JP3938445B2 - Washing soap - Google Patents

Description

【０００８】
〔式中、R¹は炭素数６のアルキル基を示す。R²、R³及びR⁴はそれぞれ炭素数１〜２のアルキル基を示す。X^-はハロゲン、アルキル硫酸、硫酸、硝酸、有機酸から選ばれる陰イオンを示す。〕
【０００９】
【発明の実施の形態】
本発明に用いられる(b) 成分の４級アンモニウム塩は、油性汚れに吸着・浸透して、汚れを衣類から離脱しやすくするが、R¹の炭素数が６であるため、界面活性能がなく、洗浄液中に可溶化、乳化、分散したり、再付着を防止する作用を有しないため、洗浄効果を示さないが、陰イオン界面活性剤が共存するとそれらの作用を有するため高い洗浄効果を示す。
【００１０】
本発明の(a) 成分の陰イオン界面活性剤は、アルキル基の炭素数が８〜22のアルキルベンゼンスルホン酸塩（以後、ＬＡＳという）、脂肪酸塩、アルキルリン酸エステル塩、炭素数８〜22の直鎖もしくは分岐鎖の１級又は２級アルコールの硫酸エステル塩、炭素数８〜22のアルコールエトキシレート化物の硫酸エステル塩、アルカンスルホン酸塩、α−オレフィンスルホン酸塩、α−スルホ脂肪酸塩及びα−スルホ脂肪酸アルキルエステル塩等が挙げられ、これらから選ばれた１種以上が好ましく、ＬＡＳ、脂肪酸塩、アルキルリン酸エステル塩が洗浄力を向上させる観点から更に好ましい。これらの陰イオン界面活性剤の対イオンとしては、Na、K 、NH₄ 、トリエタノールアミン、モノエタノールアミンが適している。
【００１１】
本発明の(b) 成分の一般式（Ｉ）で表される４級アンモニウム塩としては、R¹が炭素数６のアルキル基、R²が炭素数１〜２のアルキル基、R³及びR⁴がそれぞれ炭素数１〜２のアルキル基あるいは-(CH₂CH₂O)_nH (nは１〜10、好ましくは１〜３の数）であるものが好ましく、さらにR¹が炭素数６のアルキル基、R²がメチル基、R³及びR⁴がそれぞれメチル基あるいはヒドロキシエチル基であるものが好ましい。X^- は陰イオンであり、ハロゲン、アルキル硫酸、硫酸、硝酸、有機酸等のイオンが挙げられるが、ハロゲンイオンが好ましく、Cl^- 、Br^- が特に好ましい。
【００１２】
本発明の洗浄剤中の(a) 成分と(b) 成分の合計含有量は、洗浄力、コスト面、泡立ちや、すすぎ性の観点から１〜75重量％であり、10〜50重量％が好ましい。また本発明の洗浄剤中の(a) 成分と(b) 成分の重量比は、(a)／(b)＝99／１〜50／50である。 (a)／(b) の重量比を50／50以上とすることで汚れの再付着を防止することができ、また経済的にも有利である。また (a)／(b) の重量比を99／１以下とすることにより相乗的に洗浄力が向上する。
【００１３】
また、本発明では非イオン界面活性剤、陽イオン界面活性剤、両性界面活性剤等のその他の界面活性剤を併用することもできる。洗浄剤中の界面活性剤の総含有量は10〜60重量％が好ましい。また、十分な洗浄力を発現するために、本発明の洗浄剤にはアルカリ剤、無機ビルダー、有機ビルダー、泥分散剤等を加えることが好ましい。
【００１４】
更に、本発明の洗浄剤には、下記のような成分を配合することができる。結晶性珪酸塩とアルミノ珪酸塩は粉末状、粒状あるいは塊状の衣料用洗浄剤に、より好適に用いることができる。結晶性珪酸塩とアルミノ珪酸塩はアルカリ緩衝能の観点から好ましい併用成分である。
【００１５】
本発明に用いられる結晶性珪酸塩として好適なものは、次の一般式（Ａ）又は（Ｂ）で表される組成を有するものである。
【００１６】
x(M₂O)・y(SiO₂)・z(Me_mO_n)・w(H₂O) （Ａ）
〔式中、M は周期律表のIa族元素を示し、Meは周期律表のIIa 族元素、IIb 族元素、IIIa族元素、IVa 族元素又はVIII族元素から選ばれる１種又は２種以上の組み合わせを示し、 y／x＝ 0.5〜2.6 、 z／x＝0.01〜1.0 、w＝０〜20、 n／m＝0.5 〜2.0 である。〕
M₂O・y'(SiO₂)・w(H₂O) （Ｂ）
〔式中、M及びwは前記の意味を示し、y'＝1.5〜2.6である。〕
一般式（Ａ）において、M は周期律表のIa族元素から選ばれ、Ia族元素としては、Na、K 等が挙げられる。これらは単独で或いは例えばNa₂OとK₂O とが混合してM₂O 成分を構成してもよい。
【００１７】
Meは周期律表のIIa 族元素、IIb 族元素、IIIa族元素、IVa 族元素又はVIII族元素から選ばれ、例えばMg、Ca、Zn、Y 、Ti、Zr、Fe等が挙げられ、資源及び安全上の点から好ましくはMg、Caである。また、これらは単独で或いは２種以上混合していてもよく、例えばMgO 、CaO 等が混合してMe_mO_n成分を構成していてもよい。
【００１８】
本発明において、一般式（Ａ）又は（Ｂ）で表される結晶性珪酸塩は、それぞれ単独又は２種以上を用いることができる。
本発明の洗浄剤中の結晶性珪酸塩の配合量は洗浄力や粉末物性の観点から１〜40重量％が好ましく、５〜35重量％が更に好ましい。結晶性珪酸塩を１重量％以上配合すると十分な洗浄力の向上が見られ、また、40重量％以下の配合では吸湿性の増加を抑え、ケーキング等の粉末物性が低下するおそれはない。
【００１９】
アルミノ珪酸塩は非晶質、結晶質のいずれも用いることができる。
非晶質アルミノ珪酸塩は、珪素をSiO₂として30重量％以上、好ましくは40重量％以上含有するものが良く、また５％分散液のpHが９以上であるものを用いると、高湿度貯蔵後の洗剤の溶解性の劣化が更に改善される。
【００２０】
本発明に用いられる非晶質アルミノ珪酸塩としては、一般式（i)で表されるものが例示され、これらは高吸油性で且つ陽イオン交換能が高い。
a(M₂O)・Al₂O₃・b(SiO₂)・c(H₂O) （i)
〔式中、M は前記の意味を示し、a, b, cは各成分のモル数を示し、0.7≦a≦2.0、0.8≦b＜４、c は任意の正数である。〕
また、結晶質のアルミノ珪酸塩は、一般にゼオライトといわれているものであり、一般式(iii)
d(M₂O)・Al₂O₃・e(SiO₂)・f(H₂O) （iii)
〔式中、M は前記の意味を示し、d, e, f は各成分のモル比を示し、0.7≦d≦1.5 、0.8≦e＜６、f は任意の正数である。〕
で表されるものである。
本発明の洗浄剤中のアルミノ珪酸塩の配合量は１〜60重量％が好ましく、８〜30重量％が更に好ましい。
【００２１】
洗浄剤中に含まれるアルカリ剤は、その30〜100 重量％、好ましくは50〜100 重量％を前記の結晶性珪酸塩が占めるものが望ましい。
本発明の洗浄剤に配合されるカルボン酸系ポリマーの中ではアクリル酸−マレイン酸コポリマーの塩とポリアクリル酸の塩が好ましく、洗浄剤中に好ましくは１〜20重量％、更に好ましくは２〜10重量％配合される。
【００２２】
本発明の洗浄剤には、その他一般に洗浄剤に配合することができる成分を配合することができる。例えば有機金属イオン封鎖剤、増量剤、分散剤、色移り防止剤、漂白剤、漂白活性化剤、酵素、酵素安定剤、蛍光染料、消泡剤、酸化防止剤、青味付与剤並びに香料等を配合することができる。
本発明の洗浄剤は粉末状、粒状、塊状、液状等のいずれの形態であってもよいが、粉末状、粒状又は塊状が好ましい。
【００２３】
【発明の効果】
本発明によれば、温水を用いない場合の洗濯でも良好な油性汚れ洗浄力を示す洗浄剤が得られる。
【００２４】
【実施例】
以下の例において、％は特記しない限り重量％である。尚、実施例４、５及び７は参考例である。
【００２５】
実施例１〜５及び比較例１〜５
表１に示す組成を有する本発明又は比較の高密度粒状洗浄剤を下記方法で調製した。
＜高密度粒状洗浄剤の調製法＞
表１に示す組成になるように、酵素以外の各成分を混合し、含水量50重量％の水性スラリーを調製し、それを噴霧乾燥して得られた粉末をハイスピードミキサー（攪拌転動造粒機、深江工業（株）製）中に投入して造粒した後、得られた造粒粒子と酵素をブレンドして高密度粒状洗浄剤を得た。
【００２６】
尚、表１において、各成分の略号は以下の意味を示す。
・Ｃ_nＴＭＡＣ：モノアルキル（炭素数n）トリメチルアンモニウムクロライド
・Ｃ_nＤＭＡＣ：モノアルキル（炭素数n）ジメチルヒドロキシエチルアンモニウムクロライド
・ＬＡＳ：直鎖アルキル(C₁₀〜C₁₃)ベンゼンスルホン酸ナトリウム
・ＦＡ：脂肪酸石鹸（平均炭素数12，Na塩）
・ＡＥ：ポリオキシエチレン（エチレンオキサイド平均付加モル数＝12.7）ドデシルエーテル(HLB＝15)
・ゼオライト（結晶性アルミノ珪酸塩）：組成 M₂O・Al₂O₃・2SiO₂・2H₂O、平均粒子径４μｍ、イオン交換容量290CaCO₃mg／g 、M はNa、K
・珪酸塩（Ａ）：組成 M₂O・1.8SiO₂・0.02MeO(ここで、M：Na，K, K／Na＝0.03、Me＝Ca，Mg、Mg／Ca＝0.01) 、イオン交換容量290 CaCO₃ mg／g 、平均粒子径30μm 〔一般式（Ａ）で表わされる結晶性珪酸塩〕
・珪酸塩（Ｂ）：組成 M₂O・2SiO₂ 、イオン交換容量224CaCO₃mg／g 、平均粒子径30μm 〔一般式（Ｂ）で表わされる結晶性珪酸塩〕
・ＡＭ：アクリル酸／マレイン酸（モル比７／３）コポリマーのNa塩（平均分子量７万）
・ＰＡ：ポリアクリル酸ナトリウム、平均分子量8000
・共通成分：酵素（サビナーゼ12.0TW、ノボノルディスク社製）１％、蛍光染料 0.5％及び芒硝であり、芒硝で全体の量が100 ％になるように調整した。
【００２７】
得られた高密度粒状洗浄剤について、下記方法で油性汚れの洗浄力試験を行い、また溶液安定性を評価した。結果を表１に示す。
＜洗浄力試験＞
(1) 人工汚染布の調製
下記組成の人工汚染液を布に付着して人工汚染布を調製した。人工汚染液の布への付着は、グラビアロールコーターを用いて行った。人工汚染液を布に付着させ人工汚染布を作製する工程は、グラビアロールのセル容量 58cm³／m²、塗布速度1.0m／min 、乾燥温度 100℃、乾燥時間１分間で行った。布は木綿金巾2003布（谷頭商店製）を使用した。本人工汚染布を油性汚れの試験布とする。
【００２８】
・人工汚染液の組成
ラウリン酸 0.44％
ミリスチン酸 3.09％
ペンタデカン酸 2.31％
パルミチン酸 6.18％
ヘプタデカン酸 0.44％
ステアリン酸 1.57％
オレイン酸 7.75％
トリオレイン酸 13.06％
パルミチン酸ｎ−ヘキサデシル 2.18％
スクアレン 6.53％
卵白レシチン液晶物 1.94％
鹿沼赤土 8.11％
カーボンブラック 0.01％
水道水 バランス
(2) 洗浄条件及び評価方法
洗浄剤水溶液１リットルに、10cm×10cmの試験布を５枚入れ、ターゴトメーターにて100r/minで洗浄した。洗浄条件は次の通りである。
【００２９】
・洗浄条件
洗浄時間 10分
洗浄剤濃度 0.067 ％
水の硬度 ２°ＤＨ
水温 10℃
すすぎ 水道水にて５分間
洗浄力は汚染前の原布及び洗浄前後の試験布の 550nmにおける反射率を自記色彩計（島津製作所製）にて測定し、次式によって洗浄率（％）を求め、５枚の測定平均値を洗浄率として示した。
【００３０】
【数１】

【００３１】
＜溶液安定性＞
表１に示す比率の４級アンモニウム塩とＬＡＳのみからなる１％界面活性剤水溶液を調製し、24時間後に目視により溶液状態を下記基準で判定した。
○：均一透明液体、△：白く濁った均一液体、×：沈澱生成
【００３２】
【表１】

【００３３】
実施例６〜７及び比較例６〜７
実施例１〜５に準じて、表２に示す組成の洗浄剤を調製し、油性汚れと泥汚れに対する洗浄力試験を行った。表２中の配合成分の略号は表１と同じ意味である。試験布としては、油性汚れでは、実施例１と同様の人工汚染布を用い、また泥汚れでは、下記のようにして調製した泥汚れ汚染布を用い、洗浄力の試験方法は、実施例１と同じである。ただし、用いる洗浄剤水溶液の水温は20℃とした。結果を表２に示す。
【００３４】
・泥汚れ汚染布の調製
鹿沼園芸用赤玉土を 120℃±５℃で４時間乾燥後、粉砕し、150メッシュ（100μｍ）パスのものを 120℃±５℃で乾燥し、得られた土 150ｇを１リットルのパークレンに分散し、金巾＃2023布をこの液に接触させ、ブラッシングし分散液を除去し過剰付着汚れを脱落させる（特開昭55−26473 号参照）。
【００３５】
【表２】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cleaning agent having excellent oily soil cleaning power without using hot water, and particularly to a cleaning agent suitable for clothing.
[0002]
[Prior art and problems to be solved by the invention]
When washing dirt that adheres to clothes, especially oily dirt, it is advantageous from the viewpoint of the washing effect to use warm water, but energy is required to obtain warm water. Thus, studies have been made to improve the cleaning power.
[0003]
In the case of a quaternary ammonium salt, if the alkyl group has 6 carbon atoms, it is not used as a cleaning agent because it has no surface activity, but if it has 8 or more carbon atoms, it has surface activity and may be used. However, a quaternary ammonium salt having 8 or more carbon atoms alone does not show a great cleaning effect. In a complex system with an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant, particularly an anionic surfactant and Although it was known that the cleaning effect synergistically appeared in this composite system, its use was mainly for fiber softeners, hair rinses, bactericides and the like. This is because, in order to enhance the cleaning effect, if the amount of the quaternary ammonium salt having 8 or more carbon atoms is increased, complex precipitates are likely to be generated due to the interaction between the two, and the stability of the product is lowered. For this reason, the compounding quantity of the quaternary ammonium salt was limited to a small amount, and the improvement in detergency was small.
[0004]
Therefore, the subject of this invention is providing the cleaning agent which shows the favorable detergency with respect to oily stain | pollution | contamination without using warm water.
[0005]
[Means for Solving the Problems]
When the present inventors make a composite system with a quaternary ammonium salt having an alkyl group having 6 carbon atoms, even if the amount of the quaternary ammonium salt is large, no complex precipitate is generated, and even when hot water is not used. It has been found that the cleaning effect of oily soil is remarkably improved.
[0006]
That is, the present invention contains the following component (a) and component (b), the total content of component (a) and component (b) is 1 to 75% by weight, weight of component (a) and component (b) It is a washing | cleaning agent for clothes whose ratio is (a) / (b) = 99 / 1-50 / 50.
(a) Anionic surfactant
(b) Quaternary ammonium salt represented by the general formula (I)
[Chemical 2]

[0008]
[Wherein R ¹ represents an alkyl group having 6 carbon atoms. R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 2 carbon atoms . X ⁻ represents an anion selected from halogen, alkyl sulfuric acid, sulfuric acid, nitric acid, and organic acid . ]
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The quaternary ammonium salt of the component (b) used in the present invention adsorbs and permeates oily dirt and makes it easy to remove the dirt from clothing. However, since R ¹ has 6 carbon atoms, it has a surface activity. In addition, it has no action to solubilize, emulsify, disperse or prevent re-adhesion in the washing liquid, so it does not show a washing effect, but when an anionic surfactant coexists, it has those actions and has a high washing effect. Show.
[0010]
The anionic surfactant of component (a) of the present invention is an alkylbenzene sulfonate (hereinafter referred to as LAS) having 8 to 22 carbon atoms in the alkyl group, a fatty acid salt, an alkyl phosphate ester salt, or 8 to 22 carbon atoms. Linear or branched primary or secondary alcohol sulfate ester salt, sulfate ester salt of alcohol ethoxylate having 8 to 22 carbon atoms, alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt And α-sulfo fatty acid alkyl ester salts, and the like. One or more selected from these are preferred, and LAS, fatty acid salts, and alkyl phosphate ester salts are more preferred from the viewpoint of improving detergency. As counter ions for these anionic surfactants, Na, K, NH ₄ , triethanolamine, and monoethanolamine are suitable.
[0011]
As the quaternary ammonium salt represented by the general formula (I) of the component (b) of the present invention, R ¹ is an alkyl group having 6 carbon atoms, R ² is an alkyl group having 1 to ² carbon atoms, R ³ and R ⁴ is preferably an alkyl group having 1 to 2 carbon atoms or — (CH ₂ CH ₂ O) _n H (n is 1 to 10, preferably 1 to 3), and R ¹ is 6 carbon atoms. In which R ² is a methyl group and R ³ and R ⁴ are each a methyl group or a hydroxyethyl group. X ⁻ is an anion, and examples thereof include ions such as halogen, alkylsulfuric acid, sulfuric acid, nitric acid, and organic acids. Halogen ions are preferable, and Cl ⁻ and Br ⁻ are particularly preferable.
[0012]
The total content of the component (a) and the component (b) in the cleaning agent of the present invention is 1 to 75% by weight from the viewpoints of detergency, cost, foaming and rinsing properties, and 10 to 50% by weight. preferable. The weight ratio of the component (a) to the component (b) in the cleaning agent of the present invention is (a) / (b) = 99/1 to 50/50. By setting the weight ratio of (a) / (b) to 50/50 or more, it is possible to prevent redeposition of dirt, and it is economically advantageous. Further, when the weight ratio of (a) / (b) is 99/1 or less, the detergency is synergistically improved.
[0013]
Moreover, in this invention, other surfactants, such as a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant, can also be used together. The total content of the surfactant in the cleaning agent is preferably 10 to 60% by weight. Moreover, in order to express sufficient detergency, it is preferable to add an alkali agent, an inorganic builder, an organic builder, a mud dispersing agent, etc. to the cleaning agent of the present invention.
[0014]
Furthermore, the following components can be mix | blended with the cleaning agent of this invention. Crystalline silicates and aluminosilicates can be more suitably used in powder, granular or bulk clothing detergents. Crystalline silicate and aluminosilicate are preferred combination components from the viewpoint of alkali buffering ability.
[0015]
What is suitable as a crystalline silicate used for this invention has a composition represented by the following general formula (A) or (B).
[0016]
x (M ₂ O), y (SiO ₂ ), z (Me _m O _n ), w (H ₂ O) (A)
[Wherein M represents a group Ia element of the periodic table, and Me represents one or more selected from group IIa, IIb, IIIa, IVa, or VIII elements of the periodic table. And y / x = 0.5 to 2.6, z / x = 0.01 to 1.0, w = 0 to 20, and n / m = 0.5 to 2.0. ]
M ₂ O · y '(SiO ₂ ) · w (H ₂ O) (B)
[In formula, M and w show the said meaning, and are y '= 1.5-2.6. ]
In the general formula (A), M is selected from group Ia elements of the periodic table, and examples of the group Ia elements include Na and K 2. These may be used alone or, for example, Na ₂ O and K ₂ O may be mixed to constitute the M ₂ O component.
[0017]
Me is selected from Group IIa element, Group IIb element, Group IIIa element, Group IVa element or Group VIII element of the periodic table, and examples include Mg, Ca, Zn, Y, Ti, Zr, Fe, etc. Mg and Ca are preferable from the viewpoint of safety. Further, it may be mixed alone or two or more, for example MgO, CaO or the like may constitute the Me _m O _n component are mixed.
[0018]
In the present invention, the crystalline silicate represented by the general formula (A) or (B) may be used alone or in combination of two or more.
The blending amount of the crystalline silicate in the cleaning agent of the present invention is preferably 1 to 40% by weight, more preferably 5 to 35% by weight from the viewpoints of detergency and powder physical properties. When the crystalline silicate is blended in an amount of 1% by weight or more, a sufficient improvement in detergency is observed. In the blending of 40% by weight or less, an increase in hygroscopicity is suppressed, and there is no possibility that the powder physical properties such as caking are deteriorated.
[0019]
The aluminosilicate can be either amorphous or crystalline.
The amorphous aluminosilicate should contain silicon as SiO _{2 in an amount} of 30% by weight or more, preferably 40% by weight or more, and if a 5% dispersion having a pH of 9 or more is used, it can be stored at high humidity. The degradation of the solubility of the later detergent is further improved.
[0020]
Examples of the amorphous aluminosilicate used in the present invention include those represented by the general formula (i), which are highly oil-absorbing and have high cation exchange capacity.
a (M ₂ O) ・ Al ₂ O ₃・ b (SiO ₂ ) ・ c (H ₂ O) (i)
[Wherein M represents the above meaning, a, b and c represent the number of moles of each component, 0.7 ≦ a ≦ 2.0, 0.8 ≦ b <4, and c is an arbitrary positive number. ]
In addition, crystalline aluminosilicate is generally called zeolite, and has the general formula (iii)
d (M ₂ O) ・ Al ₂ O ₃・ e (SiO ₂ ) ・ f (H ₂ O) (iii)
[Wherein, M represents the above-mentioned meaning, d, e, f represent the molar ratio of each component, 0.7 ≦ d ≦ 1.5, 0.8 ≦ e <6, and f is an arbitrary positive number. ]
It is represented by
The blending amount of the aluminosilicate in the cleaning agent of the present invention is preferably 1 to 60% by weight, more preferably 8 to 30% by weight.
[0021]
The alkaline agent contained in the cleaning agent is desirably composed of 30 to 100% by weight, preferably 50 to 100% by weight, of the crystalline silicate.
Among the carboxylic acid-based polymers blended in the cleaning agent of the present invention, a salt of acrylic acid-maleic acid copolymer and a salt of polyacrylic acid are preferable, and preferably 1 to 20% by weight, more preferably 2 to 2% in the cleaning agent. 10% by weight is blended.
[0022]
In the cleaning agent of the present invention, other components that can generally be added to the cleaning agent can be added. For example, organometallic sequestering agents, extenders, dispersants, anti-transfer agents, bleaching agents, bleach activators, enzymes, enzyme stabilizers, fluorescent dyes, antifoaming agents, antioxidants, bluish imparting agents and perfumes Can be blended.
The cleaning agent of the present invention may be in any form such as powder, granules, lumps, and liquids, but is preferably powder, granules, or lumps.
[0023]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the washing | cleaning agent which shows the favorable oil-based dirt detergency also by the washing | cleaning when not using warm water is obtained.
[0024]
【Example】
In the following examples,% is% by weight unless otherwise specified. Examples 4, 5 and 7 are reference examples.
[0025]
Examples 1-5 and Comparative Examples 1-5
The present invention or comparative high-density granular detergent having the composition shown in Table 1 was prepared by the following method.
<Preparation method of high-density granular detergent>
Ingredients other than the enzyme are mixed so that the composition shown in Table 1 is prepared, an aqueous slurry having a water content of 50% by weight is prepared, and the powder obtained by spray drying is mixed with a high-speed mixer (stirring rolling) The resulting granulated particles and enzyme were blended to obtain a high-density granular detergent.
[0026]
In Table 1, the abbreviations of each component have the following meanings.
- C _n TMAC: monoalkyl (carbon number n) trimethylammonium chloride, C _n DMAC: ammonium monoalkyl (carbon number n) dimethyl hydroxyethyl chloride-LAS: linear alkyl (C ₁₀ -C ₁₃₎ sodium benzenesulfonate, FA: Fatty acid soap (average carbon number 12, Na salt)
・ AE: Polyoxyethylene (Ethylene oxide average added mole number = 12.7) Dodecyl ether (HLB = 15)
Zeolite (crystalline aluminosilicate): Composition _{M 2 O · Al 2 O 3} · 2SiO 2 · 2H 2 O, an average particle diameter of 4 [mu] m, the ion exchange capacity 290CaCO ₃ mg / g, M is Na, K
Silicate (A): Composition M ₂ O · 1.8SiO ₂ · 0.02MeO (where M: Na, K, K / Na = 0.03, Me = Ca, Mg, Mg / Ca = 0.01), ion exchange capacity 290 CaCO ₃ mg / g, average particle size 30μm [crystalline silicate represented by general formula (A)]
Silicate (B): Composition M ₂ O · 2SiO ₂ , ion exchange capacity 224CaCO ₃ mg / g, average particle size 30 μm [crystalline silicate represented by general formula (B)]
AM: Na salt of acrylic acid / maleic acid (molar ratio 7/3) copolymer (average molecular weight 70,000)
PA: sodium polyacrylate, average molecular weight 8000
Common components: enzyme (sabinase 12.0TW, Novo Nordisk) 1%, fluorescent dye 0.5% and mirabilite, and the total amount of mirabilite was adjusted to 100%.
[0027]
About the obtained high-density granular cleaning agent, the detergency test of the oily soil was conducted by the following method, and the solution stability was evaluated. The results are shown in Table 1.
<Detergency test>
(1) Preparation of artificially contaminated cloth An artificially contaminated cloth was prepared by attaching an artificially contaminated liquid having the following composition to the cloth. The artificial contamination liquid was attached to the cloth using a gravure roll coater. The process of producing an artificially contaminated cloth by attaching an artificially contaminated liquid to the cloth was carried out with a gravure roll cell capacity of 58 cm ³ / m ² , a coating speed of 1.0 m / min, a drying temperature of 100 ° C., and a drying time of 1 minute. As the cloth, a cotton gold cloth 2003 cloth (manufactured by Tanigami Shoten) was used. This artificially contaminated cloth is used as a test cloth for oily dirt.
[0028]
・ Artificial contamination liquid composition Lauric acid 0.44%
Myristic acid 3.09%
Pentadecanoic acid 2.31%
Palmitic acid 6.18%
Heptadecanoic acid 0.44%
Stearic acid 1.57%
Oleic acid 7.75%
Trioleic acid 13.06%
N-Hexadecyl palmitate 2.18%
Squalene 6.53%
Egg white lecithin liquid crystal 1.94%
Kanuma red soil 8.11%
Carbon black 0.01%
Tap water balance
(2) Cleaning conditions and evaluation method Five test cloths of 10 cm x 10 cm were placed in 1 liter of an aqueous cleaning solution solution, and washed with a tartometer at 100 r / min. The cleaning conditions are as follows.
[0029]
・ Cleaning conditions Cleaning time 10 minutes Detergent concentration 0.067%
Water hardness 2 ° DH
Water temperature 10 ℃
Rinsing With tap water for 5 minutes, the reflectivity at 550 nm of the untreated cloth and the test cloth before and after washing is measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the washing rate (%) is obtained by the following formula. The measurement average value of 5 sheets was shown as the cleaning rate.
[0030]
[Expression 1]

[0031]
<Solution stability>
A 1% surfactant aqueous solution consisting only of the quaternary ammonium salt and LAS in the ratios shown in Table 1 was prepared, and the solution state was visually determined after 24 hours according to the following criteria.
○: Uniform transparent liquid, △: White turbid uniform liquid, ×: Precipitate formation
[Table 1]

[0033]
Examples 6-7 and Comparative Examples 6-7
According to Examples 1-5, the cleaning agent of the composition shown in Table 2 was prepared, and the detergency test to oily dirt and mud dirt was performed. The abbreviations of the blending components in Table 2 have the same meaning as in Table 1. As the test cloth, an artificial soil similar to that in Example 1 was used for oily soil, and a mud soil contaminated fabric prepared as described below was used for mud soil. Is the same. However, the water temperature of the detergent aqueous solution used was 20 ° C. The results are shown in Table 2.
[0034]
・ Preparation of mud soil-contaminated cloth Kanuma Horticultural Akadama soil was dried at 120 ° C ± 5 ° C for 4 hours, then pulverized, and dried with a 150 mesh (100 µm) pass at 120 ° C ± 5 ° C. Is dispersed in 1 liter of parklens, and a gold width # 2023 cloth is brought into contact with this liquid and brushed to remove the dispersed liquid to remove excess adhering dirt (see JP-A-55-26473).
[0035]
[Table 2]

Claims (1)

It contains the following component (a) and component (b), the total content of component (a) and component (b) is 1 to 75% by weight, and the weight ratio of component (a) to component (b) is (a ) / (b) laundry detergent is a = 99 / 1-50 / 50.
(a) Anionic surfactant
(b) Quaternary ammonium salt represented by general formula (I)

[Wherein R ¹ represents an alkyl group having 6 carbon atoms. R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 2 carbon atoms . X ⁻ represents an anion selected from halogen, alkyl sulfuric acid, sulfuric acid, nitric acid, and organic acid . ]