JP4626927B2 - Liquid detergent composition - Google Patents

Description

【００３２】
〔式中、Ｒ⁶は平均炭素数８〜２０、好ましくは１２〜１８のアルキル基もしくはアルケニル基又はＲ⁹Ｃ(＝Ｏ)ＮＨ(ＣＨ₂)_z、Ｒ⁹は平均炭素数８〜２０（好ましくは１２〜１８）のアルキル基又はアルケニル基であり、ｚは１〜５である。またＲ⁷、Ｒ⁸はそれぞれＣＨ₃、Ｃ₂Ｈ₅又はＣ₂Ｈ₄ＯＨである。〕。
【００３３】
（ｂ２）陰イオン性界面活性剤としては、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、アルキル又はアルケニルエーテル硫酸エステル塩、α−オレフィンスルホン酸塩、α−スルホ脂肪酸塩又はこのエステル、アルキル又はアルケニルエーテルカルボン酸塩、アミノ酸型界面活性剤、Ｎ−アシルアミノ酸型界面活性剤等が例示される。特に炭素数１０〜１４の直鎖アルキルベンゼンスルホン酸塩、炭素数１０〜１８のアルキル硫酸エステル塩又はアルキルエーテル硫酸エステル塩が挙げられ、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、マグネシウム等のアルカリ土類金属、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等のアミンが好ましい。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。また、陰イオン性界面活性剤を酸形態で組成中に配合してもよく、別途添加したアルカリ剤（アルカノールアミン等）で中和してもよい。
【００３４】
陽イオン性界面活性剤としては、アルキルトリメチルアンモニウム塩等の第４アンモニウム塩等が挙げられる。
【００３５】
両性界面活性剤としては、カルボベタイン型のもの、スルホベタイン型のもの等が例示される。
【００３６】
＜（ｃ）成分＞
本発明の組成物は、（ｃ）成分を、安定性や洗浄力の点で、１〜７０質量％、更に１〜５０質量％、より更に１〜３０質量％、特に３〜１５質量％含有することが好ましい。なお、本発明において、水の含有量とは、結晶水以外の水含有量のことである。
【００３７】
＜（ｄ）成分＞
本発明の組成物は、（ｄ）成分を、分離安定性や洗浄性能の点で、好ましくは０．０１〜２０質量％、より好ましくは０．０５〜１５質量％、更に好ましくは０．１〜１０質量％、特に好ましくは０．５〜８質量％含有する。
【００３８】
（ｄ）成分としては、液相の密度調整剤、液相の粘度調整剤、（ａ）成分の二次凝集防止剤等が挙げられる。中でも、使い易さ、安定性の点で（ａ）成分の二次凝集防止剤が好ましい。
【００３９】
（ｄ）成分の具体例としては、密度２ｇ／ｃｍ³以上の粒子径５０ｎｍ以下の粒子（シリカ、二酸化チタン、硫酸バリウム、ベントナイト等）、キサンタンガム、グアガム、カルボキシメチルセルロース（塩）、ヒドロキシエチルセルロース（塩）、カチオン化セルロース、ポリビニルピロリドン、ポリビニルアルコール、ポリアクリル酸、ポリエチレングリコール、リグニンスルホン酸（塩）、ポリエチレンイミン、アクリル酸（塩）／マレイン酸（塩）ポリマー、アクリル酸（塩）／メタクリル酸（塩）ポリマー、等が挙げられるが、使い易さ及び安定性の点で、（ｂ）成分と（ｃ）成分を含む液体相に溶解性あるいは均一分散性のポリマーを構成するモノマー群と、（ａ）成分に親和性の高い官能基を有するモノマー群から選ばれる、それぞれ１種以上のモノマーを重合あるいは重縮合して得られるものが好ましい。
【００４０】
液体相に溶解性あるいは均一分散性のポリマーを構成するモノマー群の例として、（ｉ）〜（ｐ）が挙げられる。
（ｉ）炭素数１〜２２の無置換又は置換の飽和又は不飽和アルキル基、又はアラルキル基を有するビニルエーテル類。例えば、メチルビニルエーテル、エチルビニルエーテル、４−ヒドロキシブチルビニルエーテル、フェニルビニルエーテル等が好ましい。
（ｊ）無置換、あるいは窒素上に炭素数１〜１２の飽和又は不飽和のアルキル基又はアラルキル基を有する置換(メタ)アクリルアミド類。例えば、(メタ)アクリルアミド、Ｎ−メチル(メタ)アクリルアミド、Ｎ,Ｎ−ジメチル(メタ)アクリルアミド、Ｎ−エチル(メタ)アクリルアミド、Ｎ−ｔ−ブチル(メタ)アクリルアミド、(メタ)アクリロイルモルホリン、２−(Ｎ,Ｎ−ジメチルアミノ)エチル(メタ)アクリルアミド、３−(Ｎ,Ｎ−ジメチルアミノ)プロピル(メタ)アクリルアミド、２−ヒドロキシエチル(メタ)アクリルアミド、Ｎ−メチロール(メタ)アクリルアミド、Ｎ−ブトキシメチル(メタ)アクリルアミド等が好ましい。
（ｋ）Ｎ−ビニル脂肪族アミド類。例えば、Ｎ−ビニルピロリドン、Ｎ−ビニルアセトアミド、Ｎ−ビニルホルムアミド等が好ましい。
（ｌ）炭素数１〜２２の無置換又は置換の、飽和又は不飽和アルキル基、又はアラルキル基を有する(メタ)アクリル酸エステル類。例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸２−ヒドロキシエチル、(メタ)アクリル酸２−(Ｎ,Ｎ−ジメチルアミノ)エチル、(メタ)アクリル酸２−メトキシエチル等が好ましい。
（ｍ）アルキレンオキサイド類。例えばエチレンオキサイド、プロピレンオキサイド等が好ましい。
（Ｎ）環状イミノエーテル類。例えば２−メチル−２−オキサゾリン、２−フェニル−２−オキサゾリン等が好ましい。
（ｏ）スチレン類。例えば、スチレン、４−エチルスチレン、α−メチルスチレン等が好ましい。
（ｐ）ビニルエステル類。例えば、酢酸ビニル、カプロン酸ビニル等が好ましい。
【００４１】
上記モノマー群から得られるポリマーの他にも、液体相に溶解性あるいは均一分散性のポリマーとしては、（ｑ）〜（ｓ）の構造が挙げられ、これらの構造と、後述する固体成分に親和性の高い官能基を有するモノマー群１種以上とから成るポリマーも、好ましい。
（ｑ）２価アルコールと２価カルボン酸とから成るポリエステル類。例えば、ポリエチレングリコールとテレフタル酸、あるいは１，４−ブタンジオールとコハク酸の重縮合物等が好ましい。
（ｒ）ポリアミド類。例えば、Ｎ−メチルバレロラクタムの開環重合物が好ましい。
（ｓ）ポリウレタン類。例えば、ポリエチレングリコールとヘキサメチレンジイソシアナートとＮ−メチルジエタノールアミンあるいは１，４−ブタンジオールの重付加物等が好ましい。
【００４２】
（ａ）成分に親和性の高い好ましい官能基としては、カルボキシル基、スルホン酸基、ヒドロキシル基、１〜４級のアンモニウム基が挙げられる。それらの官能基を有するモノマーとして例えば、(メタ)アクリル酸及びその塩類、スチレンカルボン酸及びその塩類、マレイン酸及びその塩類、イタコン酸及びその塩類、スチレンスルホン酸及びその塩類、(メタ)アリルスルホン酸及びその塩類、２−アクリルアミド−２−メチルプロパンスルホン酸及びその塩類、ビニルスルホン酸及びその塩類、ビニルアルコール、(メタ)アクリル酸２−ヒドロキシエチル、２−ヒドロキシエチル(メタ)アクリルアミド、４−ヒドロキシメチルスチレン、リン酸モノ−2−((メタ)−アクリロイルオキシ)エチル、塩化２−((メタ)アクリロイルオキシ)エチルトリメチルアンモニウム、塩化ビニルベンジルトリメチルアンモニウム、エチル硫酸２−((メタ)アクリロイルオキシ)エチルジメチルエチルアンモニウム、塩化３−((メタ)アクリルアミド)プロピルトリメチルアンモニウム、塩化ジアリルジメチルアンモニウム、ビニルピリジン等が挙げられる。
【００４３】
中でも好ましい高分子型分散剤は、液体相に溶解性あるいは均一分散性のポリマーと、（ａ）成分に親和性の高い官能基を有するポリマーとの、ブロックあるいはグラフトポリマーである。
【００４４】
２種のセグメントが存在することにより、両者の効果が相殺されることなく発現する。両者の効果をより高く発現するためには、グラフトポリマーを用いることが特に好ましい。ブロックあるいはグラフトポリマー中の前記２種のセグメントの重量比〔(液体相に溶解性あるいは均一分散性のポリマーセグメント)／(（ａ）成分に親和性の高い官能基を有するポリマーセグメント)〕は、５／９５〜９５／５が好ましい。このようなブロックあるいはグラフトポリマーの合成法は、例えばポリマー鎖中にアゾ基を有するマクロアゾ開始剤を用いてビニル系モノマー等を重合する方法(マクロアゾ開始剤法)、ポリマー鎖の一端に重合性基を有する化合物を使用する方法(マクロモノマー法)、及びポリマーの存在下にモノマーを改めてラジカル重合し、新たに生成するポリマー鎖が、連鎖移動反応によって予め共存させたポリマー鎖に連結するようにする方法(連鎖移動法)が好ましい。これらの方法で得られる高分子型分散剤として、例えばポリエチレングリコールマクロアゾ開始剤を使用してアクリル酸(又はその塩)をラジカル重合して得られるブロックポリマー、ポリエチレングリコールモノ(メタ)アクリル酸エステルと(メタ)アクリル酸又はその塩との共重合体、ポリエチレングリコールモノ(メタ)アクリル酸エステルとスチレンスルホン酸又はその塩との共重合体、ポリエチレングリコールモノ(メタ)アクリル酸エステルと塩化２−((メタ)アクリロイルオキシ)エチルトリメチルアンモニウムとの共重合体、ポリエチレングリコールモノ(メタ)アクリル酸エステルと(メタ)アクリル酸２−ヒドロキシエチルとの共重合体、ポリエチレングリコール又はポリプロピレングリコール又はポリエチレングリコールプロピレングリコール中でアクリル酸とマレイン酸(又はその塩)とをラジカル重合して得られるグラフトポリマー、ポリ(Ｎ，Ｎ−ジメチルアクリルアミド／スチレン)共重合体水溶液中で塩化ジアリルジメチルアンモニウムをラジカル重合して得られるグラフトポリマー、ポリ(Ｎ，Ｎ−ジメチル(メタ)アクリルアミド)水溶液中でスチレンスルホン酸(又はその塩)をラジカル重合して得られるグラフトポリマー等が例として挙げられる。これら高分子型分散剤の重量平均分子量は、粘度の過度な上昇を防ぐ目的から、１００万以下、更に１０００から５０万、特に１万から３０万であることが好ましい。
【００４５】
＜その他成分＞
本発明の組成物には、（１）（ａ）成分以外のアルミノケイ酸塩０．１〜１０質量％、（２）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質量％、（３）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０．０１〜３０質量％、（４）平均分子量５０００以上のポリエチレングリコール、ナフタレンスルホン酸塩ホルマリン縮合物等の再汚染防止剤及び分散剤０．０１〜１０質量％、（５）ポリビニルピロリドン等の色移り防止剤０．０１〜１０質量％、（６）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質量％、（７）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−７）で示される漂白活性化剤等の漂白活性化剤０．０１〜１０質量％、（８）チノパールＣＢＳ（チバスペシャルティケミカルス（株）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質量％、（９）特開平１０−６０４８０号公報の請求項１記載のシリコーン等の柔軟基剤０．１〜２質量％、（１０）シリカ等の消泡剤０．０１〜２質量％、（１１）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質量％、（１２）青味付け剤、（１３）セルラーゼ、アミラーゼ、ペクチナーゼ、プロテアーゼ、リパーゼ等の酵素、（１４）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、（１５）香料、（１６）抗菌防腐剤、（１７）着色剤等を配合することができる。
【００４６】
特に洗浄性能や安定性の点で、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ミン類、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩、珪酸ナトリウム、珪酸カリウム等のアルカリ金属珪酸塩、等のアルカリ剤を配合することが好ましく、中でも炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩が洗浄性能の点で好ましい。これらのアルカリ剤は組成物中に０．５〜３０質量％含有されることが好ましく、１〜２５質量％がより好ましく、３〜２０質量％が更に好ましい。
【００４７】
＜製造方法＞
本発明の液体洗浄剤組成物は、（ａ）〜（ｃ）成分、及び要すれば（ｄ）成分やその他成分を定法により混合することによって得ることができるが、分離安定性の点で、（ａ）〜（ｃ）成分、及び要すれば（ｄ）成分やその他成分を混合する工程、及び得られた混合物を湿式粉砕機で処理する工程を設けることが好ましい。湿式粉砕機としては、特に限定されるものではなく、例えば、化学工学会編化学工学便覧（丸善、１９８８年）第五版８２６〜８３８ページ記載の粉砕機のうち湿式粉砕可能なものを用いることができる。これらのうちサンドミル、振動ミル、アトライター、ダイノーミルなど粉砕メディアを用いた粉砕機が好適に用いられる。粉砕力と生産性の点で、メディアを使用した湿式粉砕法が特に好ましい。メディアとしてはチタニア、ジルコニア、シリカ等公知の材質の物を使用することができる。メディア径としては０．１〜３ｍｍのものが特に好ましい。
【００４８】
洗浄性能及び安定性の点で、湿式粉砕機による処理前後の（ａ）成分の平均一次粒子径の減少率は、０〜５０％が好ましく、０〜２０％がより好ましい。すなわち、湿式粉砕機による処理は、（ａ）成分の平均一次粒子径をあまり減少することなく、凝集粒子径を小さくすることが好ましい。
【００４９】
【実施例】
実施例１〜６、比較例１〜３
表１に示す液体洗浄剤組成物を下記の方法によって調製し、得られた組成物について、下記のように使い易さの評価、洗浄力の評価、及び分離安定性の評価を行った。その結果を表１に示す。なお、得られた組成物の２５℃の粘度は何れも１００〜５００ｍＰａ・ｓであり、２５℃のｐＨは何れも１０〜１１であった。また、液体洗浄剤組成物に含有される固体成分の平均凝集粒子径は比較例２を除いて０．５μｍ以下であった。
【００５０】
〔液体洗浄剤組成物の調製法〕
表１に示した各液体洗浄剤組成物について、酵素及び香料を除いた配合成分を液体洗浄剤組成物１００ｇに対する比率で秤量、混合した。次に、該混合物を、バッチ式サンドミル（容量１Ｌ、アイメックス社製）を用い、直径０．５ｍｍのジルコニアビーズ５００ｇを充填し、ディスク回転数１５００ｒ／ｍｉｎで１時間粉砕（ジャケット式冷却器に１５℃の水を循環させながら）した。得られた液体−固体混合物を４０メッシュのふるいに通し、ジルコニアビーズを除去した。更に要すれば酵素及び香料を加え、常温で撹拌混合し、液体洗浄剤組成物を得た。
【００５１】
〔使い易さの評価〕
各サンプル液８０ｍＬを１００ｍＬメスシリンダーに入れ、２５℃恒温室下で静置させた後、パネラー１０名にサンプル液４０ｍＬ（約半量）を、水道水３５リットルを入れた洗濯機（東芝銀河３．６（ＶＨ−３６０Ｓ１））に投入してもらい、下記基準により使いやすさを評価した。
液の投入がしやすく、投入液量の調節もし易い。 …３点
液の投入はしやすいが、投入液量の調節が難しい。…２点
液の投入はしづらいが、投入液量の調節はし易い。…２点
液の投入がしづらく、投入液量の調節も難しい。 …１点
１０名の平均点を以て、そのサンプル液の評価を下記の如く決定した。
○；平均点２．５以上
△；平均点２以上２．５未満
×；平均点１以上２未満。
【００５２】
〔洗浄力の評価〕
ＪＩＳ Ｋ ３３６２：１９９８記載の衣料用合成洗剤の洗浄力評価方法に従って、表１の液体洗浄剤組成物と洗浄力判定用指標洗剤の洗浄力を比較した。表１の液体洗浄剤組成物の使用濃度を２０ｇ／３０Ｌとした。
○：指標洗剤と同等以上
×：指標洗剤より劣る。
【００５３】
〔分離安定性の評価〕
５０ｍＬのサンプルビン（Ｎｏ．６広口規格ビン、ガラス製、直径４０ｍｍ、高さ８０ｍｍの円筒形）に、表１の液体洗浄剤組成物を４０ｍＬ充填し、蓋をした後、４０℃の恒温室で３０日間静置した。液体の安定性は目視で外観を下記の基準で判定した。
○；均一分散している
×；分離又は沈降が認められる
【００５４】
【表１】

【００５５】
・微粒子ゼオライトＡ：以下の合成例（１）により得られたゼオライト
合成例（１）
図１に示した装置を用いた。３号水ガラスを原料槽１に入れ攪拌した。続いて原料槽１に、４８％水酸化ナトリウム水溶液を入れ、その後、３５％塩化カルシウム溶液とイオン交換水を予め混合して得た塩化カルシウム溶液を１分間かけて添加し、５０℃に昇温した。次に攪拌機３を動かしたまま、反応槽２にアルミン酸ナトリウムを入れ、５０℃に昇温した。昇温後、循環ライン５に送液ポンプ７にてアルミニウム源（アルミン酸ナトリウム）を循環させながら、混合機４の回転数を２４００ｒｐｍとし、原料槽１のシリカ源（３号水ガラス、４８％水酸化ナトリウム水溶液及び塩化カルシウム溶液からなる水ガラス溶液）を、原料供給ライン６を介して、循環ライン５に８分間かけて供給し、反応を行った。反応終了後も引き続き循環ライン５にて得られたスラリーを循環させながら８０℃に昇温し、８０℃に保持したまま１時間熟成を行った。得られたスラリーをろ液のｐＨが１１．４になるまでろ過水洗した。その後乾燥してゼオライト粉末を得た。仕込み条件及び反応条件、並びに得られたゼオライトの組成及び物性（カチオン交換能、平均一次粒子径、平均凝集粒子径の測定方法は前記の通り。以下同様）を表２に示す。なお、Ｎａ₂Ｏ／Ｈ₂Ｏのモル比は０．０６であった。
・微粒子ゼオライトＢ：以下の合成例（２）により得られたゼオライト
合成例（２）
図２に示した装置を用いた。３号水ガラスを原料槽８に入れ攪拌した。ついで３５％塩化カルシウム溶液とイオン交換水を予め混合して得た塩化カルシウム溶液を原料槽８に１分間かけて添加したのち５０℃に昇温した。次に攪拌機１０を動かしたまま、反応槽９にアルミン酸ナトリウムと４８％水酸化ナトリウム水溶液を入れ５０℃に昇温した。昇温後、循環ライン１２に送液ポンプ１４にてアルミニウム源（アルミン酸ナトリウムと４８％水酸化ナトリウム水溶液からなるアルミン酸ナトリウム溶液）を循環させながら、混合機１１の回転数を３６００ｒｐｍとし、原料槽８のシリカ源（３号水ガラスと塩化カルシウム溶液からなる水ガラス溶液）を、原料供給ライン１３を介して、循環ライン１２に３．５分間かけて供給し、反応を行った。反応終了後も引き続き循環ライン１２にて得られたスラリーを循環させながら８０℃に昇温し、８０℃に保持したまま２時間熟成を行った。得られたスラリーをろ液のｐＨが１１．４になるまでろ過水洗した。その後乾燥してゼオライト粉末を得た。仕込み条件及び反応条件、並びに得られたゼオライトの組成及び物性を表２に示す。なお、Ｎａ₂Ｏ／Ｈ₂Ｏのモル比は０．０６であった。
【００５６】
【表２】

【００５７】
・微粒子ゼオライトＣ：以下の合成例（３）により得られたゼオライト
合成例（３）
２リットルのステンレス製セパラブルフラスコに４８％ＮａＯＨを１２９７．２ｇ添加し、ついで水酸化アルミニウム１０００ｇ（純度９９％）を攪拌しながら添加した。その後昇温し１２０℃で１時間加熱したのち冷却し、アルミン酸ナトリウム（Ｎａ₂Ｏ：２１．０１％、Ａｌ₂Ｏ₃：２８．１８％）を得た。
【００５８】
上記手法で得られたアルミン酸ナトリウム３２０ｇを２リットルステンレス製セパラブルフラスコ（内径１２ｃｍ）に入れ、ついで４８％ＮａＯＨ水溶液を３１６．１ｇ添加し、アルミニウム源とした。
【００５９】
次に３号水ガラス（Ｎａ₂Ｏ：９．６８％、ＳｉＯ₂：２９．８３％）３５５．６ｇを別の２リットルステンレス製セパラブルフラスコに入れ、そこに予めイオン交換水８１９．８ｇに無水塩化カルシウム２．９４ｇを混合し調製した塩化カルシウム水溶液を攪拌しながら添加し、この溶液を、アルカリ土類金属を含有したシリカ源とした。
【００６０】
上記アルミニウム源を羽根径１１ｃｍの攪拌羽根で３００ｒｐｍで攪拌しながら５０℃に昇温した。また、シリカ源も同様に５０℃に昇温した。両原料が５０℃になったところで、ローラーポンプを用いてアルミニウム源の中にシリカ源を５分間にわたって滴下して添加した。滴下終了後１０分間５０℃〜６０℃の温度に保持し、次に８０℃まで昇温した。その後１．５時間８０℃の状態で攪拌しながら熟成を行った。なお、仕込み組成は、ＳｉＯ₂／Ａｌ₂Ｏ₃＝２、Ｎａ₂Ｏ／Ａｌ₂Ｏ₃＝４、ＣａＯ／Ａｌ₂Ｏ₃＝０．０３であった。また、反応時の固形分濃度は２３％であった。
【００６１】
得られたスラリーを、ろ液のｐＨが１１．４になるまでろ過水洗した。そして、１００℃で１３時間乾燥し、ゼオライトの粉末を得た。
【００６２】
得られたゼオライトの組成は無水物で１．０５Ｎａ₂Ｏ・２．０５ＳｉＯ₂・Ａｌ₂Ｏ₃・０．０３ＣａＯ（一般式（Ｉ）中、ｘ＝１．０５、ｙ＝２．０５、ｚ＝０．０３）であった。また、Ｘ線回折パターンから結晶形はＡＳＴＭ Ｎｏ．３８−２４１に帰属されるＡ型ゼオライトであった。
【００６３】
また平均一次粒子径は０．７５μｍ、１分間のカチオン交換能が１６５ｍｇＣａＣＯ₃／ｇ、１０分間のカチオン交換能が２１０ｍｇＣａＣＯ₃／ｇである、カチオン交換能に優れる微粒子ゼオライトであった。さらに平均凝集粒子径は３．４μｍで平均一次粒子径と平均凝集粒子径の積で定義される分散パラメータは２．６であった。
・非イオン性界面活性剤Ａ：炭素数１０〜１４の直鎖第１級アルコールにＥＯを平均３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
・非イオン性界面活性剤Ｂ：炭素数１２〜１４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（ソフタノール７０、（株）日本触媒製）
・非イオン性界面活性剤Ｃ：一般式（ｂ１−４）において、Ｒ⁴が炭素数９〜１１の分岐鎖１級アルキル基、ｘ＝０、ｙ＝１．３、Ｇがグルコース残基の化合物。
・陰イオン性界面活性剤Ａ：アルキル炭素数１０〜１４の直鎖アルキルベンゼンスルホン酸ナトリウム（平均分子量３４５）
・陰イオン性界面活性剤Ｂ：平均炭素数１２．２の分岐鎖第１級アルコールにＥＯを１分子当たり平均３モル付加させたアルキルエーテル硫酸エステルナトリウム塩
・脂肪酸：炭素数１２〜１６のヤシ油系脂肪酸（ルナックＬ−５５、花王（株）製）
・４Ａゼオライト（１）：４Ａ型ゼオライト（トヨビルダー、東ソー（株）製）、合成時の平均一次粒子径３μｍ、組成物中の平均一次粒子径２μｍ、１分間のカチオン交換能１８０ｍｇＣａＣＯ₃／ｇ以上、１０分間のカチオン交換能２００ｍｇＣａＣＯ₃／ｇ以上、アルカリ土類金属を含有する化合物の存在下で、シリカ源とアルミニウム源を反応させて得られたものではない。
・４Ａゼオライト（２）：４Ａ型ゼオライト（トヨビルダー、東ソー（株）製）を粉砕し平均一次粒子径０．８μｍに調整したもの、組成物中の平均一次粒子径０．５μｍ、１分間のカチオン交換能１８０ｍｇＣａＣＯ₃／ｇ以上、１０分間のカチオン交換能２００ｍｇＣａＣＯ₃／ｇ以上、アルカリ土類金属を含有する化合物の存在下で、シリカ源とアルミニウム源を反応させて得られたものではない。
・分散剤Ａ：アクアロックＦＣ６００Ｓ（（株）日本触媒製）を凍結乾燥させたもの、重量平均分子量６．８万（ポリエチレングリコール換算）
・分散剤Ｂ：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、重量平均分子量２２．２万（ポリエチレングリコール換算）
・分散剤Ｃ：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））の共重合体、重量平均分子量３．９万（ポリエチレングリコール換算）
・フェノールＥＯ３モル付加物：ポリオキシエチレンモノフェニルエーテル（ＥＯ平均３モル付加）
・ブチルカルビトール：ジエチレングリコールモノブチルエーテル
・ペンチルグリセリルエーテル：ｎ−ペンチルモノグリセリルエーテル
・着色剤：青色１号
・酵素：エバラーゼ１６．０Ｌ タイプＥＸ（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社製）
【図面の簡単な説明】
【図１】合成例（１）で用いた微粒子ゼオライトの製造装置の概略図である。
【図２】合成例（２）で用いた微粒子ゼオライトの製造装置の概略図である。
【符号の説明】
１、８ 原料槽
２、９ 反応槽
３、１０ 撹拌機
４、１１ 混合機
５、１２ 循環ライン
６、１３ 原料供給ライン
７、１４ 送液ポンプ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid detergent composition. Particularly preferably, it relates to a liquid detergent composition for clothing.
[0002]
[Prior art]
Liquid detergents are superior to powder detergents in terms of ease of use, such as no undissolved residue and direct application to soiled areas. However, there is also a general method in which the liquid detergent is simply dissolved in washing water without applying it to the dirt, and in this case, the cleaning power of the liquid detergent tends to be inferior to that of the powder detergent. This is because when a builder component such as an alkaline agent or a Ca scavenger is added to a liquid detergent in the same amount as the powder detergent, the system stability becomes problematic. This is because the builder amount is set low. From this point of view, the development of liquid detergents in which a larger amount of builder is stably added has been promoted.
[0003]
For example, JP-A-58-145794 discloses an aqueous, pourable fluid detergent composition containing an effective amount of a detergent builder. However, since the composition achieves storage stability by making it a high viscosity exceeding 1000 mPa · s, it can be added by pouring, but there are problems such as applicability and dripping. There was a problem with ease.
[0004]
As a method for stably blending a solid builder component such as zeolite into a liquid detergent, refinement of the primary particle diameter has been studied. For example, a method of mechanically pulverizing as disclosed in Japanese Patent Laid-Open No. Sho 62-46494, or as disclosed in Japanese Patent Laid-Open Nos. 60-127218 and 62-275016 A method for obtaining fine particles according to the charged composition and reaction conditions is being studied. However, these methods have problems in performance and production efficiency as a builder, and need to be improved.
[0005]
JP-A-3-26800 and JP-A-3-502108 disclose the use of zeolite having an average particle diameter of 1 μm or less. However, there is a problem that the cleaning performance is not sufficient.
[0006]
Accordingly, there has been a demand for a liquid detergent that achieves high detergency and that has good storage stability while taking advantage of the ease of use of the liquid detergent.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a liquid detergent that achieves a high detergency and that has good storage stability while taking advantage of the ease of use of the liquid detergent.
[0008]
[Means for Solving the Problems]
The present invention relates to (a) a fine particle zeolite obtained by reacting a silica source and an aluminum source in the presence of a compound containing an alkaline earth metal (hereinafter referred to as component (a)), (b) a surfactant [ Hereinafter, it is related with the liquid detergent composition containing (b) component] and (c) water [henceforth (c) component].
[0009]
The present invention also includes a step of mixing the component (a), the component (b), the component (c) and, if necessary, the dispersion stabilizer (hereinafter referred to as the component (d)) of the component (d) (a). The present invention relates to a method for producing the liquid detergent composition of the present invention, comprising (i) and a step (ii) of treating the mixture obtained by the step (i) with a wet pulverizer.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The liquid detergent composition of the present invention contains components (a), (b), (c) and, if necessary, (d) a dispersion stabilizer of component (a) (hereinafter referred to as component (d)). To do.
[0011]
In the present invention, the liquid is fluid at 25 ° C., but the viscosity at 25 ° C. of the composition of the present invention is 1000 mPa · s or less from the viewpoint of ease of use such as low dripping and coating properties. Is preferable, 800 mPa · s or less is more preferable, and 500 mPa · s or less is more preferable. In view of separation stability, the viscosity at 25 ° C. is preferably 50 mPa · s or more, more preferably 100 mPa · s or more, and further preferably 150 mPa · s or more. The viscosity is measured using a B-type viscometer (manufactured by TOKIMEC, VISCOMETER MODEL BM) under the conditions that the rotor used is 3 or 4, the rotation speed is 60 r / min, and the measurement time is 60 seconds.
[0012]
From the viewpoint of cleaning performance and safety, the pH of the composition of the present invention is preferably 8.5 to 11, more preferably 9 to 11, and still more preferably 10 to 11. The pH is measured according to JIS K 3362: 1998. As the measuring device, for example, a glass electrode type pH meter (manufactured by Horiba, Ltd., D-14) can be used.
[0013]
The average agglomerated particle size of the solid component contained in the liquid detergent composition of the present invention is preferably 1 μm or less, more preferably 0.8 μm or less, and even more preferably 0.5 μm or less in terms of separation stability. The average agglomerated particle size was randomly selected from 500 SEM photographs taken at a magnification of 5000 with a scanning electron microscope (SUPERSCAN-220 manufactured by Shimadzu Corp.) and digitized. (A graphitizer, digitizer KW3300) was used to measure the longest width of the aggregated particles, and the average value of the obtained measured values was defined as the average aggregated particle diameter.
[0014]
<(A) component>
The composition of the present invention contains the component (a) in the range of 5 to 50% by mass, further 10 to 50% by mass, further 15 to 45% by mass, particularly 20 to 45% by mass in terms of cleaning performance and usability. It is preferable to do.
[0015]
The average primary particle size of the component (a) is preferably 1 μm or less, more preferably 0.8 μm or less, and even more preferably 0.5 μm or less from the viewpoint of separation stability. The average primary particle size was randomly selected from 500 SEM photographs taken with a scanning electron microscope (SUPERSSCAN-220, manufactured by Shimadzu Corporation) at a magnification of 5000, and confirmed as a primary particle. The maximum width of the primary particles was measured using (Graphic, Digitizer KW3300), and the average value of the obtained measured values was defined as the average primary particle diameter.
[0016]
(A) The cation exchange capacity of the component is 120 mg CaCO for 1 minute in terms of washing performance. _Three / G or more, preferably 150 mg CaCO _Three / G or more is more preferable, 180 mg CaCO _Three / G or more is more preferable. The cation exchange capacity for 10 minutes is 170 mg CaCO _Three / G or more, preferably 190 mg CaCO _Three / G or more is more preferable, 200 mg CaCO _Three / G or more is more preferable. The cation exchange capacity was determined by accurately weighing the sample in a 100 mL beaker, and containing a 20 ° C. calcium chloride aqueous solution (CaCO _Three 100 mL in terms of conversion) was added, and after stirring for a predetermined time at 20 ° C. (rotation speed of 400 r / min with a 30 mm × 8 mm stirrer piece), filtration was performed with a 0.2 μm membrane filter, and 10 mL of the filtrate was taken. The amount of Ca in the filtrate was measured by EDTA titration, and the amount of Ca ion exchanged per 1 g of sample (CaCO) in a predetermined time (1 minute or 10 minutes) from the following equation: _Three Conversion) and determined as cation exchange capacity.
[0017]
Cation exchange capacity (mgCaCO _Three / g) = [(B−V) × M × 100.09 × 100/10] / S
[B: Calcium chloride solution (CaCO _Three EDTA titration (mL) in terms of conversion (mL), V: EDTA titration (mL) of sample solution, M: EDTA molarity (mol / L), 100.09: CaCO _Three The molecular weight (g), 100: the amount of calcium chloride solution used in the measurement (mL), 10: the amount of titrated liquid (mL), S: the amount of sample (g)].
[0018]
(A) As a reaction raw material of a component, a silica source and an aluminum source are not specifically limited, However, Those aqueous solution is preferable at the point of the uniformity and dispersibility of reaction. As the silica source, a commercially available water glass is preferably used, and a silica source with a molar ratio or concentration adjusted by adding water or caustic can also be used. Examples of the aluminum source include aluminum hydroxide, aluminum sulfate, aluminum chloride, alkali metal aluminates such as potassium aluminate and sodium aluminate. Of these, sodium aluminate is preferably used in terms of the height of the reaction. These are used as an aluminum source after adjusting to an appropriate molar ratio and concentration using caustic and water as necessary. For example, aluminum hydroxide and sodium hydroxide can be mixed in water and dissolved by heating to prepare a sodium aluminate solution, and water can be added to this solution while stirring to obtain an aqueous solution as an aluminum source. Such molar ratio and concentration adjustment can also be carried out by introducing water into the reaction vessel in advance and adding a high concentration alkali metal aluminate salt solution and caustic alkali thereto.
[0019]
In the compound containing an alkaline earth metal to be coexisted in the reaction system, Mg, Ca, Sr, Ba, etc. are used as the alkaline earth metal, and among these, Mg and Ca are suitable in terms of easy availability of raw materials and cost. Used. These may be used alone or in combination of two or more. These are added to the reaction system as alkaline earth metal hydroxides or alkaline earth metal salts such as carbonates, sulfates, chlorides and nitrates. Moreover, it is preferable from the point of the uniformity of reaction etc. to add as aqueous solution, It is especially preferable to use those water-soluble salts, and chloride aqueous solutions, such as Ca and Mg, are used especially suitably. Alkaline earth metal hydroxides and alkaline earth metal salts only need to coexist when the silica source reacts with the aluminum source, but the silica source and / or the aluminum source particularly in an aqueous solution state. It is preferable to add it in advance, and it is more preferable to add it to the silica source. Then, it is preferable to perform a zeolite synthesis reaction by mixing the silica source and the aluminum source. In particular, in order to obtain fine particles, it is preferable to carry out the reaction by supplying raw materials also into the circulation line of the reaction tank having a circulation system (circulation line) outside. In the middle of the circulation line, a wet mixer (for example, a homomic line mill, a homomic line mixer, a homogenizer, a static mixer, so that the slurry formed after each raw material is supplied to the circulation line can pass through. It is preferable to install a crusher such as a gear pump, a turbine pump, or a centrifugal pump, a disperser, and a crusher.
[0020]
The component (a) is different from the method of substituting Na ions and alkaline earth metal ions after the synthesis, by incorporating the alkaline earth metal into the structure of the zeolite at the time of synthesis, thereby acting on the zeolite network. Zeolite with a small primary particle size is produced. In this respect, the alkaline earth metal is desirably involved in the reaction at the initial stage of the reaction and / or during crystallization.
[0021]
The composition of the anhydride of component (a) is preferably general formula (I) in terms of cleaning performance.
xM ₂ O ・ ySiO ₂ ・ Al ₂ O _Three ZMeO (I)
[However, M represents an alkali metal (preferably Na and / or K, more preferably Na), Me represents an alkaline earth metal, and x = 0.2 to 2 (preferably 0.6 to 1.3). ), Y = 0.5-6 (preferably 0.9-5), z = 0.005-0.1 (preferably 0.01-0.03)].
[0022]
The crystal form of the component (a) has a known crystal form, and examples thereof include A type, X type, Y type, and P type. From the viewpoint of cleaning performance, X type and A type are preferable, and A type is more preferable. These generated crystal phases may be a single phase or a mixed phase.
[0023]
<(B) component>
The composition of the present invention has a component (b) of 5 to 60% by weight, more preferably 10 to 50% by weight, even more preferably 20 to 48% by weight, particularly 25 in terms of cleaning performance and solubility of the composition in water. It is preferable to contain -45weight%.
[0024]
As the surfactant, (b1) a nonionic surfactant, (b2) an anionic surfactant, a cationic surfactant and an amphoteric surfactant can be used. From the viewpoint of detergency such as oily dirt, it is preferable to use (b1) a nonionic surfactant. Moreover, it is preferable to use an anionic surfactant (b2) in terms of detergency such as mud dirt. It is preferable to contain the component (b1) and / or the component (b2) in terms of cleaning performance, and it is more preferable to contain the component (b1) in terms of solubility of the composition in water.
[0025]
(B1) As the nonionic surfactant, an aliphatic alcohol having 8 to 20 carbon atoms in the alkyl group, a fatty acid and fatty acid alkyl ester having 9 to 21 carbon atoms in the alkyl group, and 8 to 8 carbon atoms in the alkyl group. Ethylene oxide (hereinafter referred to as EO) and propylene oxide (hereinafter referred to as PO) were added to a compound having one or more atoms having an unshared electron pair, such as 20 aliphatic amines, according to a conventional method. And those having a sugar-derived polyol as a hydrophilic group, amine oxides or fatty acid amides. Among these, polyalkylene glycol alkyl ethers are preferable, nonionic surfactants represented by the following general formula (b1-1) and / or (b1-2) are more preferable, and the type of the general formula (b1-2) Is more preferable from the viewpoint of the usability of the composition.
[0026]
R ¹ O (EO) _m H (b1-1)
[In the formula, R ¹ Is a primary alkyl group and / or a secondary alkyl group having an average carbon number of 8 to 20, preferably 10 to 18. EO is an ethyleneoxy group, and m is 5 to 20 as an average added mole number. ]
R ² O (EO) _k / (PO) _l H (b1-2)
[In the formula, R ² Is a primary alkyl group having an average carbon number of 8 to 20, preferably 10 to 18. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group. k and l are average addition mole numbers, k is 5-15, l is 1-5. EO and PO may be added randomly or after adding EO, PO may be added, or vice versa. ].
[0027]
Among the nonionic surfactants of the general formula (b1-2), by using a nonionic surfactant represented by the following general formula (b1-3), a high detergency against Eli, Sorrow and Mouth Stain Obtainable.
[0028]
R ^Three O (EO) _p (PO) _q (EO) _r H (b1-3)
[In the formula, R ^Three Is a linear alkyl group or alkenyl group having 8 to 20 carbon atoms. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group. p, q, and r represent average added mole numbers, and are p> 0, q = 1-4, r> 0, p + q + r = 6-14, p + r = 5-12. Preferably, p + q + r = 7 to 14, p + r = 6 to 12, and q = 1 to 2. ].
[0029]
As nonionic surfactants, in addition to those shown above, alkylpolysaccharide surfactants represented by the following general formula (b1-4), and also represented by the following general formula (b1-5) Amine oxide, fatty acid alkanolamide, polyhydroxy fatty acid amide and the like can be used.
[0030]
R ^Four − (OR ^Five ) _x G _y (B1-4)
[In the formula, R ^Four Is a linear or branched alkyl group having 8 to 18 carbon atoms, alkenyl group, or alkylphenyl group, R ^Five Represents an alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms, x represents a number having an average value of 0 to 6, and y represents a number having an average value of 1 to 10. ]
[0031]
[Chemical 1]

[0032]
[In the formula, R ⁶ Is an alkyl or alkenyl group having an average carbon number of 8 to 20, preferably 12 to 18, or R ⁹ C (= O) NH (CH ₂ ) _z , R ⁹ Is an alkyl group or alkenyl group having an average carbon number of 8 to 20 (preferably 12 to 18), and z is 1 to 5. Also R ⁷ , R ⁸ Are each CH _Three , C ₂ H _Five Or C ₂ H _Four OH. ].
[0033]
(B2) As anionic surfactant, alkylbenzene sulfonate, alkyl sulfate ester salt, alkyl or alkenyl ether sulfate ester salt, α-olefin sulfonate salt, α-sulfo fatty acid salt or ester thereof, alkyl or alkenyl ether Examples thereof include carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants and the like. In particular, a linear alkylbenzene sulfonate having 10 to 14 carbon atoms, an alkyl sulfate ester salt or an alkyl ether sulfate ester salt having 10 to 18 carbon atoms, and the counter ion is an alkali metal such as sodium or potassium, or an alkali such as magnesium. Amines such as earth metals, monoethanolamine, diethanolamine, triethanolamine are preferred. In particular, liquid stability is improved by using alkanolamine. Moreover, an anionic surfactant may be mix | blended in a composition with an acid form, and you may neutralize with the alkali agent (alkanolamine etc.) added separately.
[0034]
Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts.
[0035]
Examples of amphoteric surfactants include carbobetaine type and sulfobetaine type.
[0036]
<(C) component>
The composition of the present invention contains the component (c) in an amount of 1 to 70% by mass, further 1 to 50% by mass, further 1 to 30% by mass, particularly 3 to 15% by mass in terms of stability and detergency. It is preferable to do. In the present invention, the content of water refers to the content of water other than crystal water.
[0037]
<(D) component>
In the composition of the present invention, the component (d) is preferably 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, and still more preferably 0.1% in terms of separation stability and washing performance. -10% by mass, particularly preferably 0.5-8% by mass.
[0038]
Examples of the component (d) include a liquid phase density adjusting agent, a liquid phase viscosity adjusting agent, and a secondary aggregation preventing agent of the component (a). Especially, the secondary aggregation inhibitor of (a) component is preferable at the point of ease of use and stability.
[0039]
As a specific example of the component (d), the density is 2 g / cm. ^Three Particles having a particle diameter of 50 nm or less (silica, titanium dioxide, barium sulfate, bentonite, etc.), xanthan gum, guar gum, carboxymethyl cellulose (salt), hydroxyethyl cellulose (salt), cationized cellulose, polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylic acid , Polyethylene glycol, lignin sulfonic acid (salt), polyethyleneimine, acrylic acid (salt) / maleic acid (salt) polymer, acrylic acid (salt) / methacrylic acid (salt) polymer, and the like. In terms of stability, a monomer group constituting a polymer that is soluble or uniformly dispersible in the liquid phase containing the component (b) and the component (c), and a monomer group having a functional group having a high affinity for the component (a) Polymerize or degenerate one or more monomers each selected from Those obtained by is preferred.
[0040]
Examples of the monomer group constituting a polymer that is soluble or uniformly dispersible in the liquid phase include (i) to (p).
(I) Vinyl ethers having an unsubstituted or substituted saturated or unsaturated alkyl group having 1 to 22 carbon atoms or an aralkyl group. For example, methyl vinyl ether, ethyl vinyl ether, 4-hydroxybutyl vinyl ether, phenyl vinyl ether and the like are preferable.
(J) Unsubstituted or substituted (meth) acrylamides having a saturated or unsaturated alkyl group or aralkyl group having 1 to 12 carbon atoms on nitrogen. For example, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, (meth) acryloylmorpholine, 2 -(N, N-dimethylamino) ethyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N- Butoxymethyl (meth) acrylamide and the like are preferable.
(K) N-vinyl aliphatic amides. For example, N-vinylpyrrolidone, N-vinylacetamide, N-vinylformamide and the like are preferable.
(L) C1-C22 unsubstituted or substituted (meth) acrylic acid esters having a saturated or unsaturated alkyl group or an aralkyl group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2- (meth) acrylic acid 2- Methoxyethyl and the like are preferable.
(M) Alkylene oxides. For example, ethylene oxide, propylene oxide and the like are preferable.
(N) Cyclic imino ethers. For example, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline and the like are preferable.
(O) Styrenes. For example, styrene, 4-ethylstyrene, α-methylstyrene and the like are preferable.
(P) Vinyl esters. For example, vinyl acetate and vinyl caproate are preferable.
[0041]
In addition to the polymer obtained from the above monomer group, examples of the polymer that is soluble or uniformly dispersible in the liquid phase include the structures of (q) to (s), and these structures are compatible with the solid components described later. A polymer comprising at least one monomer group having a highly functional group is also preferred.
(Q) Polyesters composed of a dihydric alcohol and a divalent carboxylic acid. For example, polyethylene glycol and terephthalic acid, or a polycondensate of 1,4-butanediol and succinic acid is preferable.
(R) Polyamides. For example, a ring-opening polymer of N-methylvalerolactam is preferable.
(S) Polyurethanes. For example, polyaddition products of polyethylene glycol, hexamethylene diisocyanate and N-methyldiethanolamine or 1,4-butanediol are preferred.
[0042]
Preferred functional groups having a high affinity for component (a) include carboxyl groups, sulfonic acid groups, hydroxyl groups, and primary to quaternary ammonium groups. Examples of monomers having these functional groups include (meth) acrylic acid and its salts, styrene carboxylic acid and its salts, maleic acid and its salts, itaconic acid and its salts, styrene sulfonic acid and its salts, (meth) allyl sulfone Acids and salts thereof, 2-acrylamido-2-methylpropanesulfonic acid and salts thereof, vinylsulfonic acid and salts thereof, vinyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylamide, 4- Hydroxymethylstyrene, mono-2-((meth) -acryloyloxy) ethyl phosphate, 2-((meth) acryloyloxy) ethyl trimethylammonium chloride, vinylbenzyltrimethylammonium chloride, 2-((meth) acryloyloxy ethyl sulfate ) Ethyldimethylethylammonium, Of 3 - ((meth) acrylamide) trimethylammonium, diallyldimethylammonium chloride, vinylpyridine, and the like.
[0043]
Among these, a preferred polymer dispersant is a block or graft polymer of a polymer that is soluble or uniformly dispersible in the liquid phase and a polymer having a functional group having a high affinity for the component (a).
[0044]
Due to the presence of the two types of segments, the effects of both can be expressed without being offset. In order to express both effects higher, it is particularly preferable to use a graft polymer. The weight ratio of the two segments in the block or graft polymer [(polymer segment soluble or uniformly dispersible in the liquid phase) / (polymer segment having a functional group with high affinity for component (a))] is: 5/95 to 95/5 are preferable. Such block or graft polymer synthesis methods include, for example, a method of polymerizing vinyl monomers using a macroazo initiator having an azo group in the polymer chain (macroazo initiator method), a polymerizable group at one end of the polymer chain. A method using a compound having a macromolecule (macromonomer method), and radical polymerization of the monomer in the presence of the polymer so that the newly generated polymer chain is linked to the previously coexisting polymer chain by a chain transfer reaction The method (chain transfer method) is preferred. As a polymer type dispersant obtained by these methods, for example, a block polymer obtained by radical polymerization of acrylic acid (or a salt thereof) using a polyethylene glycol macroazo initiator, a polyethylene glycol mono (meth) acrylate ester And a copolymer of (meth) acrylic acid or a salt thereof, a copolymer of polyethylene glycol mono (meth) acrylic acid ester and styrenesulfonic acid or a salt thereof, polyethylene glycol mono (meth) acrylic acid ester and 2-chloride Copolymer with ((meth) acryloyloxy) ethyltrimethylammonium, copolymer with polyethylene glycol mono (meth) acrylate and 2-hydroxyethyl (meth) acrylate, polyethylene glycol or polypropylene glycol or polyethylene glycol propylene Glico Radical polymerization of diallyldimethylammonium chloride in a graft polymer obtained by radical polymerization of acrylic acid and maleic acid (or a salt thereof) in aqueous solution of poly (N, N-dimethylacrylamide / styrene) copolymer Examples thereof include a graft polymer obtained, a graft polymer obtained by radical polymerization of styrenesulfonic acid (or a salt thereof) in an aqueous poly (N, N-dimethyl (meth) acrylamide) solution, and the like. The weight average molecular weight of these polymer type dispersants is preferably 1,000,000 or less, more preferably 1,000 to 500,000, and particularly preferably 10,000 to 300,000 for the purpose of preventing an excessive increase in viscosity.
[0045]
<Other ingredients>
The composition of the present invention includes (1) 0.1 to 10% by mass of an aluminosilicate other than the component (a), (2) alcohols such as ethanol, glycols such as ethylene glycol and propylene glycol, and paratoluene sulfone. 0.01-30% by weight of a thickener and solubilizer such as acid, benzoate (also effective as a preservative) and urea, (3) polyoxyalkylene benzyl ether, polyoxyalkylene phenyl ether, etc. 0.01 to 30% by mass of a regulator and a detergency improver, (4) an anti-staining agent and a dispersant of 0.01 to 10% by mass such as polyethylene glycol having an average molecular weight of 5000 or more, naphthalene sulfonate formalin condensate, (5) 0.01-10% by mass of a color transfer inhibitor such as polyvinylpyrrolidone, (6) sodium percarbonate or sodium perborate, etc. Bleach activators such as bleach activators such as 0.01 to 10% by weight of bleach, (7) tetraacetylethylenediamine, and general formulas (I-2) to (I-7) of JP-A-6-316700 0.01 to 10% by mass, (8) 0.001 to 1% by mass of a fluorescent dye such as Chino Pearl CBS (manufactured by Ciba Specialty Chemicals Co., Ltd.) and Whiteex SA (manufactured by Sumitomo Chemical Co., Ltd.), (9) No. 60480, soft base such as silicone according to claim 1, 0.1-2% by mass, (10) 0.01-2% by mass of antifoaming agent such as silica, (11) butylhydroxytoluene, distyrenation 0.01 to 2% by mass of an antioxidant such as cresol, sodium sulfite and sodium hydrogen sulfite, (12) bluing agent, (13) cellulase, amylase, pectinase, protease, liper (14) Enzyme stabilizers such as (14) calcium chloride, calcium sulfate, formic acid, boric acid (boron compounds), (15) perfumes, (16) antibacterial preservatives, (17) coloring agents, etc. Can do.
[0046]
Especially in terms of cleaning performance and stability, amines such as monoethanolamine, diethanolamine, triethanolamine, methylmonoethanolamine, dimethylethanolamine and 3-aminopropanol, alkali metal water such as sodium hydroxide and potassium hydroxide It is preferable to blend alkali agents such as oxides, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal silicates such as sodium silicate and potassium silicate, among them alkali metal carbonates such as sodium carbonate and potassium carbonate. Is preferable in terms of cleaning performance. These alkali agents are preferably contained in the composition in an amount of 0.5 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably 3 to 20% by mass.
[0047]
<Manufacturing method>
The liquid detergent composition of the present invention can be obtained by mixing the components (a) to (c), and if necessary, the component (d) and other components by a conventional method, but in terms of separation stability, It is preferable to provide a step of mixing the components (a) to (c) and, if necessary, the component (d) and other components, and a step of treating the resulting mixture with a wet pulverizer. The wet pulverizer is not particularly limited. For example, among the pulverizers described in Chemical Engineering Handbook of Chemical Engineering (Maruzen, 1988), 5th edition, pages 826-838, a wet pulverizer is used. Can do. Among these, a pulverizer using a pulverization medium such as a sand mill, a vibration mill, an attritor, or a dyno mill is preferably used. A wet pulverization method using media is particularly preferable in terms of pulverization force and productivity. As the medium, a known material such as titania, zirconia, or silica can be used. A media diameter of 0.1 to 3 mm is particularly preferable.
[0048]
In terms of cleaning performance and stability, the reduction rate of the average primary particle size of the component (a) before and after the treatment by the wet pulverizer is preferably 0 to 50%, more preferably 0 to 20%. That is, in the treatment by the wet pulverizer, it is preferable to reduce the aggregate particle diameter without significantly reducing the average primary particle diameter of the component (a).
[0049]
【Example】
Examples 1-6, Comparative Examples 1-3
The liquid detergent composition shown in Table 1 was prepared by the following method, and the obtained composition was evaluated for ease of use, evaluation of cleaning power, and evaluation of separation stability as described below. The results are shown in Table 1. In addition, all the viscosity of 25 degreeC of the obtained composition was 100-500 mPa * s, and the pH of 25 degreeC was 10-11 in all. Moreover, the average aggregate particle diameter of the solid component contained in the liquid detergent composition was 0.5 μm or less except for Comparative Example 2.
[0050]
[Method for preparing liquid detergent composition]
About each liquid detergent composition shown in Table 1, the compounding component except an enzyme and a fragrance | flavor was measured and mixed in the ratio with respect to 100 g of liquid detergent compositions. Next, the mixture was filled with 500 g of zirconia beads having a diameter of 0.5 mm using a batch type sand mill (capacity 1 L, manufactured by Imex Co., Ltd.), and pulverized for 1 hour at a disk rotational speed of 1500 r / min (15 in a jacket type cooler). While circulating water at 0 ° C.). The resulting liquid-solid mixture was passed through a 40 mesh screen to remove zirconia beads. Further, if necessary, enzymes and fragrances were added and stirred and mixed at room temperature to obtain a liquid detergent composition.
[0051]
[Evaluation of ease of use]
After putting 80 mL of each sample solution into a 100 mL graduated cylinder and letting it stand in a constant temperature room at 25 ° C., a washing machine (Toshiba Galaxy 3. 6 (VH-360S1)), and the ease of use was evaluated according to the following criteria.
It is easy to charge the liquid, and it is easy to adjust the liquid volume. ... 3 points
Although it is easy to add the liquid, it is difficult to adjust the amount of the liquid. ... 2 points
Although it is difficult to charge the liquid, it is easy to adjust the amount of the liquid. ... 2 points
It is difficult to charge the liquid and it is difficult to adjust the amount of the liquid. ... 1 point
With the average score of 10 people, the evaluation of the sample solution was determined as follows.
○: Average score of 2.5 or higher
Δ: Average score of 2 or more and less than 2.5
X: An average score of 1 or more and less than 2.
[0052]
[Evaluation of cleaning power]
According to the method for evaluating the cleaning power of a synthetic detergent for clothing described in JIS K 3362: 1998, the cleaning power of the liquid detergent composition in Table 1 and the index detergent for determining cleaning power were compared. The use concentration of the liquid detergent composition in Table 1 was 20 g / 30 L.
○: At least equivalent to index detergent
X: Inferior to index detergent.
[0053]
[Evaluation of separation stability]
A 50 mL sample bottle (No. 6 wide-mouth standard bottle, made of glass, cylindrical shape with a diameter of 40 mm and a height of 80 mm) was filled with 40 mL of the liquid detergent composition shown in Table 1 and covered, followed by a constant temperature room at 40 ° C. And left for 30 days. The stability of the liquid was visually determined based on the following criteria.
○: Uniformly dispersed
×: Separation or sedimentation is observed
[0054]
[Table 1]

[0055]
Fine particle zeolite A: zeolite obtained by the following synthesis example (1)
Synthesis example (1)
The apparatus shown in FIG. 1 was used. No. 3 water glass was put into the raw material tank 1 and stirred. Subsequently, a 48% sodium hydroxide aqueous solution is put into the raw material tank 1, and then a calcium chloride solution obtained by mixing a 35% calcium chloride solution and ion-exchanged water in advance is added over 1 minute, and the temperature is raised to 50 ° C. did. Next, with the agitator 3 kept moving, sodium aluminate was added to the reaction vessel 2 and the temperature was raised to 50 ° C. After the temperature rise, while the aluminum source (sodium aluminate) was circulated through the circulation line 5 with the liquid feed pump 7, the rotation speed of the mixer 4 was set to 2400 rpm, and the silica source in the raw material tank 1 (No. 3 water glass, 48% A water glass solution comprising an aqueous sodium hydroxide solution and a calcium chloride solution) was supplied to the circulation line 5 through the raw material supply line 6 over 8 minutes to carry out the reaction. After the completion of the reaction, the slurry obtained in the circulation line 5 was continuously circulated while the temperature was raised to 80 ° C., and the mixture was aged for 1 hour while being kept at 80 ° C. The resulting slurry was washed with filtered water until the pH of the filtrate was 11.4. Thereafter, it was dried to obtain a zeolite powder. Table 2 shows the charging conditions and reaction conditions, and the composition and physical properties of the obtained zeolite (the methods for measuring the cation exchange capacity, the average primary particle diameter, and the average aggregate particle diameter are as described above; the same applies hereinafter). Na ₂ O / H ₂ The molar ratio of O was 0.06.
Fine particle zeolite B: zeolite obtained by the following synthesis example (2)
Synthesis example (2)
The apparatus shown in FIG. 2 was used. No. 3 water glass was placed in the raw material tank 8 and stirred. Next, a calcium chloride solution obtained by mixing a 35% calcium chloride solution and ion-exchanged water in advance was added to the raw material tank 8 over 1 minute, and then the temperature was raised to 50 ° C. Next, with the agitator 10 kept moving, sodium aluminate and a 48% aqueous sodium hydroxide solution were added to the reaction vessel 9 and the temperature was raised to 50 ° C. After the temperature rise, while the aluminum source (sodium aluminate solution consisting of sodium aluminate and 48% sodium hydroxide aqueous solution) was circulated through the circulation line 12 with the feed pump 14, the rotational speed of the mixer 11 was 3600 rpm, The silica source (water glass solution consisting of No. 3 water glass and calcium chloride solution) in the tank 8 was supplied to the circulation line 12 through the raw material supply line 13 over 3.5 minutes to carry out the reaction. After the completion of the reaction, the slurry obtained in the circulation line 12 was continuously circulated, the temperature was raised to 80 ° C., and the mixture was aged for 2 hours while being kept at 80 ° C. The resulting slurry was washed with filtered water until the pH of the filtrate was 11.4. Thereafter, it was dried to obtain a zeolite powder. Table 2 shows the charging conditions and reaction conditions, and the composition and physical properties of the obtained zeolite. Na ₂ O / H ₂ The molar ratio of O was 0.06.
[0056]
[Table 2]

[0057]
Fine particle zeolite C: zeolite obtained by the following synthesis example (3)
Synthesis example (3)
1297.2 g of 48% NaOH was added to a 2 liter stainless steel separable flask, and then 1000 g of aluminum hydroxide (purity 99%) was added with stirring. Then, the temperature was raised, heated at 120 ° C. for 1 hour, cooled, and sodium aluminate (Na ₂ O: 21.01%, Al ₂ O _Three : 28.18%).
[0058]
320 g of sodium aluminate obtained by the above method was placed in a 2 liter stainless steel separable flask (inner diameter: 12 cm), and then 316.1 g of 48% NaOH aqueous solution was added to obtain an aluminum source.
[0059]
Next, No. 3 water glass (Na ₂ O: 9.68%, SiO ₂ : 29.83%) 355.6 g was put into another 2 liter stainless steel separable flask, and calcium chloride aqueous solution prepared by mixing 2.94 g of anhydrous calcium chloride with 819.8 g of ion-exchanged water therein was stirred. This solution was used as a silica source containing an alkaline earth metal.
[0060]
The aluminum source was heated to 50 ° C. while stirring at 300 rpm with a stirring blade having a blade diameter of 11 cm. Similarly, the silica source was heated to 50 ° C. When both raw materials became 50 degreeC, the silica source was dripped and added over 5 minutes in the aluminum source using the roller pump. After completion of dropping, the temperature was maintained at 50 ° C. to 60 ° C. for 10 minutes, and then the temperature was raised to 80 ° C. Thereafter, aging was performed with stirring at 80 ° C. for 1.5 hours. The charge composition is SiO ₂ / Al ₂ O _Three = 2, Na ₂ O / Al ₂ O _Three = 4, CaO / Al ₂ O _Three = 0.03. The solid content concentration during the reaction was 23%.
[0061]
The resulting slurry was washed with filtered water until the pH of the filtrate was 11.4. And it dried at 100 degreeC for 13 hours, and obtained the powder of the zeolite.
[0062]
The composition of the zeolite obtained is 1.05 Na as an anhydride. ₂ O ・ 2.05SiO ₂ ・ Al ₂ O _Three -0.03CaO (in general formula (I), x = 1.05, y = 2.05, z = 0.03). From the X-ray diffraction pattern, the crystal form is ASTM No. It was an A-type zeolite belonging to 38-241.
[0063]
The average primary particle size is 0.75 μm, and the cation exchange capacity for 1 minute is 165 mg CaCO. _Three / G cation exchange capacity for 10 minutes is 210 mg CaCO _Three It was a fine particle zeolite excellent in cation exchange capacity, which was / g. Further, the average aggregate particle size was 3.4 μm, and the dispersion parameter defined by the product of the average primary particle size and the average aggregate particle size was 2.6.
Nonionic surfactant A: a linear primary alcohol having 10 to 14 carbon atoms, in which EO is added in an average of 3 moles, PO is added in an average of 2 moles, and EO is added in blocks in the order of 3 moles
・ Nonionic surfactant B: An average of 7 moles of EO added to a linear secondary alcohol having 12 to 14 carbon atoms (Softanol 70, manufactured by Nippon Shokubai Co., Ltd.)
Nonionic surfactant C: In the general formula (b1-4), R ^Four Is a branched primary alkyl group having 9 to 11 carbon atoms, x = 0, y = 1.3, and G is a glucose residue.
Anionic surfactant A: alkyl alkyl C10-14 linear alkylbenzene sulfonate sodium (average molecular weight 345)
Anionic surfactant B: an alkyl ether sulfate sodium salt obtained by adding an average of 3 moles of EO to a branched primary alcohol having an average carbon number of 12.2 per molecule
Fatty acid: Coconut oil fatty acid having 12 to 16 carbon atoms (Lunac L-55, manufactured by Kao Corporation)
4A zeolite (1): Type 4A zeolite (Toyo Builder, manufactured by Tosoh Corporation), average primary particle size of 3 μm during synthesis, average primary particle size of 2 μm in composition, cation exchange capacity of 180 mg CaCO for 1 minute _Three / G or more, cation exchange capacity 200 mg CaCO for 10 minutes _Three / G or more, and not obtained by reacting a silica source and an aluminum source in the presence of a compound containing an alkaline earth metal.
4A zeolite (2): 4A type zeolite (Toyo Builder, manufactured by Tosoh Corp.) pulverized and adjusted to an average primary particle size of 0.8 μm, an average primary particle size of 0.5 μm in the composition for 1 minute Cation exchange capacity 180mgCaCO _Three / G or more, cation exchange capacity 200 mg CaCO for 10 minutes _Three / G or more, and not obtained by reacting a silica source and an aluminum source in the presence of a compound containing an alkaline earth metal.
-Dispersant A: Aqualock FC600S (manufactured by Nippon Shokubai Co., Ltd.) freeze-dried, weight average molecular weight 68,000 (in terms of polyethylene glycol)
Dispersant B: Block polymer of polyethylene glycol and polyacrylic acid (40/60 (mass ratio)), weight average molecular weight 222,000 (in terms of polyethylene glycol)
Dispersant C: Polyethylene glycol (EO addition mole number 9) copolymer of monomethacrylic acid ester / methacrylic acid (80/20 (mass ratio)), weight average molecular weight 39,000 (in terms of polyethylene glycol)
・ Phenol EO 3 mol adduct: Polyoxyethylene monophenyl ether (EO average 3 mol addition)
・ Butyl carbitol: Diethylene glycol monobutyl ether
Pentyl glyceryl ether: n-pentyl monoglyceryl ether
・ Coloring agent: Blue No. 1
Enzyme: Evalase 16.0L type EX (protease, manufactured by Novozyme)
・ Fluorescent dye: Chino Pearl CBS-X (manufactured by Ciba Specialty Chemicals)
[Brief description of the drawings]
FIG. 1 is a schematic view of an apparatus for producing fine particle zeolite used in Synthesis Example (1).
FIG. 2 is a schematic view of an apparatus for producing fine particle zeolite used in Synthesis Example (2).
[Explanation of symbols]
1, 8 Raw material tank
2, 9 Reaction tank
3, 10 Agitator
4,11 Mixer
5,12 Circulation line
6, 13 Raw material supply line
7, 14 Liquid feed pump

Claims (5)

(A) 5-50% by mass of fine particle zeolite having an average primary particle size of 1 μm or less obtained by reacting a silica source and an aluminum source in the presence of a compound containing an alkaline earth metal, (b) a surfactant 20-20 A liquid detergent composition for clothing containing 60% by mass and (c) 1 to 50% by mass of water , having a viscosity at 25 ° C. of 50 to 500 mPa · s and a pH at 25 ° C. of 8.5 to 11 . The liquid detergent composition for clothing according to claim 1, wherein the composition of the anhydrous fine particle zeolite is the general formula (I).
_{xM 2 O · ySiO 2 · Al} 2 O 3 · zMeO (I)
[However, M represents an alkali metal, Me represents an alkaline earth metal, x = 0.2-2, y = 0.5-6, z = 0.005-0.1] Furthermore, the liquid cleaning composition for clothes in any one of Claim 1 or 2 containing the dispersion stabilizer of (d) (a). Step (i) of mixing (a), (b), (c) and, if necessary, (d), and step (ii) of treating the mixture obtained in step (i) with a wet pulverizer The manufacturing method of the liquid cleaning composition for garments in any one of Claims 1-3 . The manufacturing method of the liquid cleaning composition for clothes of Claim 4 whose average aggregate particle diameter of the solid component in the liquid cleaning composition for clothes is 1 micrometer or less.

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