましく、２０００ｍＰａ・ｓ以下であることがさらに好ましく、１０００ｍＰａ・ｓ以下であることが特に好ましく、７００ｍＰａ・ｓ以下が最も好ましい。液体洗浄剤の飛散を防止し、無機ビルダー粒子の安定性を高めるために、１０ｍＰａ・ｓ以上が好ましく、５０ｍＰａ・ｓ以上が更に好ましい。
【００８１】
【実施例】
分子量の測定はゲル浸透型液体クロマトグラフィー（ＧＰＣ）によって行い、次の条件を用いた。溶離液及び添加塩類はいずれも液体クロマトグラフィー用のグレードの試薬から調製した。
カラム：東ソー（株）製 Ｇ４０００ＰＷＸＬ＋Ｇ２５００ＰＷＸＬの２本、
溶離液：０．２Ｍリン酸緩衝液（ｐＨ６．９）／アセトニトリル＝９／１（容量比）、
検出器：示差屈折率計、
温度：４０℃、
標準：ポリエチレングリコール、ポリエチレンオキシド、
測定濃度：５ｍｇ／ｍｌ、
注入量：１００μｌ
【００８２】
合成例１：合成ポリマー（１）［ポリエチレングリコールとポリアクリル酸（４０／６０（質量比））のブロックポリマー］の合成例
ポリ[ポリオキシエチレン４，４’−アゾビス（４−シアノペンタノエート）]（ＶＰＥ−０２０１、和光純薬（株）製）４０ｇ、アクリル酸６０ｇをイオン交換水３００ｇに溶解し、窒素雰囲気下で１０分間撹拌後、加熱し、６５〜７０℃に保って６時間撹拌を続けた。これを氷冷しながら、６Ｎ水酸化ナトリウム水溶液１１０ｍＬを徐々に加えて中和し、このポリマーのカルボキシル基の約８０％をナトリウム塩とした。この水溶液を凍結乾燥し、合成ポリマー（１）を得た。得られた合成ポリマー（１）のＧＰＣ測定の結果、重量平均分子量は２２．２万（ポリエチレングリコール換算）であった。合成ポリマー（１）には、カラムはＴＳＫ ＧＭＰＷＸＬ（東ソー（株）製）２本を用い、その他の条件は、前述に示したものである。
【００８３】
合成例２：合成ポリマー（２）［ポリエチレングリコール（ＥＯ付加モル数９）モノメタクリル酸エステル／メタクリル酸＝８０／２０（質量比）共重合体］の合成例
イオン交換水１００ｇを窒素雰囲気下で１００℃に昇温したところに、ポリエチレングリコール（ＥＯ付加モル数９）モノメタクリル酸エステル（ＮＫ−エステルＭ−９０Ｇ、新中村化学（株）製）８０ｇ、４８％水酸化ナトリウム７．８ｇにて中和したメタクリル酸２０ｇ、２−メルカプトエタノール４．５ｇをイオン交換水４０ｇに溶解したものと、過硫酸ナトリウム４．６ｇをイオン交換水４２ｇに溶解したものとを、１００〜１０５℃に保ちながら、別々に２時間かけて滴下し、その後１００℃に保ちながらさらに１時間撹拌を続けた。これを室温に戻した後、３５％過酸化水素水１０．８ｇにて脱臭し、余剰の過酸化水素水を３５％亜硫酸水素ナトリウム１．９ｇにて還元した。この水溶液を凍結乾燥し、合成ポリマー（２）を得た。得られた合成ポリマー（２）のＧＰＣ測定の結果、重量平均分子量は３．９万（ポリエチレングリコール換算）であった。
【００８４】
合成例３：合成ポリマー（３）［ポリエチレングリコールとポリ（アクリル酸／マレイン酸＝７０／３０（モル比））（５０／５０（質量比））のグラフトポリマー］の合成例
ポリエチレングリコール（ポリエチレングリコール２，０００、和光純薬（株）製）５０ｇ、マレイン酸２０．４ｇを窒素雰囲気下に加熱溶解し、さらに撹拌を続けながら１５０℃に昇温した。温度を１４５〜１５０℃に保ちながら、この溶液にアクリル酸２９．６ｇと、ジ−ｔ−ブチルパーオキシド４．３ｇとを別々に１時間かけて滴下し、さらに１５０℃に保ちながら３時間撹拌を続け、室温に戻した。イオン交換水２００ｍＬを加えて希釈し、これを氷冷しながら、６Ｎ水酸化ナトリウム水溶液１００ｍＬを徐々に加えて中和し、このポリマーのカルボキシル基の約８０％をナトリウム塩とした。この水溶液を凍結乾燥し、合成ポリマー（３）を得た。得られた合成ポリマー（３）のＧＰＣ測定の結果、重量平均分子量は４．５万（ポリエチレングリコール換算）であった。
【００８５】
合成例４：合成ポリマー（４）［ポリエチレングリコール（ＥＯ付加モル数２３）モノメタクリル酸エステル／メタクリル酸＝５０／５０（質量比）共重合体］の合成例
ポリエチレングリコール（ＥＯ付加モル数２３）モノメタクリル酸エステル５０ｇ、メタクリル酸５０ｇをポリエチレングリコール（ＥＯ付加モル数３）モノフェニルエーテル（ＰＨＧ−３０、日本乳化剤（株）製）７５０ｇに溶解し、窒素雰囲気下で１０分間撹拌した。これに、２，２’−アゾビス−(２，４−ジメチルバレロニトリル)（Ｖ−６５、和光純薬（株）製）８ｇを加えて窒素雰囲気下で加熱し、７５〜８０℃に保って６時間撹拌を続けた。その後室温に戻し、合成ポリマー（４）溶液（ポリマー（４）濃度：１１．７質量％）を得た。得られた合成ポリマー（４）のＧＰＣ測定の結果、重量平均分子量は３．１万（ポリエチレングリコール換算）であった。
【００８６】
合成例５：合成ポリマー（５）［ポリエチレングリコール（ＥＯ付加モル数９）モノメタクリル酸エステル／アクリル酸＝２０／８０（質量比）共重合体］の合成例
イオン交換水２００ｇを窒素雰囲気下で６０℃に昇温したところに、ポリエチレングリコール（ＥＯ付加モル数９）モノメタクリル酸エステル（ＮＫ−エステルＭ−９０Ｇ、新中村化学（株）製）２０ｇ、アクリル酸８０ｇをイオン交換水８０ｇに溶解したものと、２，２’−アゾビス−（２−メチルプロピオンアミジン）２塩酸塩（Ｖ−５０、和光純薬（株）製）１．６ｇをイオン交換水１２０ｇに溶解したものとを、６０〜６５℃に保ちながら、別々に２時間かけて滴下し、その後６５℃に保ちながらさらに６時間撹拌を続けた。これを室温に戻した後、氷冷しながら６Ｎ水酸化ナトリウム水溶液１５０ｍＬを徐々に加えて中和し、このポリマーのカルボキシル基の約８０％をナトリウム塩とした。この水溶液を凍結乾燥し、合成ポリマー（５）を得た。得られた合成ポリマー（５）のＧＰＣ測定の結果、重量平均分子量は４．９万（ポリエチレングリコール換算）であった。
【００８７】
合成例６：合成ポリマー（６）［ポリエチレングリコール（ＥＯ付加モル数２３）モノメタクリル酸エステル／メタクリル酸／スチレンスルホン酸ナトリウム＝５０／２５／２５（質量比）共重合体］の合成例
エタノール１００ｇを窒素雰囲気下で８０℃に昇温したところに、エタノール６０ｇ、ポリエチレングリコール（ＥＯ付加モル数２３）モノメタクリル酸エステル（ＮＫ−エステルＭ−２３０Ｇ、新中村化学（株）製）４０ｇ、メタクリル酸２０ｇ、スチレンスルホン酸ナトリウム２０ｇをイオン交換水１２０ｇに溶解したものを混合したものと、２，２’−アゾビス−(２，４−ジメチルバレロニトリル)（Ｖ−６５、和光純薬（株）製）２．７ｇをエタノール２４ｇに溶解したものとを、８０〜８５℃に保ちながら、別々に２時間かけて滴下し、その後さらに８０℃に保ちながら１時間撹拌を続け、室温に戻した。この混合液をアセトンにて再沈殿精製し、乾燥して合成ポリマー（６）を得た。得られた合成ポリマー（６）のＧＰＣ測定の結果、重量平均分子量は１１．４万（ポリエチレングリコール換算）であった。
【００８８】
合成例７：合成ポリマー（７）［ポリエチレングリコール（ＥＯ付加モル数３４）アリルエーテル／マレイン酸＝２０／８０（モル比）共重合体］の合成例
無水マレイン酸１５６．８ｇ、ポリエチレングリコール（ＥＯ付加モル数３４）アリルエーテル３１３．６ｇをイオン交換水４００ｇに溶解した後、槽内温度を７０℃に昇温し、４８％水酸化ナトリウム水溶液６０ｇを加えた。更に槽内を窒素置換後、９８℃まで昇温し、３５％過酸化水素水４２．８ｇ、過硫酸ナトリウム４．７７ｇからなる開始剤水溶液を６時間かけて上記反応槽に滴下し、更に４時間槽内温度を９８℃に保った。この水溶液を凍結乾燥して合成ポリマー（７）を得た。得られた合成ポリマー（７）のＧＰＣ測定の結果、重量平均分子量は１．８万（ポリエチレングリコール換算）であった。
【００８９】
合成例８：合成ポリマー（８）［ポリエチレングリコール（ＥＯ付加モル数１２０）モノメタクリル酸エステル／メタクリル酸＝７０／３０（質量比）共重合体］の合成例
イオン交換水２００ｇを窒素雰囲気下で６０℃に昇温したところに、ポリエチレングリコール（ＥＯ付加モル数１２０）モノメタクリル酸エステル７０ｇ、メタクリル酸３０ｇをイオン交換水１００ｇに溶解したものと、２，２’−アゾビス−（２−メチルプロピオンアミジン）２塩酸塩（Ｖ−５０、和光純薬（株）製）１．６ｇをイオン交換水１００ｇに溶解したものとを、６０〜６５℃に保ちながら、別々に２時間かけて滴下し、その後６５℃に保ちながらさらに６時間撹拌を続けた。これを室温に戻した後、氷冷しながら６Ｎ水酸化ナトリウム水溶液４６．５ｍＬを徐々に加えて中和し、このポリマーのカルボキシル基の約８０％をナトリウム塩とした。この水溶液を凍結乾燥し、合成ポリマー（８）を得た。得られた合成ポリマー（８）のＧＰＣ測定の結果、重量平均分子量は１２．７万（ポリエチレングリコール換算）であった。
【００９０】
合成例９：合成ポリマー（９）［ポリエチレングリコール（ＥＯ付加モル数２３）モノメタクリル酸エステル／リン酸エチルメタクリレート／メタクリル酸＝５０／２５／２５（質量比）共重合体］の合成例
エタノール３００ｇを窒素雰囲気下で８０℃に昇温したところに、ポリエチレングリコール（ＥＯ付加モル数２３）モノメタクリル酸エステル１００ｇ、リン酸エチルメタクリレート（ユニケミカル社製、Ｐｈｏｓｍｅｒ Ｍ）５０ｇ、メタクリル酸５０ｇをエタノール１５０ｇに溶解したものと、２，２’−アゾビス−(２，４−ジメチルバレロニトリル)（Ｖ−６５、和光純薬（株）製）５．８ｇをエタノール３００ｇに溶解したものとを、８０℃に保ちながら、別々に２時間かけて滴下し、その後８０℃に保ちながら更に１時間撹拌を続けた。これを室温に戻したのち、ヘキサンで再沈殿精製し、合成ポリマー（９）を得た。得られた合成ポリマー（９）のＧＰＣ測定の結果、重量平均分子量は３．１万（ポリエチレングリコール換算）であった。
【００９１】
実施例１
第一工程：表１の非イオン性界面活性剤（１）６０ｇ、水溶性有機溶剤（１）３０ｇ、水溶性有機溶剤（２）１０ｇ、イオン交換水１２ｇの混合液を５０℃に加熱し、これに５時間かけて合成ポリマー（２）４ｇを溶解し、液体分散媒を得た。
【００９２】
第二工程：ゼオライト（１）３０ｇ、炭酸ナトリウム１０ｇを、第一工程で得られた液体分散媒６０ｇに懸濁し、直径０．８ｍｍのジルコニアビーズ８００ｇを充填した容量１Ｌのバッチ式サンドミル（アイメックス社製）を用いて、ディスク回転数１５００ｒ／ｍｉｎで１時間の湿式粉砕を行った。その後、４０メッシュのふるいを通してメディアを除去して液体洗浄剤組成物を得た。この液体洗浄剤組成物を一部採取して、エタノールで希釈し、粒径を粒度分布測定装置（堀場製作所製、ＬＡ−９１０、相対屈折率：１．２）により測定したところ、平均粒径は０．８μｍであった。
【００９３】
第三工程：第二工程で得られた分散液に、香料を微量添加して室温で充分に撹拌して溶解させ、液体洗浄剤組成物を得た。
【００９４】
実施例２〜９及び比較例１〜４
表１に示す成分を用い、実施例１と同様の方法により、第一、第二、更に第三工程により、各種液体洗浄剤組成物を製造した。一部の例において、第三工程は、後述の実施例１０と同様に行った。なお、合成ポリマー（１）、（３）は、本発明の範囲外のものであるが、便宜的に、これらを用いた例を実施例として示したものである。
【００９５】
実施例１０
第一工程：表１の非イオン性界面活性剤（１）３０ｇ、非イオン性界面活性剤（２）３０ｇ、水溶性有機溶剤（１）２５ｇ、水溶性有機溶剤（２）１０ｇ、イオン交換水１１ｇ、合成ポリマー（８）４ｇを混合し、液体分散媒を得た。
【００９６】
第二工程：ゼオライト（２）２５ｇ、結晶性ケイ酸塩化合物１５ｇを、第一工程で得られた液体分散媒５５ｇに懸濁し、直径０．８ｍｍのジルコニアビーズ８００ｇを充填した容量１Ｌのバッチ式サンドミル（アイメックス社製）を用いて、ディスク回転数１５００ｒ／ｍｉｎで７時間の湿式粉砕を行った。その後、４０メッシュのふるいを通してメディアを除去して分散液を得た。この分散液を一部採取して、エタノールで希釈し、粒径を粒度分布測定装置（堀場製作所製、ＬＡ−９１０、相対屈折率：１．２、温度２０℃）により測定したところ、平均粒径は０．９μｍであった。
【００９７】
第三工程：第二工程で得られた分散液に、式(１１)
【００９８】
【化４】

【００９９】
で表される漂白活性化剤２．０ｇ、香料を微量添加して室温で充分に撹拌して溶解させた。さらに過炭酸ナトリウム２．０ｇ、酵素（１）０．５ｇ、酵素（２）０．５ｇを添加して室温で充分に撹拌してこれを分散させ、液体洗浄剤組成物を得た。
【０１００】
実施例１〜１０及び比較例１〜４で得られた液体洗浄剤組成物の体積分離率及び粘度を下記方法で測定し、洗浄試験を行った。結果を表１に示す。
【０１０１】
（１）体積分離率
目盛り付きガラス製沈降管に、深さ３０ｃｍとなるように液体洗浄剤組成物を満たして密栓し、各サンプルを２５℃の室内で１ヶ月間静置保存した。保存終了後のサンプルの透明液相と固体分散相の境界線を目視で判断し、相分離して上層部に生じた透明液体相の厚みｘ（ｃｍ）を測定した。体積分離率ｙ（％）を、次式（Ｖ）により求めた。
ｙ＝（ｘ／３０）×１００ （Ｖ）
【０１０２】
（２）粘度
２００ｍＬビーカーに液体洗浄剤組成物２００ｇを満たし、東京計器（株）製Ｂ型粘度計により、Ｎｏ．２（又は３）のローターを粘度に応じて６〜６０ｒ／ｍｉｎの速度条件（２５℃）において測定した。
【０１０３】
（３）洗浄試験
カーボンブラック１５質量％、綿実油６０質量％、コレステロール５質量％、オレイン酸５質量％、パルミチン酸５質量％、流動パラフィン１０質量％の混合物１００ｇを、８Ｌのパークレンに溶解分散し、１０ｃｍ×１０ｃｍに裁断した木綿の白布（金巾２００３布）を浸漬して汚れを付着させた後、パークレンを乾燥除去することにより、皮脂／カーボン汚れ汚染布（人工汚染布）を調製した。
【０１０４】
上記皮脂／カーボン汚れ汚染布を５枚１組とし、評価用洗剤水溶液１Ｌにこれを入れ、ターゴトメーターにて以下の条件で洗浄試験を行った。
洗浄時間：１０分
洗浄剤組成物：０．８ｇ／評価用洗剤水溶液１Ｌ
水の硬度：７１．２ｍｇＣaＣＯ₃／Ｌ
水の温度：２０℃
ターゴトメーター回転数：１００ｒ／ｍｉｎ
すすぎ：２０℃水道水にて５分間流水すすぎ。
【０１０５】
洗浄力は、汚染前の原布及び洗浄前後の汚染布の５５０ｎｍにおける反射率を自記色彩計（島津製作所製）を用いて測定し、次式によって洗浄率（％）を求めた。
洗浄率（％）＝｛（洗浄後の反射率−洗浄前の反射率）／（原布の反射率−洗浄前の反射率）｝×１００
【０１０６】
【表１】

【０１０７】
＊ 非イオン性界面活性剤（１）：エマルゲン１０８(花王（株）製）
＊ 非イオン性界面活性剤（２）：エマルゲンＬＳ−１０６(花王（株）製）
＊ 水溶性有機溶剤（１）：ポリオキシエチレンフェニルエーテル（日本乳化剤（株）製、ＰＨＧ−３０）
＊ 水溶性有機溶剤（２）：プロピレングリコール
＊ アニオン性界面活性剤：アルキルの炭素数１０〜１４の直鎖アルキルベンゼンスルホン酸ナトリウム
＊ 合成ポリマー（１）：合成例１で合成したポリマー
＊ 合成ポリマー（２）：合成例２で合成したポリマー
＊ 合成ポリマー（３）：合成例３で合成したポリマー
＊ 合成ポリマー（４）溶液：合成例４で合成したポリマー溶液（濃度：１１．８％）
＊ 合成ポリマー（５）：合成例５で合成したポリマー
＊ 合成ポリマー（６）：合成例６で合成したポリマー
＊ 合成ポリマー（７）：合成例７で合成したポリマー
＊ 合成ポリマー（８）：合成例８で合成したポリマー
＊ 合成ポリマー（９）：合成例９で合成したポリマー
＊ ポリマー（１）：ポリエチレングリコール（ポリエチレングリコール２，０００、和光純薬（株）製）
＊ ポリマー（２）：ポリメタクリル酸ナトリウム（重量平均分子量；９，５００、Ａｌｄｒｉｃｈ社製）
＊ 過炭酸ナトリウム：平均粒径１６μｍ、第一工程で製造した液体中に分散して堀場製作所製、ＬＡ−９１０にて測定、相対屈折率：１．２
＊ 漂白活性化剤：前記式（１１）で表される漂白活性化剤
＊ 結晶性ケイ酸塩化合物：特開平５−１８４９４６号公報の実施例１に記載の結晶性ケイ酸塩化合物
＊ ゼオライト（１）：トヨビルダー（東洋曹達（株）製）
＊ ゼオライト（２）：トヨビルダー（東洋曹達（株）製）を４５０℃で１時間焼成して、脱水したもの
＊ 酵素（１）：エバラーゼ１６．０Ｌ−ＥＸ（プロテアーゼ、ノボノルディスクバイオインダストリー社製）
＊ 酵素（２）：リポラーゼ１００Ｌ（リパーゼ、ノボノルディスクバイオインダストリー社製）
【０１０８】
表１より、本発明の液体洗浄剤組成物は、（ｂ）成分を用いることによって、（ａ）成分を含む固体分散質混合物を安定に分散して、１ヶ月後の体積分離率を５％以下とすることができ、かつ優れた洗浄力を有することがわかった。
【０１０９】
実施例１１
第一工程：合成ポリマー（５）２ｇを１００ｇのエタノールに溶解し、ゼオライト（１）３０ｇと炭酸ナトリウム１０ｇを添加して３時間撹拌し、分散液を得た。得られた分散液を６０℃に昇温した後、減圧乾燥し、完全にエタノールを留去して、ポリマー被覆無機粉体を得た。
【０１１０】
第二工程：非イオン性界面活性剤（１）６０ｇ、水溶性有機溶剤（１）３０ｇ、水溶性有機溶剤（２）１０ｇ、イオン交換水１２ｇを混合し、液体分散媒を得た。
【０１１１】
第三工程：第二工程で得られた液体分散媒６０ｇに第一工程で得られたポリマー被覆無機粉体４２ｇを懸濁し、直径０．８ｍｍのジルコニアビーズ８００ｇを充填した容量１Ｌのバッチ式サンドミル（アイメックス社製）を用いて、ディスク回転数１５００ｒ／ｍｉｎで１時間の湿式粉砕を行った。その後、４０メッシュのふるいを通してメディアを除去して液体洗浄剤組成物を得た。
【０１１２】
この液体洗浄剤組成物を一部採取して、エタノールで希釈し、粒径を粒度分布測定装置（堀場製作所製、ＬＡ−９１０、相対屈折率：１．２、温度２０℃）により測定したところ、平均粒径は０．６μｍであった。また、得られた液体洗浄剤組成物は、粘度（２５℃）が３２０ｍＰａ・ｓと低く、高洗浄力を示し、分散安定性の高いものであった。
【０１１３】
【発明の効果】
本発明の液体洗浄剤組成物は、界面活性剤等を含有する液体分散媒中に、（ａ）成分を含む微細な無機粒子が、製品粘度を高めることなく、（ｂ）成分により安定に分散しており、容易に洗濯槽に注入され、迅速に洗浄用水に溶解される。その結果、洗浄力も向上する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid detergent composition useful in a wide range of fields such as laundry detergents for textiles, kitchen detergents, residential detergents, various hard surface cleaning detergents, liquid cleansers and the like.
[0002]
[Prior art and problems to be solved by the invention]
Liquid detergents are generally more soluble in water than powder detergents and have the advantage of being able to be applied directly to soiled parts. In addition, there is no drying process during production, and heat that cannot be added to powder detergents. It is advantageous in that an unstable substance can be blended with the product, and complicated production equipment such as drying equipment is not required.
[0003]
It is desired to mix alkaline agents, calcium scavengers, bleaching agents, enzymes, abrasives, etc., which have cleaning assisting effects, in liquid detergents, and these are usually used as solids in liquid detergents. It is an existing component. However, particularly in the case of liquid detergents containing solid components, the solid components are not easily redispersed due to precipitation and separation during storage, or the product viscosity is too high to be easily injected into the washing tub. Is likely to occur. In order to suppress sedimentation of the solid component, methods such as increasing the viscosity of the liquid component or reducing the particle size of the solid have been conventionally used, but there is a limit to increasing the viscosity due to problems during injection. Stable dispersion could not be realized only by reducing the solid particle size.
[0004]
For the purpose of stabilizing the dispersion of solid components, JP-B-60-39319 discloses a copolymer of maleic anhydride hydrolyzed with at least 30% and ethylene or vinyl methyl ether, and JP-A-3-86800 discloses amphiphilicity. A carboxy-containing polymer, a copolymer having a monomer containing a group capable of extending from the solid surface and a monomer containing a group capable of associating with the solid phase is disclosed in Japanese Patent Application Laid-Open No. 5-140599. A liquid detergent composition is disclosed that uses a polymer having an association group and a soluble monomer in the liquid phase. However, in these compositions, since the solid component is stabilized by the network structure formed by the polymer, the viscosity becomes high and it is difficult to handle. It is difficult to reduce the viscosity of this system without impairing the dispersion stability of the solid component. That is, even if a solvent or the like can be added to reduce the viscosity, the dispersion stability of the solid component is lowered, and the composition is often unsuitable as a cleaning agent.
[0005]
An object of the present invention is to provide a liquid detergent composition having excellent detergency, low viscosity that is easy to handle, and good dispersion stability.
[0006]
[Means for Solving the Problems]
The present invention is a liquid detergent composition comprising a liquid dispersion medium and a solid dispersoid dispersed in the liquid dispersion medium, wherein at least a part of the solid dispersoid is 30% by mass or more in the composition. One or more inorganic builder particles selected from aluminosilicate compounds, crystalline silicate compounds and carbonates (a) [hereinafter referred to as component (a)], and the liquid dispersion medium and / or solid dispersoid is A block-type or graft-type polymer (b) having a carboxyl group or a salt thereof (a) and a polymer chain (b) having an alkyleneoxy group as a structural unit (hereinafter referred to as component (b)), and a viscosity ( (25 ° C.) provides a liquid detergent composition having a viscosity of 3000 mPa · s or less and a volume separation rate (25 ° C., standing for 30 days) of 5% or less.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
[(A) component]
In the liquid detergent composition of the present invention, the total proportion of the component (a) is preferably 30 to 69% by mass, and more preferably 30 to 50% by mass.
[0008]
Among the components (a), the aluminosilicate compound is preferably at least one aluminosilicate compound represented by the general formula (1).
(M¹ _pM² _qM^Three _rO)_u・ (M^Four _sM^Five _tO)_v・ (Al₂O_Three)_w・ (SiO₂(1)
[Where M¹, M², M^ThreeEach represents Na, K or H, and M^FourAnd M^FiveRepresents Ca or Mg, respectively. p, q and r are each a number of 0 to 2 (where p + q + r = 2), s and t are each a number of 0 to 1 (where s + t = 1), u is 0 to 1, preferably 0.1 to 0. The number of 5, v is 0 to 1, preferably 0 to 0.1, and w is 0 to 0.6, preferably 0.1 to 0.5. ].
[0009]
Examples of such aluminosilicate compounds include types A, X, and P of various zeolites that are generally blended in detergents, and type A is particularly preferred. Zeolite is a very excellent detergent builder because it has a high cation exchange capacity, and blending it is preferable because the cleaning power of the detergent composition is greatly enhanced. An example of such a zeolite is Toyo Builder commercially available from Toyo Soda Co., Ltd. In addition, it is also preferable to use a fine particle zeolite produced by the method of JP-A No. 2001-139322 because it can be easily pulverized in the production process of the cleaning composition of the present invention described later and thereby improve the dispersion stability. . Generally, commercially available zeolite contains about 20% of water. When this moisture exceeds the amount of moisture desired to be contained in the composition, it is preferable to use such commercially available zeolite after calcining at 450 to 600 ° C. to remove the moisture.
[0010]
Moreover, among (a) component, as a crystalline silicate compound, 1 or more types of the crystalline silicate compound represented by General formula (2) are preferable.
(M¹ _pM² _qM^Three _rO) ・ (M^Four _sM^Five _tO)_x・ (SiO₂)_y      (2)
[Where M¹, M², M^Three, M^Four, M^Five, P, q, r, s, and t are the same as those in the general formula (1). x represents a number from 0 to 1, and y represents a number from 0.9 to 3.5. ].
[0011]
Specific examples of the crystalline silicate compound include layered sodium silicate such as SKS-6 (manufactured by Hoechst), Japanese Patent No. 2525318, Japanese Patent No. 2759243, Japanese Patent No. 2618799, and Japanese Patent No. 2525342. What is described in the claim of the gazette and Unexamined-Japanese-Patent No. 5-184946 is mentioned.
[0012]
The carbonate of component (a) is preferably an alkali metal salt (Na, K, etc.), and more preferably a sodium salt. Examples of sodium carbonate (soda ash) include commonly available dense ash and light ash.
[0013]
The average particle size of the component (a) is preferably 10 μm or less, preferably 0.01 to 5 μm, more preferably 0.05 to 2 μm, particularly preferably 0.1 to 1.0 μm, most preferably 0. 1 to 0.7 μm. Here, the average particle diameter is an average of volume-based particle diameters measured with a laser diffraction / scattering particle size distribution measuring apparatus LA-910 (relative refractive index: 1.2, temperature: 20 ° C. in ethanol) manufactured by HORIBA, Ltd. This is the particle size and means this unless otherwise noted.
[0014]
The component (a) exemplified above is used singly or as a mixture of plural kinds. In the component (a), the aluminosilicate compound and / or the crystalline silicate compound is preferably 50 to 100% by mass, and more preferably 70 to 100% by mass. In particular, in the present invention, it is preferable to contain an aluminosilicate compound as the component (a), and it is preferable to further contain this and a carbonate, particularly sodium carbonate.
[0015]
[Component (b)]
In the liquid detergent composition of the present invention, the ratio of the component (b) is obtained in order to obtain good dispersibility, in particular, to achieve a volume separation ratio of 5% or less, and to prevent an excessive increase in viscosity. 0.1-10 mass% is preferable, 0.3-7 mass% is still more preferable, 0.5-5 mass% is especially preferable.
[0016]
The component (b) is preferably soluble or homogeneously dispersible in the liquid dispersion medium used in the composition in which it is blended, which is obtained by placing 5 g of the polymer in a 300 mL beaker, (B) Pour 95 g of the liquid dispersion medium used in the composition in which the component is blended, and use Teflon (registered trademark) coated magnet (length 3 cm) at 150 r / min at 20 to 80 ° C. (depending on the component, It can be confirmed by the fact that no precipitate is visually observed at the bottom of the beaker when the mixture is heated to 50 ° C. and stirred for 5 hours, and then allowed to stand for 30 minutes (room temperature, 25 ° C.).
[0017]
Further, the component (b) has the stable dispersibility of the component (a). Stable dispersibility indicates that the volume separation rate after storage of the liquid detergent composition of the present invention at room temperature (25 ° C.) for 1 month is 5% or less. The volume separation rate is the ratio of the volume of the transparent liquid phase portion generated at the top of the solid dispersoid by sedimentation to the total volume of the composition. Specifically, it is measured by the method described later.
[0018]
This component (b) has a carboxyl group or a salt thereof (a) as a site considered to be adsorbed to the component (a), and a polymer chain having an alkyleneoxy group as a structural unit as a site considered to be dissolved in the liquid dispersion medium. It is a block-type or graft-type polymer having (b), and may have any structure as long as it has stable dispersion of the component (a), but is preferably a graft-type polymer, more preferably Is a polymer having no hydrocarbon group having 4 or more carbon atoms in order to suppress structural viscosity.
[0019]
In the component (b), the mass ratio of the polymer chain having a carboxyl group or a salt thereof (I) and the polymer chain (B) having an alkyleneoxy group as a structural unit is (I) / (B) = 5/95 to 95. / 5 is preferable, and 5/95 to 60/40 is more preferable from the viewpoint of solubility in the liquid dispersion medium. Within this range, the component (b) is considered to maintain a balance between the structure (b) responsible for adsorption to the dispersoid and the structure (b) dissolved in the liquid part and responsible for the steric repulsion effect. Indicates.
[0020]
The liquid detergent composition of the present invention contains the component (a) at a high ratio of 30% by mass or more in order to have a high detergency, and for the dispersion stabilization of the liquid detergent composition (b The component is required to have high dispersion performance.
[0021]
In the polymer chain (b), the alkyleneoxy group is preferably an ethyleneoxy group and / or a propyleneoxy group, and the ethyleneoxy group and the propyleneoxy group may each be a homopolymer, a block, or a random copolymer. The average degree of polymerization of the polymer chain (b) is preferably 3 to 200, more preferably 6 to 150, and particularly preferably 8 to 50 from the dispersion stability of the component (a). The terminal of the alkyleneoxy group is not limited, and may have a hydrogen atom or may have a hydrocarbon group, for example, an ether bond such as a methoxy group or an ethoxy group. The hydrocarbon group is preferably an alkyl group having 1 to 3 carbon atoms.
[0022]
For the site having a carboxyl group or a salt thereof, a (co) polymer of a vinyl monomer having a carboxyl group or a salt thereof (the (co) polymer refers to a single polymer or a copolymer) is preferable. The vinyl monomer having a carboxyl group or a salt thereof is (meth) acrylic acid [(meth) acrylic acid is acrylic acid, methacrylic acid or a mixture thereof] and salts thereof, styrene carboxylic acid and salts thereof, malee Acidic monomers [maleic anhydride, maleic acid, maleic acid monoester, maleic acid monoamide or a mixture thereof] and salts thereof, itaconic acid and salts thereof, and the like, and one or more selected from these can be used . Examples of the salts include metals, ammonium, alkyl or alkenyl ammonium having 1 to 22 carbon atoms, alkyl or alkenyl substituted pyridinium having 1 to 22 carbon atoms, alkanol ammonium having 1 to 22 carbon atoms, or basic amino acid. Alkali metal salts such as sodium and potassium are preferred.
[0023]
The method for synthesizing the block type or graft type polymer is not particularly limited, and a known method can be selected. The component (b) is preferably obtained by polymerizing monomers using one or more liquids constituting the liquid dispersion medium as a solvent. Among them, a method of polymerizing vinyl monomers using a macroazo initiator having an azo group in a polymer chain (macroazo initiator method) using one or more liquids constituting a liquid dispersion medium as a solvent, A method using a compound having a polymerizable group at one end (macromonomer method), radical polymerization of a monomer in the presence of a polymer, and a newly generated polymer chain linked to a polymer chain previously coexisted by a chain transfer reaction And a method of grafting by reacting another polymer terminal with a functional group in the polymer chain.
[0024]
(B) component obtained by these methods includes the following 1 to 5 in order of preference. In addition, vinyl monomers having hydrophilic groups such as sulfonic acid groups, hydroxyl groups, ester groups, amide groups, and phosphoric acid groups can be copolymerized with the following polymers.
1. Copolymer of ester (preferably monoester) of polyalkylene glycol and vinyl monomer having carboxyl group or salt thereof and vinyl monomer having carboxyl group or salt thereof
More preferable is a copolymer of a polyalkylene glycol (meth) acrylic acid ester and a vinyl monomer having a carboxyl group or a salt thereof, and a copolymer of a polyalkylene glycol (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof. Coalescence is particularly preferred. For example, a copolymer of polyethylene glycol mono (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof, poly (ethylene glycol / propylene glycol) mono (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof And a copolymer thereof.
2. Copolymer of polyalkylene glycol ether having reactive unsaturated group and vinyl monomer having carboxyl group or salt thereof
A copolymer of a polyalkylene glycol ether having a reactive unsaturated group and (meth) acrylic acid or a salt thereof and / or a maleic monomer is preferred. Examples thereof include a copolymer of polyethylene glycol allyl ether and maleic acid (or a salt thereof).
3. Copolymer obtained by grafting a monomer having a carboxyl group or a salt thereof onto polyalkylene glycol
For example, a graft polymer obtained by radical polymerization of acrylic acid and maleic acid or a salt thereof in polyethylene glycol, polypropylene glycol or poly (ethylene glycol / propylene glycol) is preferred.
4). Vinyl monomer having carboxyl group or salt thereof using polyethylene glycol macroazo initiator
A block polymer obtained by radical polymerization of (meth) acrylic acid or a salt thereof is preferable.
5. Graft polymer obtained by linking a polymer of a vinyl monomer having a carboxyl group or a salt thereof and a polyalkylene glycol having a hydroxyl group at the terminal by a dehydration reaction
Preferably, a graft polymer obtained by linking poly (meth) acrylic acid or a salt thereof and polyethylene glycol having a hydroxyl group at a terminal by a dehydration reaction can be used.
[0025]
2. In the polyalkylene glycol ether having a reactive unsaturated group, the reactive unsaturated group is preferably an unsaturated group capable of radical polymerization. The polyalkylene glycol ether having a reactive unsaturated group is preferably represented by the following general formula (3).
[0026]
[Chemical 1]

[0027]
[In the formula, R₁, R₂, R_ThreeAre the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. R_FourRepresents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, an alkylaryl group having 7 to 22 carbon atoms or an arylalkyl group. n AO's are the same or different and each represents an alkyleneoxy group. n shows the number of 3-200. p represents 0 or 1. X is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or the following general formula (4).
[0028]
[Chemical formula 2]

[0029]
The bivalent group represented by these is shown. (Wherein R_FiveRepresents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, an alkylaryl group having 7 to 22 carbon atoms or an arylalkyl group. m AO's are the same or different and each represents an alkyleneoxy group. q shows the number of 1-10. m shows the number of 0-200. )]
[0030]
In general formula (3), R₁, R₂, R_ThreeAre the same or different and are preferably a hydrogen atom or a methyl group.
[0031]
R in general formula (3)_FourAnd R in the general formula (4)_FiveAre the same or different and are preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl group and the like.
[0032]
X in the general formula (3) is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and examples thereof include methylene, ethylene, propylene, and trimethylene groups. preferable.
[0033]
AO in the general formulas (3) and (4) are the same or different and are preferably an alkyleneoxy group having 2 to 4 carbon atoms, and may be a block, random, or alternating polymer. m and n are the same or different and are preferably 3 to 100, more preferably 3 to 50. m + n is preferably 3 to 200, more preferably 6 to 100. When AO is a homopolymer of a oxyethylene group having 2 carbon atoms, the aforementioned R_Four, R_FiveAre the same or different and are preferably other than a hydrogen atom. In particular, (AO) in general formulas (3) and (4)_n, (AO)_mAre the same or different and are preferably a block polymer or a random polymer represented by the following general formula (5), particularly a block polymer. In the case of a block polymer, a reactive unsaturated group R₁R₂C = C (R_ThreeIt is preferable that an ethyleneoxy group is bonded at a position closer to the above.
[0034]
-[(C₂H_FourO)_r/ (C_ThreeH₆O)_s]-(5)
(In the formula, r represents 3-130, and s represents a number of 1-50.)
Here, r in the general formula (5) is preferably 3 to 50, and s is preferably 1 to 30.
[0035]
P of general formula (3) is preferably 1, and q of general formula (4) is preferably 1 to 5, and more preferably 1.
[0036]
For example, when p = 0, the compound represented by the general formula (3) can be obtained by addition polymerization of alkylene oxide to allyl alcohol under alkaline conditions. In the case of p = 1, for example, it can be obtained by adding glycidol to allyl alcohol and then subjecting alkylene oxide to addition polymerization under alkaline conditions. R_Four, R_FiveWhen is a group other than a hydrogen atom, a compound having an ether bond can be synthesized by a so-called Williamson reaction in which an alkylating agent is reacted in the presence of an amine.
[0037]
The weight average molecular weight of the component (b) is preferably 1,000,000 or less, more preferably 1,000 to 500,000, particularly preferably 5,000 to 300,000 for the purpose of preventing an excessive increase in viscosity. This weight average molecular weight was calculated | required by the measuring method mentioned later.
[0038]
In the liquid detergent composition of the present invention, the mass ratio of the component (a) to the component (b) is (b) / (a) = 1/80 to 1/4 from the dispersion stability of the component (a). 1/60 to 1/5 is more preferable, and 1/40 to 1/8 is particularly preferable.
[0039]
[Liquid dispersion medium]
In the liquid detergent composition of the present invention, the ratio of the liquid dispersion medium is preferably 30 to 69% by mass, and more preferably 40 to 69% by mass. Approximately, the ratio of the liquid dispersion medium can be regarded as the ratio of the total amount of the nonionic surfactant, the hydroxyl group-containing water-soluble organic solvent, and water in the liquid detergent composition. The amount of the liquid dispersion medium can be usually determined by precipitating a solid content by centrifugation and optionally filtering.
[0040]
The liquid dispersion medium is composed of a liquid and components dissolved in the liquid, preferably contains a surfactant as an essential component, and contains water and a water-soluble organic solvent. Although this liquid dispersion medium may contain water, the ratio of water in the liquid dispersion medium is preferably 40% by mass or less, more preferably 3 to 20 in order to make the cleaning composition compact. % By mass, particularly preferably 3 to 15% by mass, most preferably 3 to 12% by mass. The lower limit is preferably 0.1% by mass or more and more preferably 1% by mass or more from the viewpoint of ease of production.
[0041]
In the liquid dispersion medium, the ratio of the surfactant is preferably 10 to 90% by mass, more preferably 30 to 80% by mass, and particularly preferably 50 to 70% by mass. The ratio of the total surfactant (including those insoluble in the liquid dispersion medium described later) in the liquid detergent composition is preferably 3 to 65% by mass, more preferably 15 to 60% by mass, and particularly 20 to 50% by mass. % Is preferred. As the surfactant, a nonionic surfactant is preferable, and an anionic surfactant, a cationic surfactant, and a zwitterionic surfactant are liquid together with the nonionic surfactant as long as they do not inhibit the stability of the product. It can be used by dissolving in a dispersion medium.
[0042]
In the liquid detergent of the present invention, the mass ratio between the total surfactant and the component (b) is (b) component / total surfactant = 1/80 to 1/4. 1 is preferable, 1/60 to 1 / 4.5 is more preferable, and 1/30 to 1/5 is particularly preferable.
[0043]
In the present invention, components that can constitute the liquid dispersion medium are shown below.
[0044]
(1) Nonionic surfactant
Mixing and using a nonionic surfactant in a detergent composition has been conventionally performed, and is suitable in terms of excellent detergency and stability. The ratio of the nonionic surfactant in the total surfactant is preferably 70 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably 100% by mass.
[0045]
As the nonionic surfactant, for example, a known nonionic surfactant described in “Patents of Chapter 3 of Known and Conventional Techniques (Powder Detergent for Clothing)” of the Japan Patent Office can be used.
[0046]
In the liquid detergent composition of the present invention, it is particularly preferable to use a nonionic surfactant of the polyethylene oxide and / or polypropylene oxide type, and in particular, a linear or branched first chain having 8 to 18 carbon atoms. A polyoxyethylene alkyl ether obtained by adding 5 to 20 moles of ethylene oxide (hereinafter referred to as EO) on average to a secondary or secondary alcohol, and 5 to 15 moles of EO and propylene oxide (hereinafter referred to as PO) on the alcohol. ) Is added from 1 to 5 moles on average (provided that EO and PO may be added randomly or in blocks). It is preferable to use the above.
[0047]
Other nonionic surfactants include polyoxyethylene alkylphenyl ethers, N-polyoxyethylene alkylamines, sucrose fatty acid esters, fatty acid glycerin monoesters, higher fatty acid alkanolamides, polyoxyethylene higher fatty acid alkanolamides , Amine oxides, alkyl glycosides, alkyl glyceryl ethers, N-alkyl gluconamides and the like can also be used.
[0048]
(2) Anionic surfactant
In the liquid detergent composition of the present invention, for example, a known anionic surfactant described in “Patents of Chapter 3 of the well-known / conventional technique collection (powder detergent for clothing)” of the Japan Patent Office can be used. . In particular, a sulfonate type, sulfate type, phosphate type and / or carboxylate type anionic surfactant is preferably blended.
[0049]
Specifically, an alkyl or alkenyl benzene sulfonate, alkyl or alkenyl sulfate ester salt, polyoxyethylene alkyl or alkenyl ether sulfate ester having a linear or branched alkyl or alkenyl group having an average carbon number of 8 to 22 One or more anionic surfactants selected from salts (average EO addition mole number of 0.5 to 6 mol), monoalkyl or alkenyl phosphates and fatty acid salts are preferred.
[0050]
Examples of counterions of these anionic surfactants include cations obtained by protonating amines such as sodium, potassium, magnesium, calcium, and ethanolamines, quaternary ammonium salts, and mixtures thereof. When an anionic surfactant is blended, a method of blending in an acid form and adding an alkali (such as ethanolamine) separately may be used.
[0051]
(3) Cationic surfactant
For the liquid detergent composition of the present invention, for example, a known cationic surfactant described in the “Patents of Chapter 3 of the well-known / conventional technique collection (powder detergent for clothing)” of the Japan Patent Office can be used. For example, a quaternary ammonium salt such as benzalkonium type is suitably blended.
[0052]
(4) Zwitterionic surfactant
For the liquid detergent composition of the present invention, for example, a known zwitterionic surfactant described in “Patents of Chapter 3 of Known and Conventional Techniques (Powder Detergent for Clothing)” of the Japan Patent Office can be used. For example, an alkylbetaine type zwitterionic surfactant is suitably blended.
[0053]
(5) Hydroxyl-containing water-soluble organic solvent
The hydroxyl group-containing water-soluble organic solvent is blended in the liquid detergent composition of the present invention for the purpose of adjusting the viscosity of the product, preventing gelation of the nonionic surfactant, and adjusting the solubility in washing water. Furthermore, when manufacturing (b) component, it can be used as a part of polymerization solvent and can also play the role which adjusts the molecular weight of (b) component.
[0054]
Although a hydroxyl-containing water-soluble organic solvent is not specifically limited, What is represented by General formula (6) and / or (7) and / or (8) and / or (9) is preferable.
HO [CH₂CH₂O]_a[CH_2-b(CH_Three)_bCH_2-c(CH_Three)_cO]_dH (6)
HO [CH₂CH₂O]_a[CH_2-b(CH_Three)_bCH_2-c(CH_Three)_cO]_d-Ph (7)
CH_3-e(OH)_eCH_2-f(OH)_fCH_3-g(OH)_g                    (8)
CH_3-h(OH)_hCH_2-i(OH)_iCH_2-j(OH)_jCH_3-k(OH)_k       (9)
(In the formula, a represents an average value of 1 to 120, and d represents an average value of 0 to 30. However, a> d. B, c, e, f, g, h, i, j, k represents an integer of 0 or 1, respectively, provided that b + c = 1, e + f + g = 2 or 3, and h + i + j + k = 2. Ph is a phenyl group.)
[0055]
In the liquid dispersion medium, the ratio of the hydroxyl group-containing water-soluble organic solvent is preferably 7 to 60% by mass, more preferably 7 to 50% by mass, and particularly preferably 15 to 40% by mass. In the total liquid detergent composition, 2.1 to 41.4% by mass is preferable, 2.8 to 34.5% by mass is more preferable, and 6 to 27.6% by mass is particularly preferable.
[0056]
Specifically, polyhydric alcohols such as butanediol, pentanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, mono-, di- or tri-alkyl ethers of polyhydric alcohols, ethylene glycol, propylene glycol , Polyethylene glycol, polypropylene glycol, glycols such as ethylene oxide / propylene oxide copolymer, monoalkyl ethers of glycols, monoaryl ethers, particularly monophenyl ether, and the like. These hydroxyl group-containing water-soluble organic solvents are blended as one kind or a mixture of two or more kinds.
[0057]
(5) Other organic solvents
In addition, alkylamines, aliphatic amines, amides or alkyl esters of aliphatic or aromatic carboxylic acids, lower alkyl esters, ketones, aldehydes, glycerides and the like are blended as organic solvents. In the liquid dispersion medium, the ratio of the other organic solvent is preferably 0 to 50% by mass, more preferably 0 to 20% by mass, and particularly preferably 0 to 10% by mass from the viewpoint of detergency and compacting of the cleaning composition. .
[0058]
(6) Water
Water is blended for the purpose of adjusting the viscosity of the product, preventing gelation of the nonionic surfactant, and adjusting the solubility in washing water. In addition to the amount of water adsorbed on the inorganic builder particles of component (a), the amount of water blended in the liquid detergent composition of the present invention is preferably 1 to 30% by mass in the liquid detergent composition. 1 to 15% by mass is more preferable, and 2 to 12% by mass is particularly preferable.
[0059]
In the liquid detergent composition of the present invention, the mass ratio of the liquid dispersion medium and the component (a) is such that the liquid dispersion medium / (a) component = 1/3 to 3/1 because of the dispersion stability of the component (a). 1/2 to 2/1 is more preferable.
[0060]
[Other ingredients]
The liquid detergent composition of the present invention can contain, as other components, a surfactant insoluble in the liquid dispersion medium, an inorganic builder, an organic builder, a bleaching agent, and a general detergent additive. Two or more of these may be used in combination. These can be dispersed and blended in the present detergent composition in the same manner as the component (a). At that time, the component (a) may be mixed before pulverization and pulverized and dispersed together with the component (a), or the component (a) may be mixed after pulverization. Specific examples of other components are shown below.
[0061]
Other-1: Surfactant insoluble in liquid dispersion medium
The liquid detergent composition of the present invention preferably contains a surfactant in the liquid dispersion medium, but separately from this, a surfactant that is insoluble in the liquid dispersion medium is dispersed and blended as a solid dispersoid. May be.
[0062]
Other-2: Inorganic builder
A detergent builder such as a known silicate or metasilicate can be arbitrarily blended. These are preferably alkali metal salts. For example, phosphates such as tripolyphosphate, pyrophosphate, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or their Salts can also be used.
[0063]
Other-3: Organic Builder
The liquid detergent composition of the present invention can also contain a known organic builder that dissolves and / or does not dissolve in the liquid dispersion medium. Specifically, polycarboxylic acids such as citric acid, succinic acid and malonic acid, amino acids such as aspartic acid and glutamic acid, aminopolyacetic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyacrylic acid, acrylic acid / maleic acid Examples thereof include polymer polyvalent carboxylic acids such as polymers, and these are preferably in the form of salts such as alkali metal salts, ammonium salts, and substituted ammonium salts. The ratio of the organic builder is preferably 0.5 to 15.0% by mass in the liquid detergent composition, more preferably 1.0 to 10.0% by mass, and particularly preferably 2.0 to 7.0% by mass.
[0064]
Other-4: Bleach
The liquid detergent composition of the present invention preferably contains a bleaching agent. As the bleaching agent, an inorganic peroxygen bleaching agent or a combination of an inorganic peroxygen bleaching agent and a bleaching activator can be used.
[0065]
Examples of inorganic peroxygen bleaches include alkali metal perborates, percarbonates, persilicates, and perphosphates, with sodium perborate and sodium percarbonate being particularly preferred. Further, in order to improve the dispersion stability of the product, it is coated with a carboxylic acid polymer and / or a polyvalent carboxylic acid as listed in JP-A No. 11-279593, page 2, column 2, lines 13 to 44. Percarbonate can be used.
[0066]
When an inorganic peroxygen bleach and a bleach activator are used in combination, the bleach activator is usually an organic compound having at least one reactive acyl group that forms a peracid, and used alone as an inorganic peroxygen bleach. Instead, the bleaching action is more effective. The structure of the bleach activator is not particularly limited, but a structure represented by the general formula (10) is preferable.
[0067]
[Chemical Formula 3]

[0068]
[Wherein R⁶Represents a linear or branched alkyl group having 1 to 15 carbon atoms, and X represents COOM or SO_ThreeM represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom. ].
[0069]
The bleach activator represented by the general formula (10) is represented by R in the general formula (10).⁶Is a linear or branched alkyl group having 7 to 11 carbon atoms, and X is COOH or SO_ThreeWhat is Na is preferable. Examples of such bleach activators include sodium lauroyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium octanoyloxybenzenesulfonate, lauroyloxybenzoic acid, decanoyloxybenzoic acid, octanoyloxybenzoic acid and the like. I can list them.
[0070]
Other polymers such as polyethylene glycol and carboxymethyl cellulose used for general cleaning agents, color transfer inhibitors such as polyvinylpyrrolidone, enzymes such as protease, cellulase and lipase, enzyme stabilizers such as calcium chloride, formic acid and boric acid, silicone Antifoaming agents such as butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium bisulfite, and other antioxidants, perfume ingredients, dyes, fluorescent dyes, pigments and the like may be included as necessary.
[0071]
[Production method]
The production of the liquid detergent composition of the present invention includes a step of obtaining a finely divided solid dispersoid slurry by wet-grinding the solid component containing the component (a). In this case, it is preferable to stir and mix all the components into a slurry and wet pulverize, or wet pulverize the mixture of component (a) and a part of other components, and then add the remaining components. More preferably, after the components (a) and (b) are brought into contact with each other, preferably in a solvent, the solvent is distilled off, then mixed with a liquid dispersion medium and wet pulverized. It is a manufacturing method. Solvents include lower alcohol solvents such as ethanol and methanol, or aliphatic hydrocarbons such as hexane, heptane, dodecane, cyclohexane, methylcyclohexane, isooctane, hydrogenated triisobutylene, and aromatic carbons such as benzene, toluene, xylene, and ethylbenzene. Hydrogen etc. are illustrated.
[0072]
Alternatively, it is also preferable that the solid dispersoid is refined in advance by dry pulverization or the like, mixed with a liquid dispersion medium, and then stirred or wet pulverized for production. In the case of using a solid dispersoid having a sufficiently small particle size by dry pulverization or the like, a liquid detergent composition can be easily obtained by using a disperser such as a flow jet mixer.
[0073]
As the wet pulverization method, a stone mill, a colloid mill, a caddy mill, a slasher mill, a high speed disperser, a media mill, a roll mill, a kneader, an extruder, and a pulverizer having a liquid jet interaction chamber (for example, a micro fly dic made by Microfly Dix) Fly dizers), ultrasonic dispersers, and the like. Among them, wet pulverization using media, for example, a method using a sand mill, a sand grinder, a wet vibration mill, an attritor or the like is preferable from the viewpoint of pulverization efficiency. A known material such as titania or zirconia can be used as the medium.
[0074]
In the case of pulverization using a sand mill, a media having a diameter of 0.1 to 1.0 mm is particularly suitable. When the particle size of the solid builder used as a raw material is particularly large, it is possible to effectively pulverize by using a medium having a large diameter, for example, 2 mm in diameter, and then using a medium having a smaller diameter. In some cases, crushing can be performed.
[0075]
In order to increase the pulverization efficiency of the solid dispersoid during wet pulverization, the solid dispersoid mixture / liquid dispersion medium (mass ratio) is preferably 30/70 to 60/40.
[0076]
The wet pulverization time ends when the average particle size sufficient for stable dispersion is reached, but is preferably 3 minutes or more. More preferably, it is 5 minutes or more.
[0077]
During wet pulverization, the liquid dispersion medium can be added in several portions in order to keep the viscosity of the system low and increase the pulverization efficiency.
[0078]
The average particle size of the finely divided solid dispersoid after wet pulverization is preferably 10 μm or less, preferably 0.01 to 5 μm, more preferably 0.05 to 2 μm, particularly preferably 0.1 to 1.0 μm, most preferably. Is 0.1 to 0.7 μm.
[0079]
(Liquid detergent composition)
The component (b) blended in the liquid detergent composition of the present invention acts as a dispersant having sufficient chemical stability of the solid dispersoid in the blend, and together with that, a dispersant for dirt during washing. That is, it acts as a recontamination preventing agent that prevents the dirt peeled off from the object to be cleaned from adhering to the object to be cleaned again. This is because in the liquid detergent composition, the carboxyl group of the component (b) or a salt thereof (a) is adsorbed on the dispersoid, and the polymer chain (B) having an alkyleneoxy group as a structural unit is dissolved in the liquid component. By taking the state, it is considered that the steric effect prevents aggregation and networking of the dispersoid, and maintains a good dispersion state to create a low viscosity. On the other hand, in the washing water, this copolymer is adsorbed to the soil component, and it is considered that the soil component is dispersed in the water by an ionic repulsion effect by making the surface of the soil anionic, thereby preventing recontamination of the object to be cleaned. Since the liquid detergent composition of the present invention can provide a stable dispersion, it can be reduced in viscosity.
[0080]
In order to improve workability, the liquid detergent composition of the present invention is preferably 3000 mPa · s or less, more preferably 2000 mPa · s or less, and particularly preferably 1000 mPa · s or less, Most preferred is 700 mPa · s or less. In order to prevent scattering of the liquid detergent and increase the stability of the inorganic builder particles, the viscosity is preferably 10 mPa · s or more, and more preferably 50 mPa · s or more.
[0081]
【Example】
The molecular weight was measured by gel permeation liquid chromatography (GPC), and the following conditions were used. Both eluents and added salts were prepared from grades for liquid chromatography.
Column: Two pieces of G4000PWXL + G2500PWXL manufactured by Tosoh Corporation
Eluent: 0.2M phosphate buffer (pH 6.9) / acetonitrile = 9/1 (volume ratio),
Detector: differential refractometer,
Temperature: 40 ° C
Standard: Polyethylene glycol, polyethylene oxide,
Measurement concentration: 5 mg / ml,
Injection volume: 100 μl
[0082]
Synthesis example 1: Synthesis example of synthetic polymer (1) [block polymer of polyethylene glycol and polyacrylic acid (40/60 (mass ratio))]
40 g of poly [polyoxyethylene 4,4′-azobis (4-cyanopentanoate)] (VPE-0201, manufactured by Wako Pure Chemical Industries, Ltd.) and 60 g of acrylic acid were dissolved in 300 g of ion-exchanged water, and the atmosphere was nitrogen. The mixture was stirred for 10 minutes and then heated and kept at 65 to 70 ° C. for 6 hours. While cooling this with ice, 110 mL of 6N aqueous sodium hydroxide solution was gradually added to neutralize it, and about 80% of the carboxyl groups of this polymer were converted to sodium salts. This aqueous solution was freeze-dried to obtain a synthetic polymer (1). As a result of GPC measurement of the obtained synthetic polymer (1), the weight average molecular weight was 222,000 (in terms of polyethylene glycol). For the synthetic polymer (1), two columns of TSK GMPWXL (manufactured by Tosoh Corporation) were used, and the other conditions were as described above.
[0083]
Synthesis example 2: Synthesis example of synthetic polymer (2) [polyethylene glycol (EO addition mole number 9) monomethacrylic acid ester / methacrylic acid = 80/20 (mass ratio) copolymer]
When 100 g of ion-exchanged water was heated to 100 ° C. under a nitrogen atmosphere, 80 g, 48 g of polyethylene glycol (EO addition mole number 9) monomethacrylate (NK-ester M-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 g of methacrylic acid neutralized with 7.8 g of% sodium hydroxide, 4.5 g of 2-mercaptoethanol dissolved in 40 g of ion-exchanged water, and 4.6 g of sodium persulfate dissolved in 42 g of ion-exchanged water Were added separately over 2 hours while maintaining the temperature at 100 to 105 ° C., and then the stirring was further continued for 1 hour while maintaining the temperature at 100 ° C. This was returned to room temperature, deodorized with 10.8 g of 35% hydrogen peroxide solution, and excess hydrogen peroxide solution was reduced with 1.9 g of 35% sodium hydrogen sulfite. This aqueous solution was freeze-dried to obtain a synthetic polymer (2). As a result of GPC measurement of the obtained synthetic polymer (2), the weight average molecular weight was 39,000 (in terms of polyethylene glycol).
[0084]
Synthesis example 3: Synthesis example of synthetic polymer (3) [graft polymer of polyethylene glycol and poly (acrylic acid / maleic acid = 70/30 (molar ratio)) (50/50 (mass ratio))]
50 g of polyethylene glycol (polyethylene glycol 2,000, manufactured by Wako Pure Chemical Industries, Ltd.) and 20.4 g of maleic acid were dissolved by heating in a nitrogen atmosphere, and the temperature was raised to 150 ° C. while stirring was continued. While maintaining the temperature at 145 to 150 ° C., 29.6 g of acrylic acid and 4.3 g of di-t-butyl peroxide were separately added dropwise to this solution over 1 hour, and further stirred for 3 hours while maintaining the temperature at 150 ° C. The temperature was returned to room temperature. 200 mL of ion-exchanged water was added for dilution, and the mixture was neutralized by gradually adding 100 mL of 6N aqueous sodium hydroxide while cooling with ice, so that about 80% of the carboxyl groups of the polymer were converted to sodium salts. This aqueous solution was freeze-dried to obtain a synthetic polymer (3). As a result of GPC measurement of the resulting synthetic polymer (3), the weight average molecular weight was 45,000 (in terms of polyethylene glycol).
[0085]
Synthesis example 4: Synthesis example of synthetic polymer (4) [polyethylene glycol (EO addition mole number 23) monomethacrylic acid ester / methacrylic acid = 50/50 (mass ratio) copolymer]
Polyethylene glycol (EO addition mole number 23) monomethacrylic acid ester 50g, methacrylic acid 50g was dissolved in 750g polyethylene glycol (EO addition mole number 3) monophenyl ether (PHG-30, manufactured by Nippon Emulsifier Co., Ltd.), nitrogen atmosphere Stirred under for 10 minutes. To this, 8 g of 2,2′-azobis- (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated in a nitrogen atmosphere and kept at 75-80 ° C. Stirring was continued for 6 hours. Thereafter, the temperature was returned to room temperature to obtain a synthetic polymer (4) solution (polymer (4) concentration: 11.7% by mass). As a result of GPC measurement of the obtained synthetic polymer (4), the weight average molecular weight was 31,000 (in terms of polyethylene glycol).
[0086]
Synthesis example 5: Synthesis example of synthetic polymer (5) [polyethylene glycol (EO addition mole number 9) monomethacrylic acid ester / acrylic acid = 20/80 (mass ratio) copolymer]
When 200 g of ion-exchanged water was heated to 60 ° C. under a nitrogen atmosphere, 20 g of polyethylene glycol (EO addition mole number 9) monomethacrylate (NK-ester M-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.), acrylic 80 g of acid dissolved in 80 g of ion-exchanged water and 1.6 g of 2,2′-azobis- (2-methylpropionamidine) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) What was melt | dissolved in 120g was dripped separately over 2 hours, keeping at 60-65 degreeC, and stirring was further continued for 6 hours, keeping at 65 degreeC after that. After returning this to room temperature, 150 mL of a 6N aqueous sodium hydroxide solution was gradually added to neutralize while cooling with ice, and about 80% of the carboxyl groups of this polymer were converted to sodium salts. This aqueous solution was freeze-dried to obtain a synthetic polymer (5). As a result of GPC measurement of the obtained synthetic polymer (5), the weight average molecular weight was 49,000 (in terms of polyethylene glycol).
[0087]
Synthesis example 6: Synthesis example of synthetic polymer (6) [polyethylene glycol (EO addition mole number 23) monomethacrylate ester / methacrylic acid / sodium styrenesulfonate = 50/25/25 (mass ratio) copolymer]
When 100 g of ethanol was heated to 80 ° C. under a nitrogen atmosphere, 60 g of ethanol, 40 g of polyethylene glycol (EO addition mole number 23) monomethacrylate (NK-ester M-230G, manufactured by Shin-Nakamura Chemical Co., Ltd.), A mixture of 20 g of methacrylic acid and 20 g of sodium styrenesulfonate dissolved in 120 g of ion-exchanged water and 2,2′-azobis- (2,4-dimethylvaleronitrile) (V-65, Wako Pure Chemical Industries, Ltd.) )) 2.7 g dissolved in 24 g of ethanol was added dropwise over 2 hours while maintaining at 80 to 85 ° C., and then stirred for 1 hour while maintaining at 80 ° C. to return to room temperature. . This mixed solution was purified by reprecipitation with acetone and dried to obtain a synthetic polymer (6). As a result of GPC measurement of the obtained synthetic polymer (6), the weight average molecular weight was 114,000 (in terms of polyethylene glycol).
[0088]
Synthesis example 7: Synthesis example of synthetic polymer (7) [polyethylene glycol (EO addition mole number 34) allyl ether / maleic acid = 20/80 (molar ratio) copolymer]
After dissolving 156.8 g of maleic anhydride and 313.6 g of polyethylene glycol (EO addition mole number 34) allyl ether in 400 g of ion-exchanged water, the temperature in the tank was raised to 70 ° C., and 60 g of 48% sodium hydroxide aqueous solution was added. added. Further, after the inside of the tank was replaced with nitrogen, the temperature was raised to 98 ° C., and an initiator aqueous solution consisting of 42.8 g of 35% hydrogen peroxide solution and 4.77 g of sodium persulfate was dropped into the reaction tank over 6 hours. The temperature inside the tank was kept at 98 ° C. This aqueous solution was lyophilized to obtain a synthetic polymer (7). As a result of GPC measurement of the obtained synthetic polymer (7), the weight average molecular weight was 18,000 (in terms of polyethylene glycol).
[0089]
Synthesis example 8: Synthesis example of synthetic polymer (8) [polyethylene glycol (EO addition mole number 120) monomethacrylic acid ester / methacrylic acid = 70/30 (mass ratio) copolymer]
When 200 g of ion-exchanged water was heated to 60 ° C. in a nitrogen atmosphere, 70 g of polyethylene glycol (EO addition mole number 120) monomethacrylic acid ester and 30 g of methacrylic acid were dissolved in 100 g of ion-exchanged water; While maintaining 1.6-g of '-azobis- (2-methylpropionamidine) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) in 100 g of ion-exchanged water at 60 to 65 ° C, The solution was dropped separately over 2 hours, and then stirred for another 6 hours while maintaining the temperature at 65 ° C. After returning to room temperature, the solution was neutralized by gradually adding 46.5 mL of 6N aqueous sodium hydroxide while cooling with ice, and about 80% of the carboxyl groups of the polymer were converted to sodium salts. This aqueous solution was freeze-dried to obtain a synthetic polymer (8). As a result of GPC measurement of the resulting synthetic polymer (8), the weight average molecular weight was 1270,000 (in terms of polyethylene glycol).
[0090]
Synthesis example 9: Synthesis example of synthetic polymer (9) [polyethylene glycol (EO addition mole number 23) monomethacrylate ester / ethyl methacrylate phosphate / methacrylic acid = 50/25/25 (mass ratio) copolymer]
When 300 g of ethanol was heated to 80 ° C. in a nitrogen atmosphere, 100 g of polyethylene glycol (EO addition mole number: 23) monomethacrylic acid ester, 50 g of ethyl methacrylate (Phosmer M manufactured by Unichemical Co., Ltd.), and 50 g of methacrylic acid were added. What melt | dissolved in ethanol 150g and what melt | dissolved 5.8g of 2,2'- azobis- (2,4-dimethylvaleronitrile) (V-65, Wako Pure Chemical Industries Ltd.) in ethanol 300g, While maintaining at 80 ° C., the solution was dropped separately over 2 hours, and then the stirring was further continued for 1 hour while maintaining at 80 ° C. This was returned to room temperature and then purified by reprecipitation with hexane to obtain a synthetic polymer (9). As a result of GPC measurement of the obtained synthetic polymer (9), the weight average molecular weight was 31,000 (in terms of polyethylene glycol).
[0091]
Example 1
First step: 60 g of nonionic surfactant (1) in Table 1, water-soluble organic solvent (1) 30 g, water-soluble organic solvent (2) 10 g, and ion-exchanged water 12 g are heated to 50 ° C., 4 g of the synthetic polymer (2) was dissolved in this over 5 hours to obtain a liquid dispersion medium.
[0092]
Second step: 30 g of zeolite (1) and 10 g of sodium carbonate are suspended in 60 g of the liquid dispersion medium obtained in the first step and filled with 800 g of zirconia beads having a diameter of 0.8 mm. Was used, and the wet pulverization was performed for 1 hour at a disc rotational speed of 1500 r / min. Thereafter, the media was removed through a 40-mesh sieve to obtain a liquid detergent composition. A part of this liquid detergent composition was sampled, diluted with ethanol, and the particle size was measured with a particle size distribution analyzer (LA-910, relative refractive index: 1.2, manufactured by Horiba, Ltd.). Was 0.8 μm.
[0093]
Third step: A small amount of a fragrance was added to the dispersion obtained in the second step and dissolved by sufficiently stirring at room temperature to obtain a liquid detergent composition.
[0094]
  Examples 2-9 and Comparative Examples 1-4
  Using the components shown in Table 1, various liquid detergent compositions were produced in the same manner as in Example 1 by the first, second, and third steps. In some examples, the third step was performed in the same manner as Example 10 described below.The synthetic polymers (1) and (3) are outside the scope of the present invention, but for convenience, examples using them are shown as examples.
[0095]
Example 10
First step: 30 g of nonionic surfactant (1) in Table 1, 30 g of nonionic surfactant (2), 25 g of water-soluble organic solvent (1), 10 g of water-soluble organic solvent (2), ion-exchanged water 11 g and 4 g of the synthetic polymer (8) were mixed to obtain a liquid dispersion medium.
[0096]
Second step: 25 g of zeolite (2) and 15 g of crystalline silicate compound are suspended in 55 g of the liquid dispersion medium obtained in the first step, and a batch type of 1 L capacity filled with 800 g of zirconia beads having a diameter of 0.8 mm is filled. Using a sand mill (manufactured by Imex Co., Ltd.), wet grinding was performed for 7 hours at a disc rotational speed of 1500 r / min. Thereafter, the media was removed through a 40-mesh sieve to obtain a dispersion. A part of this dispersion was sampled, diluted with ethanol, and the particle size was measured with a particle size distribution analyzer (LA-910, relative refractive index: 1.2, temperature 20 ° C., manufactured by Horiba, Ltd.). The diameter was 0.9 μm.
[0097]
Third step: In the dispersion obtained in the second step, the formula (11)
[0098]
[Formula 4]

[0099]
A small amount of a bleaching activator represented by the formula (2.0 g) and a fragrance were added, and the mixture was sufficiently stirred and dissolved at room temperature. Further, 2.0 g of sodium percarbonate, 0.5 g of enzyme (1) and 0.5 g of enzyme (2) were added and sufficiently stirred at room temperature to disperse it, thereby obtaining a liquid detergent composition.
[0100]
The volume separation rate and the viscosity of the liquid detergent compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 4 were measured by the following methods, and a washing test was performed. The results are shown in Table 1.
[0101]
(1) Volume separation rate
A graduated glass sedimentation tube was filled with a liquid detergent composition so as to have a depth of 30 cm and sealed, and each sample was stored in a room at 25 ° C. for 1 month. The boundary line between the transparent liquid phase and the solid dispersed phase of the sample after storage was visually judged, and the thickness x (cm) of the transparent liquid phase generated in the upper layer portion after phase separation was measured. The volume separation rate y (%) was determined by the following formula (V).
y = (x / 30) × 100 (V)
[0102]
(2) Viscosity
A 200 mL beaker was filled with 200 g of the liquid detergent composition, and a No. Two (or three) rotors were measured under speed conditions (25 ° C.) of 6 to 60 r / min depending on the viscosity.
[0103]
(3) Cleaning test
100 g of a mixture of 15% by mass of carbon black, 60% by mass of cottonseed oil, 5% by mass of cholesterol, 5% by mass of oleic acid, 5% by mass of palmitic acid, and 10% by mass of liquid paraffin is dissolved and dispersed in 8 L of parklene to 10 cm × 10 cm. A cut white cotton cloth (gold cloth 2003 cloth) was dipped to deposit dirt, and then the parklens were dried and removed to prepare a sebum / carbon dirt contaminated cloth (artificial contaminated cloth).
[0104]
A set of five sebum / carbon soil contaminated cloths was put into 1 L of a detergent aqueous solution for evaluation, and a cleaning test was performed with a tergotometer under the following conditions.
Cleaning time: 10 minutes
Detergent composition: 0.8 g / detergent solution for evaluation 1 L
Water hardness: 71.2mgCaCO_Three/ L
Water temperature: 20 ° C
Targotometer rotation speed: 100r / min
Rinse: Rinse with running water at 20 ° C. for 5 minutes.
[0105]
The detergency was determined by measuring the reflectance at 550 nm of the raw cloth before contamination and the contaminated cloth before and after cleaning using a self-recording colorimeter (manufactured by Shimadzu Corporation), and calculating the cleaning rate (%) by the following formula.
Washing rate (%) = {(reflectance after washing−reflectance before washing) / (reflectance of base fabric−reflectivity before washing)} × 100
[0106]
[Table 1]

[0107]
* Nonionic surfactant (1): Emulgen 108 (manufactured by Kao Corporation)
* Nonionic surfactant (2): Emulgen LS-106 (manufactured by Kao Corporation)
* Water-soluble organic solvent (1): polyoxyethylene phenyl ether (manufactured by Nippon Emulsifier Co., Ltd., PHG-30)
* Water-soluble organic solvent (2): Propylene glycol
* Anionic surfactant: alkyl linear C10-14 sodium alkylbenzene sulfonate
* Synthetic polymer (1): Polymer synthesized in Synthesis Example 1
* Synthetic polymer (2): Polymer synthesized in Synthesis Example 2
* Synthetic polymer (3): polymer synthesized in Synthesis Example 3
* Synthetic polymer (4) solution: polymer solution synthesized in Synthesis Example 4 (concentration: 11.8%)
* Synthetic polymer (5): polymer synthesized in Synthesis Example 5
* Synthetic polymer (6): polymer synthesized in Synthesis Example 6
* Synthetic polymer (7): polymer synthesized in Synthesis Example 7
* Synthetic polymer (8): polymer synthesized in Synthesis Example 8
* Synthetic polymer (9): polymer synthesized in Synthesis Example 9
* Polymer (1): Polyethylene glycol (polyethylene glycol 2,000, manufactured by Wako Pure Chemical Industries, Ltd.)
* Polymer (2): Sodium polymethacrylate (weight average molecular weight; 9,500, manufactured by Aldrich)
* Sodium percarbonate: average particle diameter 16 μm, dispersed in the liquid produced in the first step, measured by LA-910, manufactured by HORIBA, relative refractive index: 1.2
* Bleach activator: Bleach activator represented by the formula (11)
* Crystalline silicate compound: crystalline silicate compound described in Example 1 of JP-A-5-184946
* Zeolite (1): Toyo Builder (manufactured by Toyo Soda Co., Ltd.)
* Zeolite (2): Toyobuilder (Toyo Soda Co., Ltd.) calcined at 450 ° C for 1 hour and dehydrated
* Enzyme (1): Everase 16.0L-EX (protease, manufactured by Novo Nordisk Bio Industry)
* Enzyme (2): Lipolase 100L (lipase, manufactured by Novo Nordisk Bio-Industry)
[0108]
From Table 1, by using the component (b), the liquid detergent composition of the present invention stably disperses the solid dispersoid mixture containing the component (a), and the volume separation rate after one month is 5%. It has been found that it has the following detergency and excellent detergency.
[0109]
Example 11
First step: 2 g of the synthetic polymer (5) was dissolved in 100 g of ethanol, 30 g of zeolite (1) and 10 g of sodium carbonate were added and stirred for 3 hours to obtain a dispersion. The obtained dispersion was heated to 60 ° C. and then dried under reduced pressure, and ethanol was completely distilled off to obtain a polymer-coated inorganic powder.
[0110]
Second step: 60 g of nonionic surfactant (1), 30 g of water-soluble organic solvent (1), 10 g of water-soluble organic solvent (2), and 12 g of ion-exchanged water were mixed to obtain a liquid dispersion medium.
[0111]
Third step: A batch type sand mill with a capacity of 1 L, in which 42 g of the polymer-coated inorganic powder obtained in the first step is suspended in 60 g of the liquid dispersion medium obtained in the second step and filled with 800 g of zirconia beads having a diameter of 0.8 mm. (Imex Co., Ltd.) was used, and wet grinding was performed for 1 hour at a disc rotational speed of 1500 r / min. Thereafter, the media was removed through a 40-mesh sieve to obtain a liquid detergent composition.
[0112]
A part of this liquid detergent composition was sampled, diluted with ethanol, and the particle size was measured with a particle size distribution analyzer (LA-910, relative refractive index: 1.2, temperature 20 ° C., manufactured by Horiba, Ltd.). The average particle size was 0.6 μm. Further, the obtained liquid detergent composition had a viscosity (25 ° C.) as low as 320 mPa · s, high detergency, and high dispersion stability.
[0113]
【The invention's effect】
In the liquid detergent composition of the present invention, fine inorganic particles containing the component (a) are stably dispersed in the component (b) without increasing the product viscosity in the liquid dispersion medium containing a surfactant or the like. It is easily poured into the washing tub and quickly dissolved in the washing water. As a result, the cleaning power is also improved.

Claims (13)

An aluminosilicate compound comprising a liquid dispersion medium and a solid dispersoid dispersed in the liquid dispersion medium, wherein at least a part of the solid dispersoid is 30% by mass or more in the composition , One or more inorganic builder particles (a) selected from a crystalline silicate compound and a carbonate, wherein the liquid dispersion medium and / or the solid dispersoid has a carboxyl group or a salt thereof (I) and an alkyleneoxy group. A block-type or graft-type polymer having a polymer chain (b) as a structural unit, comprising a copolymer (b) selected from the following (b1) and (b2), and the ratio of water in the liquid dispersion medium Is a liquid detergent composition having a viscosity (25 ° C.) of 3000 mPa · s or less and a volume separation rate (25 ° C., standing for 30 days) of 5% or less.
(B1) A copolymer of an ester of a polyalkylene glycol and a vinyl monomer having a carboxyl group or a salt thereof, and a vinyl monomer having a carboxyl group or a salt thereof (b2) Reactivity not represented by the following general formula (3) Copolymer of polyalkylene glycol ether having a saturated group and a vinyl monomer having a carboxyl group or a salt thereof

[In formula, R < ₁ >, R < ₂ >, R < ₃ > is the same or different, and shows a hydrogen atom, a C1-C4 alkyl group, or a phenyl group. R ₄ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, an alkylaryl group or arylalkyl group having 7 to 22 carbon atoms. . n AO's are the same or different and each represents an alkyleneoxy group. n shows the number of 3-200. p represents 1. X is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or the following general formula (4).

The bivalent group represented by these is shown. (In the formula, R ₅ is a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, an alkylaryl group having 7 to 22 carbon atoms, or aryl. Represents an alkyl group, m AO's are the same or different and represent an alkyleneoxy group, q represents a number of 1 to 10, and m represents a number of 0 to 200.)]   The liquid detergent composition according to claim 1, wherein (b) is a polymer having no hydrocarbon group having 4 or more carbon atoms.   The liquid detergent composition according to claim 1 or 2, wherein (b) is obtained by a polymerization reaction of a monomer using one or more liquids constituting the liquid dispersion medium as a solvent. The mass ratio of the polymer chain (b) having the carboxyl group of (b) or a salt thereof (b) and the polymer chain (b) having an alkyleneoxy group as a structural unit is (a) / (b) = 5/95 to 95/5. in it, according to claim 1 to 3 liquid detergent composition of any of claim wherein.   The liquid detergent composition according to claim 1, wherein the viscosity (25 ° C.) is 1000 mPa · s or less. The liquid detergent composition in any one of Claims 1-5 whose aluminosilicate compound is 1 or more types represented by General formula (1).
^{_{(M 1 p M 2 q M}} 3 r O) u · (M 4 s M 5 t O) v · (Al 2 O 3) w · (SiO 2) (1)
[Wherein M ¹ , M ² and M ³ each represent Na, K or H, and M ⁴ and M ⁵ each represent Ca or Mg. p, q, and r are each a number from 0 to 2 (where p + q + r = 2), s and t are each a number from 0 to 1 (where s + t = 1), u is a number from 0 to 1, and v is a number from 0 to 1. The number and w are numbers from 0 to 0.6. ] The liquid detergent composition according to any one of claims 1 to 6, wherein the crystalline silicate compound is one or more kinds represented by the general formula (2).
^{_{(M 1 p M 2 q M}} 3 r O) · (M 4 s M 5 t O) x · (SiO 2) y (2)
[Wherein, M ¹ , M ² , M ³ , M ⁴ , M ⁵ , p, q, r, s and t are the same as those in the general formula (1). x represents a number from 0 to 1, and y represents a number from 0.9 to 3.5. ]   The liquid detergent composition according to any one of claims 1 to 7, wherein the average particle size of (a) is 2 µm or less. Furthermore, surfactant is contained, The ratio of the nonionic surfactant in all the surfactants is 70-100 mass%, The liquid detergent composition in any one of Claims 1-8. . Furthermore, the liquid detergent composition of any one of Claims 1-9 containing a hydroxyl-containing water-soluble organic solvent. The liquid detergent composition according to any one of claims 1 to 10, wherein the amount of water is 1 to 15% by mass in addition to the amount of water adsorbed in (a). The method for producing a liquid detergent composition according to any one of claims 1 to 11 , comprising a step of bringing (a) and (b) into contact with each other and then mixing with a liquid dispersion medium. The method for producing a liquid detergent according to any one of claims 1 to 11 , comprising a step of wet pulverizing (a) and (b) in a liquid dispersion medium.