JP3776312B2 - Liquid detergent composition - Google Patents

Description

【００２１】
〔式中、Ｒ¹は炭素数８〜１６、好ましくは１０〜１６、特に好ましくは１０〜１４の直鎖アルキル基又はアルケニル基であり、Ｒ³、Ｒ⁴は炭素数１〜３のアルキル基又はヒドロキシアルキル基である。Ｒ²は炭素数１〜５、好ましくは２又は３のアルキレン基である。Ａは−ＣＯＯ−、−ＣＯＮＨ−、−ＯＣＯ−、−ＮＨＣＯ−、−Ｏ−から選ばれる基であり、ｒは０又は１の数である。〕。
【００２２】
Ｒ⁵−Ｏ(ＥＯ)_nＨ （ii）
〔式中、Ｒ⁵は平均炭素数８〜１６、好ましくは１０〜１６の直鎖アルキル基である。ＥＯはエチレンオキサイドであり、ｎは平均付加モル数として５〜２０である。〕
Ｒ⁶−Ｏ[(ＥＯ)_p／(ＰＯ)_q]Ｈ （iii）
〔式中、Ｒ⁶は平均炭素数８〜１６、好ましくは１０〜１６の直鎖アルキル基である。ＥＯはエチレンオキサイド、ＰＯはプロピレンオキサイドを示す。ｐは５〜１５、ｑは１〜５である。ＥＯとＰＯはランダム付加又はＥＯを付加した後、ＰＯを付加してもよく、またその逆のようなブロック付加体でもよい。〕
Ｒ⁷−(ＯＲ⁸)_xＧ_y （iv）
〔式中、Ｒ⁷は直鎖の炭素数８〜１６のアルキル基、アルケニル基、又はアルキルフェニル基、Ｒ⁸は炭素数２〜４のアルケニル基、Ｇは炭素数５又は６の還元糖に由来する残基、ｘは平均値０〜６の数、ｙは平均値１〜１０の数を示す。〕。
【００２３】
本発明では分岐型及び直鎖型の界面活性剤を混合して使用するが、洗浄効果及び適度な粘度が得られる点から、分岐鎖と直鎖を合わせた全アミンオキシドを組成物中に１〜１０重量％、特に３〜９重量％含有することが好ましく、全非イオン界面活性剤の含有量が組成物中１〜２０重量％、特に３〜１５重量％であることが好ましい。更に、適度な粘度が得られる点から、全ポリオキシアルキレンアルキルエーテル硫酸エステル塩／全アミンオキシドの重量比は、好ましくは２／１〜１０／１、特に好ましくは３／１〜１０／１である。
【００２４】
本発明では上記界面活性剤以外の界面活性剤を配合することができるが、目的の粘度を損なわないことが重要である。陰イオン界面活性剤としては通常液体洗浄剤に使用する直鎖アルキルベンゼンスルホン酸塩、α−スルホ脂肪酸エステル塩、α−オレフィンスルホン酸塩、アルカンスルホン酸塩を配合しても差し支えないが、これら陰イオン界面活性剤の配合量は上記性質を満足するために５重量％以下、好ましくは３重量％以下が好ましい。また、両性界面活性剤としてカルボベタイン、スルホベタインを配合することができるが、これら両性界面活性剤の配合量は好ましくは５重量％以下、より好ましくは３重量％以下である。
【００２５】
本発明の組成物は、粘度及び粘度安定性の点から、さらに組成物中にアルカリ金属陽イオン及び／又はアルカリ土類金属陽イオンを好ましくは２〜１０重量％、より好ましくは３〜８重量％含有することが望ましい。アルカリ金属陽イオンとしてはナトリウムイオン、カリウムイオンが良好であり、アルカリ土類金属としてはマグネシウムイオンが良好である。本発明では特にマグネシウムイオンを好ましくは０．２〜２重量％、より好ましくは０．３〜１．５重量％の濃度で配合すること好ましい。本発明において、陽イオンの量は、陰イオン界面活性剤の対イオンや他の成分から取り込まれたものすべてを含み、含有量が足りない場合は、硫酸ナトリウム、硫酸カリウム、硫酸マグネシウム、塩化ナトリウム、塩化カリウム、塩化マグネシウム、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウムから選ばれる１種以上の水溶性無機塩を上記範囲に入るように添加すればよい。また、これら陽イオンが多すぎる場合には電気透析などの手法を用いて塩を除去することが好ましい。このような無機の陽イオンの量は、例えば組成物全体を通常の原子吸光法などの無機分析法により定量することで求めることができる。
【００２６】
本発明では水への溶解性と目的の粘度に調整するために水溶性有機溶媒を配合する。水溶性有機溶媒としては（１）炭素数１〜５の１価アルコール、（２）炭素数４〜１２の多価アルコール、（３）下記の一般式（ｖ）で表される化合物、（４）下記の一般式（vi）で表される化合物、（５）下記の一般式（vii）で表される化合物が好ましい。
【００２７】
【化２】

【００２８】
〔式中、Ｒ⁹及びＲ¹⁰は、それぞれ水素原子、炭素数１〜６のアルキル基、フェニル基又はベンジル基を示すが、Ｒ⁹及びＲ¹⁰の双方が水素原子となる場合を除く。ｓは０〜１０の数を、ｔは０〜１０の数を示すが、ｓ及びｔの双方が０である場合を除く。Ｒ¹¹及びＲ¹²は炭素数１〜３のアルキル基を示す。Ｒ¹³は炭素数１〜８のアルキル基を示す。〕。
【００２９】
（１）の炭素数２〜５の１価アルコールとしては、エタノール、プロピルアルコール、イソプロピルアルコールが挙げられる。これらの低級アルコールを配合することにより低温における系の安定性を更に向上させることができる。
【００３０】
（２）の炭素数４〜１２の多価アルコールとしては、イソプレングリコール、２，２，４−トリメチル−１，３−ペンタンジオール、１，８−オクタンジオール、１，９−ノナンジオール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、グリセリン等が挙げられる。
【００３１】
（３）の化合物は、一般式（ｖ）において、Ｒ⁹、Ｒ¹⁰がアルキル基である場合の炭素数は１〜４が特に好ましい。また、一般式（ｖ）中、ＥＯ及びＰＯの平均付加モル数のｓ及びｔは、それぞれ０〜１０の数である（ｓ及びｔの双方が０である場合を除く）が、これらの付加順序は特に限定されず、ランダム付加したものであってもよい。（３）の化合物の具体例としては、エチレングリコールモノブチルエーテル、ジプロピレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールジメチルエーテル、ポリオキシエチレン（ｐ＝２〜３）ポリオキシプロピレン（ｐ＝２〜３）グリコールジメチルエーテル（ｐは平均付加モル数を示す）、ポリオキシエチレン（ｐ＝３）グリコールフェニルエーテル、フェニルカルビトール、フェニルセロソルブ、ベンジルカルビトール等が挙げられる。このうち、洗浄力及び使用感の点から、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、ポリオキシエチレン（ｐ＝１〜４）グリコールフェニルエーテルが好ましい。
【００３２】
また、（４）の化合物としては、１，３−ジメチル−２−イミダゾリジノン、１，３−ジエチル−２−イミダゾリジノンが好適なものとして例示され、（５）の化合物としてはアルキルグリセリルエーテル化合物が好適なものとして例示され、中でもＲ¹³が炭素数３〜８のアルキル基の化合物が好ましい。
【００３３】
これらのなかでも本発明の性質を満たすために（１）、（２）、（３）及び（５）の水溶性有機溶媒が好ましく、特にエタノール、イソプロピルアルコール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、グリセリン、イソプレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ペンチルグリセリルエーテル、オクチルグリセリルエーテルから選ばれる水溶性有機溶媒が好ましい。
【００３４】
本発明の組成物では、溶解性の点より、このような水溶性有機溶媒を１〜１０重量％、好ましくは２〜８重量％配合するが、エタノールの配合量は洗浄力の点で組成物中５重量％、好ましくは３重量％を超えないことが好ましい。水溶性有機溶媒を多く配合すると、粘度低下だけでなく流動性が増すため低温において結晶が発生しやすくなったり、室温で放置した場合、表面から水溶性有機溶媒の揮発により造膜する傾向が強くなる。また、これら水溶性有機溶媒は粘度を低下させる上で効果的な成分であるが、本発明では、水溶性有機溶媒を配合する場合は、液体洗浄剤組成物の粘度が４００ｍＰ・ｓ未満にならないように適宜調整される。粘度が４００ｍＰ・ｓ未満になる量で配合すると、洗浄力の持続性の効果を得ることができない。
【００３５】
本発明の組成物は、更に貯蔵安定性、粘度調整及び粘度安定性（経時に粘度が変化しないこと）の上でハイドロトロープ剤を含有することが好ましい。ハイドロトロープ剤としてはトルエンスルホン酸、キシレンスルホン酸、クメンスルホン酸及びこれらのナトリウム、カリウムあるいはマグネシウム塩が良好であり、特にｐ−トルエンスルホン酸及びその塩が良好である。
【００３６】
本発明の組成物は、ハイドロトロープ剤を好ましくは０．５〜５重量％、特に好ましくは１〜５重量％含有する。
【００３７】
本発明の組成物は、上記成分及び水を配合した水溶液の形態であり、水の含有量は、適度な粘度が得られる点から、２０〜６０重量％、好ましくは３０〜６０重量％、より好ましくは４０〜６０重量％、特に好ましくは４５〜５５重量％である。また、該組成物の２０℃におけるｐＨを６〜８、好ましくは６．５〜７．５にすることが貯蔵安定性や皮膚への安全性の点から好ましい。ｐＨ調整剤としては塩酸や硫酸などの無機酸や、クエン酸、コハク酸、リンゴ酸、フマル酸、酒石酸、マロン酸、マレイン酸などの有機酸などの酸剤や、水酸化ナトリウムや水酸化カリウム、アンモニアやその誘導体、モノエタノールアミンやジエタノールアミン、トリエタノールアミンなどのアミン塩など、炭酸ナトリウム、炭酸カリウムなどのアルカリ剤を、単独もしくは複合して用いることが好ましく、特に塩酸、硫酸、クエン酸から選ばれる酸と水酸化ナトリウム、水酸化カリウムから選ばれるアルカリ剤を用いることが好ましい。
【００３８】
本発明の液体洗浄剤組成物は、２０℃における粘度が４００〜１０００ｍＰａ・ｓ、好ましくは４００〜９００ｍＰａ・ｓ、特に５００〜９００ｍＰａ・ｓであり、このような粘度に調整することにより、直接、可撓性吸収体に含浸させて洗浄するような方法において、洗浄力の持続性を高めることができる。粘度の調整は、分岐鎖を有する界面活性剤の種類や界面活性剤の組み合わせ又は分岐率の調整の他に、前記ハイドロトロープ剤、水溶性有機溶媒、水溶性無機塩及び水の配合量を調整することによって行ってもよい。
【００３９】
なお、本発明でいう粘度は以下のようにして測定する。まずＴＯＫＩＭＥＣ.ＩＮＣ製Ｂ型粘度計モデルＢＭに、ローター番号Ｎｏ.３のローターを備え付けたものを準備する。試料をトールビーカーに充填し２０℃の恒温槽内にて２０℃に調製する。恒温に調製された試料を粘度計にセットする。ローターの回転数を３０ｒ／ｍに設定し、回転を始めてから６０秒後の粘度を本発明の粘度とする。
【００４０】
本発明の液体洗浄剤組成物には、香料成分、着色剤、分散剤、研磨剤及び防菌・防カビ剤等の一般に液体洗浄剤に配合されている成分を、粘度及び安定性に影響しない範囲で配合することができる。
【００４１】
【実施例】
表１に示す成分を用いて洗浄剤組成物を調製した。これら組成物の粘度、洗浄効果の持続性及び水への溶解性を下記の方法で評価した。結果を表１に示す。
【００４２】
＜洗浄力試験＞
・モデル汚れの調整
サラダ油／牛脂を１／１の重量比で混合し、さらに０．１重量％の色素（スタンレッド）を均一に混ぜ込んだモデル油汚れ２ｇをメラミン皿に均一に塗り広げたものをモデル汚染食器とした。
・洗浄方法及び評価方法
市販のスポンジ（金鳥クリーナーＮｏ．５００５、ポリウレタンフォーム）に界面活性剤が０．４４ｇとなる量で、表１の液体洗浄剤組成物及び水道水１５ｇを含浸させ２〜３回手でもみ泡立たせた。これを用いてモデル汚染食器を擦り洗いし、洗浄（食器に付着した色が消えることにより確認）できた皿の枚数を求めた。
【００４３】
＜溶解性試験＞
高さ１３ｍｍ、幅５ｍｍ、厚さ２ｍｍの脚を３本取り付けた直径３５ｍｍの円形ガラス板を２００ｍｌのガラス製ビーカーの中央部に設置し、イオン交換水２００ｍｌ及びテフロン製撹拌子（長さ２５ｍｍ、直径８ｍｍ）を入れ、２５℃の撹拌装置付き恒温水槽で温度が平衡に達するまで放置した。予め２５℃の恒温水槽中で温度を平衡化した組成物０．２５ｍｌを、シリンジを用い、上記ガラス板上面の中央部に静かに静置した。注入後、直ちに回転数１０００回転／分にて３０分間撹拌した。３０分後に組成物が完全に溶解している場合を○、ガラス板上及び液中に組成物が残っている場合を×とした。
【００４４】
【表１】

【００４５】
（注）表中の記号は以下のものを表す。
・ａ−１：イソトリデカノールにＥＯを平均２モル付加させた化合物から得たポリオキシアルキレン分岐鎖アルキルエーテル硫酸エステルナトリウム
・ａ−２：イソトリデカノールにＥＯを平均７モル付加させた非イオン界面活性剤
・ａ−３：Ｎ−イソノナノイルアミノプロピル−Ｎ，Ｎ−ジメチルアミンオキシド
・ｂ−１：ポリオキシエチレンラウリルエーテル硫酸エステルナトリウム（ＥＯ平均付加モル数２）
・ｂ−２：アルキル基の組成が炭素数１２／炭素数１４＝６０／４０の直鎖混合アルキルであり、グルコシド平均縮合度１のアルキルグルコシド
・ｂ−３：ポリオキシエチレンラウリルエーテル（ＥＯ平均付加モル数７）
・ｂ−４：ラウリルジメチルアミンオキシド
・ポリプロピレングリコール：重量平均分子量１２００
・防腐剤：プロキセルＢＤＮ（アビシア株式会社製）
・無機陽イオン量：原子吸光法にて定量したアルカリ金属陽イオン及び／又はアルカリ土類金属陽イオンの量。
・ＥＳ：ポリオキシアルキレンアルキルエーテル硫酸エステル塩
・ｐＨ：１／１０Ｎ−硫酸水溶液又は１／１０Ｎ−水酸化ナトリウムを用いて調整した。[0001]
BACKGROUND OF THE INVENTION
The present invention provides a liquid cleaning composition.
[0002]
[Prior art and problems to be solved by the invention]
Today, as consumers are becoming more aware of the environment, efforts are being made to reduce waste in detergents, increasing the concentration of the composition and reducing the amount of detergent used per time. A technology for reducing the amount of waste by making the container compact has been developed.
[0003]
Further, in addition to the cleaning performance, the cleaning agent is required to have a detergency sustainability. For example, when washing dishes by hand, it is preferable that the number of dishes that can be washed by one impregnation is greater after the flexible absorbent is impregnated with the detergent. As for the dishwashing method, use an aqueous solution obtained by diluting the cleaning agent with water, rub it with a flexible absorbent material such as a sponge or towel while contacting the object to be cleaned such as tableware, or use a cleaning solution and a small amount of water. There is a method of scrubbing tableware or the like using a flexible absorbent directly impregnated with the latter, and the latter method is generally performed.
[0004]
Polyoxyalkylene alkyl ether sulfates, on the other hand, have high detergency and low irritation to the skin, so they are used in dishwashing detergents for hand washing (hereinafter abbreviated as dishwashing detergents) and body washing agents. The However, when the surfactant concentration of the composition containing the polyoxyalkylene alkyl ether sulfate salt is increased, there is a problem that the viscosity of the composition is remarkably increased. As a method for solving this, it is conceivable to use a solvent and a hydrotrope in combination, but there is a problem that the effect is low in a composition having a high content of polyoxyalkylene alkyl ether sulfate.
[0005]
JP-A-53-64209 discloses a highly concentrated liquid detergent composition containing a secondary alcohol ethoxylate sulfate, but the effect of suppressing an increase in viscosity is still unsatisfactory. In addition, the cleaning effect does not last in a method in which a cleaning liquid and a small amount of water are soaked in a flexible absorbent body and rubbed directly onto an object to be cleaned such as tableware.
[0006]
Japanese Patent Application Laid-Open No. 56-141400 discloses a composition containing an amine oxide having a branched alkyl group. However, increasing the surfactant concentration of such a composition also increases the viscosity. cause.
[0007]
Japanese Patent Publication No. 11-513067 discloses a technique relating to a dishwashing detergent that dissolves a detergent having a high surfactant concentration in water without gelation. This technique prevents the gelation of the detergent at a high surfactant concentration by blending an antigelling agent. However, the composition disclosed in the publication cannot clean many dishes when the flexible absorbent is impregnated with a small amount of water and a cleaning liquid.
[0008]
Therefore, the problem of the present invention is that, even if the surfactant concentration is high, it has an appropriate viscosity, not only has excellent solubility when used in water, but also exhibits a high cleaning effect and maintains the cleaning power. The object is to provide an excellent liquid cleaning composition.
[0009]
[Means for Solving the Problems]
The present invention contains 25 to 55% by weight of a polyoxyalkylene alkyl ether sulfate having an alkyl group having 8 to 16 carbon atoms, a total amount of surfactants of 30 to 60% by weight, and a water-soluble organic solvent. A liquid detergent composition containing 1 to 10% by weight (ethanol does not exceed 5% by weight in the composition) and having a viscosity at 20 ° C. of 400 to 1000 mPa · s, which is branched with respect to the total weight of the surfactant Provided is a liquid detergent composition in which the proportion of a surfactant having a chain alkyl group is 20 to 80% by weight.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The composition of the present invention contains 25 to 55% by weight, preferably 25 to 50% by weight of a polyoxyalkylene alkyl ether sulfate ester salt having an alkyl group having 10 to 16 carbon atoms, and the total amount of surfactant, preferably Is a liquid detergent mainly composed of a polyoxyalkylene alkyl ether sulfate salt, wherein the total amount of surfactant having an alkyl group having 8 to 16 carbon atoms is 30 to 60% by weight, preferably 35 to 60% by weight. It is a composition. Such compositions have high detergency and persistence and low skin irritation.
[0011]
The composition of the present invention preferably contains the polyoxyalkylene alkyl ether sulfate ester salt in an amount of 50 to 100% by weight, more preferably 55 to 95% by weight, based on the total weight of the surfactant in the composition. More preferably, it is 60 to 90% by weight.
[0012]
The alkyl group of the polyoxyalkylene alkyl ether sulfate ester salt has 8 to 16 carbon atoms, preferably 10 to 16 carbon atoms, and may be either linear or branched. The alkylene oxide is preferably ethylene oxide, and the average added mole number of ethylene oxide is preferably 1.5 to 6.0, more preferably 1.6 to 4.0, and particularly preferably 2.0 to 3.5.
[0013]
In the present invention, the surfactant having a branched chain alkyl group is contained in an amount of 20 to 80% by weight, preferably 20 to 60% by weight, particularly preferably 20 to 50% by weight, based on the total weight of the surfactant. . Here, the branched alkyl group is an alkyl group having at least 1, preferably 1 to 5, carbon atoms to which 3 or 4 carbon atoms are bonded. The total number of carbon atoms in the branched alkyl group is preferably 8 to 16, more preferably 10 to 16.
[0014]
As the surfactant having a branched chain alkyl group used in the present invention, a surfactant derived from an alcohol or a fatty acid obtained by an oxo reaction or a Gelbe reaction is preferable. In the oxo reaction, a methyl branched primary alcohol or a methyl branched fatty acid obtained from a reaction between a C1-C15 1-alkene and carbon monoxide can be obtained. It is also possible to obtain multimethyl branched alcohols and multimethyl branched fatty acids obtained by reaction of diisobutylene, triisobutylene, tetraisobutylene and carbon monoxide. In the Gerbe reaction, a primary alcohol having an alkyl group branched at the 2-position by an aldehyde and an alkali can be obtained. It is also possible to perform a Gelbe reaction by simultaneously using a dehydrogenation reaction and a hydrogenation reaction of alcohol using a Ni catalyst or the like.
[0015]
In the present invention, a surfactant obtained by further derivatizing such alcohol or fatty acid is used. Specifically, branched alkyl sulfates obtained by sulfating the alcohol obtained above with SO ₃ or chlorosulfonic acid, ethylene oxide (hereinafter referred to as EO) and / or propylene oxide (hereinafter referred to as “EO”). Polyoxyethylene (and / or propylene) branched chain alkyl ether to which (PO) is added can be obtained. Furthermore, a polyoxyethylene (and / or propylene) branched alkyl ether sulfate ester salt obtained by sulfating this with SO ₃ or chlorosulfonic acid or the like can also be used.
[0016]
As a branched-chain fatty acid derivative, a quaternization obtained by subjecting an amidation reaction product with dimethylaminopropylamine to a quaternization reaction using an alkylating agent such as alkyl chloride, alkyl bromide, dialkyl sulfuric acid, alkylene oxide, etc. An amine oxide compound oxidized with an oxidizing agent such as hydrogen peroxide can be used for the ammonium salt or the amidation reaction product.
[0017]
Of these, a branched alkyl surfactant selected from the following (I) to (IV) is preferable in the present invention, and (I), (II), and (IV) are particularly preferable.
(I) A branched alkyl primary alcohol having 8 to 16 carbon atoms in all alkyl groups, 7 to 15 carbon atoms in the longest linear alkyl chain, and 1 to 5 methyl groups or ethyl groups branched. Polyoxyethylene (and / or propylene) branched chain alkyl ether (II) having an average of 4 to 50, preferably 5 to 20 EO and / or PO added to the total alkyl group having 8 to 16 carbon atoms and the longest straight chain The branched chain alkyl primary alcohol having 7 to 15 carbon atoms in the alkyl chain and 1 to 5 methyl groups or ethyl groups branched to EO and / or PO, preferably EO in an average of 1.5 to 6. 0, more preferably 1.6 to 4.0, particularly preferably 2.0 to 3.5 mol added to polyoxyethylene (and / or propylene) branched with SO ₃ or chlorosulfonic acid Chain alkyl Ruether sulfate ester salt,
(III) A branched alkyl primary alcohol having 8 to 16 carbon atoms in all alkyl groups, 7 to 15 carbon atoms in the longest linear alkyl chain, and 1 to 5 methyl groups or ethyl groups branched. Branched chain alkyl sulfate ester sulfated with SO ₃ or chlorosulfonic acid,
(IV) A branched chain fatty acid having 8 to 16 carbon atoms in all alkyl groups, 7 to 15 carbon atoms in the longest linear alkyl chain, and 1 to 5 methyl groups or ethyl groups branched Alkanoylaminopropyl-N, N-dimethylamine oxide.
[0018]
When the compound (II) and / or (III) is used, the counter ion is preferably at least one selected from sodium salts, potassium salts, and magnesium salts.
[0019]
In the present invention, it is preferable to use a linear surfactant in combination with the branched surfactant. In particular, as the linear surfactant, the alkyl group has 10 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and the average degree of condensation of the alkylene oxide is preferably 1.5 to 6.0, more preferably 1.6. To 4.0, particularly preferably 2.0 to 3.5 polyoxyalkylene alkyl ether sulfates, amine oxide compounds represented by general formula (i), and the following general formulas (ii) to (iv) It is preferable to blend one or more selected from nonionic surfactants.
[0020]
[Chemical 1]

[0021]
[Wherein R ¹ is a linear alkyl group or alkenyl group having 8 to 16 carbon atoms, preferably 10 to 16 carbon atoms, particularly preferably 10 to 14 carbon atoms, and R ³ and R ⁴ are alkyl groups having 1 to 3 carbon atoms. Or it is a hydroxyalkyl group. R ² is an alkylene group having 1 to 5 carbon atoms, preferably 2 or 3 carbon atoms. A is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and r is a number of 0 or 1. ].
[0022]
R ⁵ —O (EO) _n H (ii)
[Wherein, R ⁵ represents a linear alkyl group having an average carbon number of 8 to 16, preferably 10 to 16. EO is ethylene oxide, and n is 5 to 20 as an average added mole number. ]
R ⁶ —O [(EO) _p / (PO) _q ] H (iii)
[Wherein, R ⁶ is a linear alkyl group having an average carbon number of 8 to 16, preferably 10 to 16. EO represents ethylene oxide and PO represents propylene oxide. p is 5 to 15, and q is 1 to 5. EO and PO may be random addition or EO addition followed by PO addition and vice versa. ]
R ⁷ − (OR ⁸ ) _x G _y (iv)
[Wherein R ⁷ is a linear alkyl group having 8 to 16 carbon atoms, an alkenyl group, or an alkylphenyl group, R ⁸ is an alkenyl group having 2 to 4 carbon atoms, and G is a reducing sugar having 5 or 6 carbon atoms. Derived residues, x is the number of average values 0-6, y is the number of average values 1-10. ].
[0023]
In the present invention, branched and linear surfactants are mixed and used. From the viewpoint of obtaining a cleaning effect and an appropriate viscosity, all amine oxides combined with branched and linear surfactants are combined in the composition. It is preferable to contain 10 to 10 weight%, especially 3 to 9 weight%, and it is preferable that content of all the nonionic surfactants is 1 to 20 weight%, especially 3 to 15 weight% in a composition. Furthermore, the weight ratio of total polyoxyalkylene alkyl ether sulfate ester salt / total amine oxide is preferably 2/1 to 10/1, particularly preferably 3/1 to 10/1, from the viewpoint of obtaining an appropriate viscosity. is there.
[0024]
In the present invention, surfactants other than the above-mentioned surfactants can be blended, but it is important that the intended viscosity is not impaired. As the anionic surfactant, linear alkylbenzene sulfonate, α-sulfo fatty acid ester salt, α-olefin sulfonate, and alkane sulfonate, which are usually used in liquid detergents, may be added. The amount of the ionic surfactant is 5% by weight or less, preferably 3% by weight or less in order to satisfy the above properties. Carbobetaine and sulfobetaine can be blended as amphoteric surfactants, and the blending amount of these amphoteric surfactants is preferably 5% by weight or less, more preferably 3% by weight or less.
[0025]
The composition of the present invention is preferably 2 to 10% by weight, more preferably 3 to 8% by weight of an alkali metal cation and / or an alkaline earth metal cation in the composition from the viewpoint of viscosity and viscosity stability. % Content is desirable. As the alkali metal cation, sodium ion and potassium ion are preferable, and as the alkaline earth metal, magnesium ion is preferable. In the present invention, it is particularly preferable to add magnesium ions at a concentration of preferably 0.2 to 2% by weight, more preferably 0.3 to 1.5% by weight. In the present invention, the amount of the cation includes everything taken from the counter ion and other components of the anionic surfactant, and when the content is insufficient, sodium sulfate, potassium sulfate, magnesium sulfate, sodium chloride One or more water-soluble inorganic salts selected from potassium chloride, magnesium chloride, sodium hydroxide, potassium hydroxide, and magnesium hydroxide may be added within the above range. Moreover, when there are too many these cations, it is preferable to remove a salt using techniques, such as electrodialysis. The amount of such an inorganic cation can be determined, for example, by quantifying the entire composition by an inorganic analysis method such as a normal atomic absorption method.
[0026]
In the present invention, a water-soluble organic solvent is blended in order to adjust the solubility in water and the target viscosity. As the water-soluble organic solvent, (1) a monohydric alcohol having 1 to 5 carbon atoms, (2) a polyhydric alcohol having 4 to 12 carbon atoms, (3) a compound represented by the following general formula (v), (4 ) A compound represented by the following general formula (vi), and (5) a compound represented by the following general formula (vii) are preferred.
[0027]
[Chemical 2]

[0028]
[Wherein, R ⁹ and R ¹⁰ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, except that both R ⁹ and R ¹⁰ are hydrogen atoms. s represents a number from 0 to 10, and t represents a number from 0 to 10, except when both s and t are 0. R ¹¹ and R ¹² represent an alkyl group having 1 to 3 carbon atoms. R ¹³ represents an alkyl group having 1 to 8 carbon atoms. ].
[0029]
Examples of (1) monohydric alcohol having 2 to 5 carbon atoms include ethanol, propyl alcohol, and isopropyl alcohol. By blending these lower alcohols, the stability of the system at low temperatures can be further improved.
[0030]
Examples of the polyhydric alcohol having 4 to 12 carbon atoms of (2) include isoprene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol, 1,9-nonanediol, and ethylene glycol. , Propylene glycol, diethylene glycol, dipropylene glycol, glycerin and the like.
[0031]
In the general formula (v), the compound (3) preferably has 1 to 4 carbon atoms when R ⁹ and R ¹⁰ are alkyl groups. In addition, in the general formula (v), s and t of the average added moles of EO and PO are each a number of 0 to 10 (except when both s and t are 0). The order is not particularly limited, and may be randomly added. Specific examples of the compound (3) include ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, Polyoxyethylene (p = 2 to 3) polyoxypropylene (p = 2 to 3) glycol dimethyl ether (p represents the average number of moles added), polyoxyethylene (p = 3) glycol phenyl ether, phenyl carbitol, phenyl Examples include cellosolve and benzyl carbitol. Among these, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, and polyoxyethylene (p = 1 to 4) glycol phenyl ether are preferable from the viewpoints of detergency and usability.
[0032]
Examples of the compound (4) include 1,3-dimethyl-2-imidazolidinone and 1,3-diethyl-2-imidazolidinone, and examples of the compound (5) include alkyl glyceryl. An ether compound is exemplified as a preferable compound, and among them, a compound having an alkyl group having 3 to 8 carbon atoms as R ¹³ is preferable.
[0033]
Among these, the water-soluble organic solvents (1), (2), (3) and (5) are preferable in order to satisfy the properties of the present invention, and particularly ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, diethylene glycol. A water-soluble organic solvent selected from propylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, pentyl glyceryl ether, and octyl glyceryl ether is preferred.
[0034]
In the composition of the present invention, 1 to 10% by weight, preferably 2 to 8% by weight of such a water-soluble organic solvent is blended from the viewpoint of solubility, but the blending amount of ethanol is a composition in terms of detergency. It is preferred not to exceed 5% by weight, preferably 3% by weight. When a large amount of water-soluble organic solvent is blended, not only the viscosity decreases but also the fluidity increases, so crystals tend to be generated at low temperatures, and when left at room temperature, there is a strong tendency to form a film due to volatilization of the water-soluble organic solvent from the surface. Become. Further, these water-soluble organic solvents are effective components for reducing the viscosity. However, in the present invention, when the water-soluble organic solvent is blended, the viscosity of the liquid detergent composition does not become less than 400 mP · s. Is adjusted as appropriate. If blended in such an amount that the viscosity is less than 400 mP · s, it is not possible to obtain a detergency effect.
[0035]
The composition of the present invention preferably further contains a hydrotrope agent in view of storage stability, viscosity adjustment and viscosity stability (the viscosity does not change with time). As the hydrotrope, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid and their sodium, potassium or magnesium salts are preferable, and p-toluenesulfonic acid and its salts are particularly preferable.
[0036]
The composition of the present invention preferably contains a hydrotrope agent in an amount of 0.5 to 5% by weight, particularly preferably 1 to 5% by weight.
[0037]
The composition of the present invention is in the form of an aqueous solution in which the above components and water are blended, and the content of water is 20 to 60% by weight, preferably 30 to 60% by weight, from the point that an appropriate viscosity is obtained. Preferably it is 40-60 weight%, Most preferably, it is 45-55 weight%. Moreover, it is preferable from the point of storage stability and the safety | security to skin that pH of this composition shall be 6-8, preferably 6.5-7.5 at 20 degreeC. Examples of pH adjusters include inorganic acids such as hydrochloric acid and sulfuric acid, acid agents such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, and maleic acid, and sodium hydroxide and potassium hydroxide. It is preferable to use alkali agents such as sodium carbonate and potassium carbonate alone or in combination, such as ammonia and derivatives thereof, amine salts such as monoethanolamine, diethanolamine, and triethanolamine, particularly from hydrochloric acid, sulfuric acid, and citric acid. It is preferable to use an alkali agent selected from an acid selected, sodium hydroxide, and potassium hydroxide.
[0038]
The liquid detergent composition of the present invention has a viscosity at 20 ° C. of 400 to 1000 mPa · s, preferably 400 to 900 mPa · s, particularly 500 to 900 mPa · s. By adjusting to such a viscosity, In the method of impregnating and cleaning the flexible absorbent, the durability of the cleaning power can be increased. Viscosity is adjusted by adjusting the blending amount of the hydrotrope, water-soluble organic solvent, water-soluble inorganic salt and water in addition to the type of surfactant having a branched chain, the combination of surfactants or the branching rate. It may be done by doing.
[0039]
The viscosity as used in the present invention is measured as follows. First, a B-type viscometer model BM manufactured by TOKIMEC. INC is prepared with a rotor of rotor number No. 3. The sample is filled into a tall beaker and prepared at 20 ° C. in a constant temperature bath at 20 ° C. A sample prepared at a constant temperature is set in a viscometer. The rotational speed of the rotor is set to 30 r / m, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the present invention.
[0040]
The liquid detergent composition of the present invention does not affect the viscosity and stability of ingredients generally added to liquid detergents such as fragrance ingredients, colorants, dispersants, abrasives and antibacterial / antifungal agents. It can mix | blend in the range.
[0041]
【Example】
A cleaning composition was prepared using the components shown in Table 1. The following methods evaluated the viscosity of these compositions, the durability of the cleaning effect, and the solubility in water. The results are shown in Table 1.
[0042]
<Detergency test>
・ Adjustment of model stains Salad oil / beef tallow was mixed at a weight ratio of 1/1, and further 2 g of model oil stains mixed uniformly with 0.1% by weight of pigment (stan red) were spread evenly on the melamine dish. The thing was used as a model contaminated tableware.
Cleaning method and evaluation method A commercially available sponge (Kintori Cleaner No. 5005, polyurethane foam) is impregnated with 15 g of liquid cleaning composition and tap water in Table 1 in an amount of 0.44 g of surfactant. It was also bubbled 3 times by hand. Using this, the model-contaminated tableware was scrubbed and the number of dishes that could be washed (confirmed by the disappearance of the color attached to the tableware) was determined.
[0043]
<Solubility test>
A circular glass plate having a diameter of 35 mm with three legs having a height of 13 mm, a width of 5 mm, and a thickness of 2 mm was placed in the center of a 200 ml glass beaker. 8 mm in diameter) was placed in a constant temperature water bath with a stirrer at 25 ° C. until the temperature reached equilibrium. Using a syringe, 0.25 ml of a composition whose temperature had been equilibrated in advance in a constant temperature water bath at 25 ° C. was gently left at the center of the upper surface of the glass plate. Immediately after the injection, the mixture was stirred for 30 minutes at 1000 rpm. The case where the composition was completely dissolved after 30 minutes was marked as ◯, and the case where the composition remained on the glass plate and in the liquid was marked as x.
[0044]
[Table 1]

[0045]
(Note) The symbols in the table represent the following.
A-1: Sodium polyoxyalkylene branched alkyl ether sulfate obtained from a compound obtained by adding 2 mol of EO to isotridecanol on average. A-2: 7 mol of EO added to isotridecanol on average. Nonionic surfactant a-3: N-isononanoylaminopropyl-N, N-dimethylamine oxide b-1 sodium polyoxyethylene lauryl ether sulfate (EO average addition mole number 2)
B-2: Alkyl glucoside whose alkyl group composition is straight chain mixed alkyl having 12/14 carbon atoms = 60/40 and having an average glucoside condensation degree of 1 b-3: Polyoxyethylene lauryl ether (EO average) Addition mole number 7)
B-4: Lauryldimethylamine oxide, Polypropylene glycol: Weight average molecular weight 1200
-Preservative: Proxel BDN (Avisia Co., Ltd.)
Inorganic cation amount: The amount of alkali metal cation and / or alkaline earth metal cation determined by atomic absorption method.
ES: polyoxyalkylene alkyl ether sulfate ester pH: adjusted using 1/10 N-sulfuric acid aqueous solution or 1/10 N sodium hydroxide.

Claims (1)

A polyoxyalkylene alkyl ether sulfate having an alkyl group of 8-16 carbon atoms containing 25 to 55 wt%, the surfactant containing 30 to 60 wt% in total, 2 ethanol and propylene glycol in a total A liquid detergent composition containing ˜8 wt% (however, ethanol does not exceed 3 wt% in the composition) and having a viscosity at 20 ° C. of 400 to 1000 mPa · s, and branched chain with respect to the total weight of the surfactant The liquid detergent composition whose ratio of surfactant which has an alkyl group is 20 to 60 weight%.