JP4846095B2 - Cleaning product - Google Patents

Description

【００５１】
〈漂白力の測定法〉
黒カビ（Cladosporium cladosporioides）を培養し、被着させた素焼きタイル〔イナックス（INAX）社製：SPKC-1060〕をモデルプレートとして用いた（素焼きタイルのＬ値を１００として計算したときのモデルカビプレートのＬ値＝３０〜４０）。このモデルカビプレートを垂直に置き、トリガー式スプレーヤーを用いて各種漂白剤組成物を１ストローク（約０．８ｇ）プレートの中央部に１０ｃｍの距離から噴霧した。３分間放置し、水洗、風乾した後、色彩色差計〔ミノルタ（MINOLTA）社製；CR-200〕を用いて明度（Ｌ値）を測定した。
【００５２】
（造泡筒の内径について）
造泡筒３９の適切な内径を評価するため、まず、突条４０ａもスクリーン４２もない状態で、実施例１〜５、比較例１〜２の評価を行った。結果は表１に示すように、内径２〜８ｍｍの範囲で、吐出性、付着滞留率、漂白力について良好な結果が得られた。
【００５３】
【表１】

【００５４】
次に、上記において適切であると評価された造泡筒３の内径の範囲で、突条４０ａを設けた実施例６〜８の評価を行った。結果は表２に示すように、いずれも、吐出性、付着滞留率、漂白力について良好な結果が得られた。
なお、以下において、突条の形状（ａ），（ｂ）とは、各々図７に示す縦断面形状（ａ），（ｂ）をいう。また、突条の位置とは、造泡筒３９のノズル孔２７側端部から、一番近い突条までの長さについて示すもので、「奥」とはその長さが４．０ｍｍである場合、「中間」とはその長さが４．５ｍｍである場合、「出口」とはその長さが５．０ｍｍである場合をいう。また、突条の本数が複数の場合、各々のピッチは０．７ｍｍである。
【００５５】
【表２】

【００５６】
次に、上記において適切であると評価された造泡筒３の内径の範囲で、突条４０ａを設けず、スクリーン４２（メッシュの形状：（ａ））を設けた実施例９〜１２の評価を行った。結果は表３に示すように、いずれも、吐出性、付着滞留率、漂白力について良好な結果が得られた。なお、上記及び以下において、メッシュの形状（ａ）〜（ｇ）とは、図８に示す（ａ）〜（ｇ）の形状を示すものである。
【００５７】
【表３】

【００５８】
次に、洗浄剤７０の粘度の影響を評価するため、実施例１３〜１５、比較例３〜４の評価を行った。結果は表４に示すように、粘度２０以上において、吐出性、付着滞留率、漂白力について良好な結果が得られた。一方、粘度５以下では、突条４０ａやスクリーン４２を設けて泡を形成しても、付着滞留率が著しく劣っていた。
【００５９】
【表４】

【００６０】
次に、突条４０ａの本数、形状、位置の影響を評価するため、実施例１６〜２４の評価を行った。結果は表５に示すように、いずれも良好な結果が得られた。ただし、実施例２４においては、付着滞留率がやや低めの値だった。これは、突条４０ａが出口付近に形成された場合、洗浄剤７０が衝突しにくく、充分な泡が形成されなかったためと考えられる。
【００６１】
【表５】

【００６２】
次に、スクリーン７０のメッシュの形状の影響を評価するため、実施例２５〜３１の評価を行った。結果は表６に示すように、いずれも良好な結果が得られた。なお、傾向としては、メッシュが細かいほど付着滞留性の向上が見られた。これは、メッシュが細かいほど、より泡を形成しやすくなるためと考えられる。
【００６３】
【表６】

【００６４】
【発明の効果】
本発明の洗浄剤製品は、吐出容器に、（１）次亜塩素酸アルカリ金属塩；０．１〜１０質量％、（２）アルカリ剤；０．１〜５質量％、（３）（ａ）炭素数が８〜２０の直鎖または分岐鎖の不飽和を含む脂肪酸のアルカリ金属塩、（ｂ）アミンオキサイド、及び、（ｃ）アルキル基の炭素数が１２〜１４のアルキルベンゼンスルホン酸塩を含む界面活性剤混合物、；０．１〜１０質量％を含有してなるために、チキソトロピー性を有し、かつＢ型粘度計を用いて２５℃、回転数６０ｒｐｍにおいて測定した粘度が２０ｍＰａ・ｓ〜１５００ｍＰａ・ｓである洗浄剤を収納したので、吐出装置から吐出させる際に、ノズルより何ら抵抗無く良好かつ均一に洗浄剤を吐出できる。
即ち、洗浄剤がチキソトロピー性を有することで、吐出装置からの吐出が困難となることが無く、付着滞留性の低下を防止し、容器本体から吐出装置への洗浄剤の連続的な汲み上げが困難とならないようにすることができる。また、吐出装置を、噴射ノズルに設けられたノズル穴と、該ノズル穴の上流側に設けられたスピン領域と、該ノズル穴から射出される洗浄剤の飛翔通路上に設けられた造泡筒を有する造泡機構を備えるものとし、該造泡筒の内径の上限を８ｍｍとすることにより造泡筒内壁に洗浄剤を確実に衝突させて吐出した洗浄剤に十分な泡を含ませることができ、下限を２ｍｍとすることで目詰まりを防止でき、適度な洗浄剤の吐出パターンにすることができる。
また、造泡機構を有する吐出装置に前述の特性の洗浄剤を用いたので、吐出された洗浄剤の組成物は垂直面や傾斜面の汚れ対象物を均一に覆うことができると共に、付着滞留性と漂白性に優れる。
従って本発明の洗浄剤製品によれば、何度も同じ場所に洗浄剤をかける必要がなく、手首の疲労感が軽減でき、洗浄剤の無駄な浪費がなくなると共に、非常に良好な洗浄効果が得られるので、特に、浴室、台所、トイレなどの硬質表面の漂白、カビ取りに好適に使用される。
【図面の簡単な説明】
【図１】 本発明の実施形態の洗浄剤製品を示す概略構成図である。
【図２】 図１の洗浄剤製品の泡モードにおける噴射ノズルを示す縦断面図である。
【図３】 図１の洗浄剤製品の直モードにおける噴射ノズルを示す縦断面図である。
【図４】 図１の洗浄剤製品の閉モードにおける噴射ノズルを示す縦断面図である。
【図５】 ミセル構造物の概念図である。
【図６】 洗浄対象物への洗浄剤の付着状況を示す説明図で、（ａ）は、従来の洗浄剤製品を用いた場合の付着状況、（ｂ）は、本実施形態の泡モードを用いた場合の付着状況である。
【図７】 実施例に用いた突条のパターン（ａ）（ｂ）を示す図である。
【図８】 実施例に用いたスクリーンのメッシュのパターン（ａ）〜（ｇ）を示す平面図である。
【符号の説明】
１・・・吐出容器、１１・・・トリガーレバー、１２・・・ピストン部、１３・・・容器本体、１３ａ・・・頸部、１４・・・射出筒、１７・・・送液チューブ、１５・・噴射ノズル、２０・・・トリガーポンプ、２７・・・ノズル孔、２８・・・ノズル本体、３１・・・洗浄剤ガイド体、３２・・・栓体、３３・・・内筒部、３９・・・造泡筒、３９ａ・・・噴射口、４０・・・内壁、４０ａ・・・突条、４１・・・取付筒、４２・・・スクリーン、４３・・・網穴、５０・・・周壁、５２・・・空気導入路、６０・・・浅溝、６６・・・深溝、７０・・・洗浄剤[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a detergent product in which a detergent is stored in a discharge container having a foam-forming mechanism, and in particular, it can stably hold a bleaching detergent or the like on a surface to be cleaned, and exhibits excellent cleaning power. It is related with the detergent product which can be made to make.
[0002]
[Prior art]
Conventionally, dirt in bathrooms, bathtubs, kitchen tiles, joints, plastics, pottery, drainage pipes, etc. where water is frequently used is often caused by organic substances caused by mold, and surfactants are not used. In order to remove these stains, bleach detergents based on alkali metal hypochlorite as the main base are frequently used because they cannot be easily removed with ordinary detergents having a main component (Japanese Patent Application Laid-Open No. 2005-318867). JP-A 62-57494, JP-A 06-256798, JP-A 10-204495, etc.).
[0003]
At that time, in order to use it easily, a method of storing a bleaching detergent in a discharge container equipped with a discharge device such as a trigger sprayer and spraying the bleaching detergent using this discharge device is often employed. In this case, it is required to improve the adhesion and retention of vertical surfaces and inclined surfaces.
[0004]
As a method for improving the adhesion retention property, a foam-forming cylinder (Japanese Utility Model Publication No. 6-34858) or a mesh screen (Japanese Examined Patent Publication No. 63-2668) is provided to foam a relatively low viscosity cleaning agent. Things have been done. In this case, since the viscosity is low, the discharge property is good, and the cleaning agent can be attached so as to cover the surface of the cleaning object relatively uniformly. Further, since the apparent specific gravity is reduced by the bubbles, it is possible to stay in the same position to some extent without being immediately drained by its own weight after adhering to the surface of the object to be cleaned.
[0005]
On the other hand, attempts have been made to increase the viscosity of the cleaning agent and improve adhesion retention. As a composition for increasing the viscosity, a composition containing a specific cross-linked polymer (JP 06-235000 A), a composition containing sodium magnesium silicate (JP 11-217596 A), a specific interface A composition containing an activator and a hydrophobic organic counter ion (Japanese Patent Laid-Open No. 11-279591) is disclosed.
[0006]
[Problems to be solved by the invention]
However, as described above, in the method of foaming a cleaning agent having a relatively low viscosity, although adhesion retention can be ensured to some extent, in particular, the bleaching cleaning agent is mainly based on an alkali metal hypochlorite salt. In this case, sufficient detergency cannot be exhibited.
The cause is considered as follows. That is, a cleaning agent having a relatively low viscosity has a high foaming property, and as shown in FIG. 6A, a large amount of bubbles B 'adhere to the surface of the object to be cleaned in a state where many layers overlap. Therefore, the cleaning agent component L ′ comes into contact with the cleaning object S only at the contact point with the bubble B ′, and the contact area becomes small.
Furthermore, the bleaching detergent mainly composed of alkali metal hypochlorite lowers pH by taking in carbon dioxide in the atmosphere, and generates hypochlorous acid having bleaching activity. However, when the bubbles B ′ overlap with each other, the cleaning agent component L ′ that is in contact with the surface of the object to be cleaned is less likely to come into contact with the atmosphere, and hypochlorous acid having bleaching activity is not sufficiently generated. It is done.
[0007]
On the other hand, in the method of increasing the viscosity of the cleaning agent, the viscosity at the time of discharge is too high, and the discharged liquid is sprayed linearly in a water gun shape or sprayed on spots, so that the surface of the object to be cleaned cannot be covered uniformly. There was a problem. In addition, dripping due to its own weight occurred, and the adhesion retention was not sufficient.
[0008]
In view of the above circumstances, the present invention is a detergent product capable of attaching a bleaching detergent or the like so as to uniformly cover dirt on the surface of the object to be cleaned, stably holding it, and exhibiting excellent cleaning power. It is an issue to provide.
[0009]
[Means for Solving the Problems]
  In order to solve the above problems, the present invention discharges the cleaning agent stored in the container main body and the container main body that stores the cleaning agent.Trigger type using trigger pumpA cleaning product comprising a discharge container having a discharge device and a cleaning agent housed in the container body,
The cleaning agent contained in the container body is
(1) alkali metal hypochlorite: 0.1 to 10% by mass,
(2) Alkaline agent: 0.1 to 5% by mass,
(3) (a)Includes linear or branched unsaturation with 8-20 carbon atomsAn alkali metal salt of a fatty acid, (b) an amine oxide, and (c)The alkyl group has 12 to 14 carbon atomsA surfactant mixture comprising an alkylbenzene sulfonate; comprising 0.1 to 10% by weight;The viscosity of the cleaning agent measured at 25 ° C. and a rotation speed of 60 rpm using a B-type viscometer is 20 mPa · s to 1500 mPa · s,
The discharge device isThe nozzle hole provided in the injection nozzle, the spin area provided upstream of the nozzle hole, and the nozzle hole are injectedProvided on the cleaning agent flight passageInner wall minimum diameter is 2-8mmHaving a foam tube,A cleaning agent flows in from the periphery of the spin region toward the central portion communicating with the nozzle hole of the spin region, and then is injected into the conical flow shape while rotating from the nozzle hole, and then the foam-forming It is configured to discharge while colliding with the inner wall of the cylinderA cleaning product characterized by the above is provided.
The cleaning agent in the present invention has thixotropic properties. Moreover, the said discharge apparatus has a foam making mechanism provided with a foam making cylinder.
[0010]
The thixotropic property means a property that fluidity increases (decreases viscosity) when subjected to shear stress, and returns to its original state (increased viscosity) when the force is removed. In this way, if the cleaning agent has thixotropic properties, even if it has a high viscosity at the time of standing, the fluidity is increased due to a high shear stress at the time of discharge, so the discharge liquid is injected linearly in a water gun shape. Or sprayed on spots, the problem that the surface of the object to be cleaned cannot be covered uniformly can be solved.
Further, after the discharge, when the surface of the cleaning object is reached, the shear stress disappears, so that the viscosity increases again. In addition, since the foaming mechanism allows foaming to be included in the cleaning agent, the apparent specific gravity is reduced, and it is possible to prevent liquid from dripping immediately by its own weight after adhering to the surface of the object to be cleaned. That is, a high viscosity when reaching the surface of the object to be cleaned and an apparent decrease in specific gravity make it possible to ensure adhesion retention.
[0011]
Furthermore, although the viscosity at the time of discharge is lower than that at the time of standing still, because of the relatively high viscosity, at the time of adhering to the surface of the object to be cleaned, moderate foaming that includes fine bubbles in the cleaning agent The amount is suppressed. That is, unlike the case where a cleaning agent having a low viscosity is originally foamed, a large amount of bubbles do not adhere to the surface of the object to be cleaned in a state where many layers overlap. For this reason, since the cleaning component can be brought into surface contact with the object to be cleaned, it is possible to uniformly cover the dirt and exhibit high cleaning power.
[0012]
In the present invention, the viscosity of the cleaning agent measured at 25 ° C. and a rotation speed of 60 rpm using a B-type viscometer is preferably 20 mPa · s or more. Thereby, adhesion staying property can be secured. Moreover, it can also prevent that the bubble is generated and the contact area to the cleaning object is reduced.
A more preferable value of the viscosity is 50 mPa · s or more, and a more preferable value is 100 mPa · s or more. Although there is no restriction | limiting in particular regarding the upper limit of the said viscosity, when the discharge property from a discharge device is considered, since the usability at the time of discharging from a container tends to be inferior when it exceeds 1500 mPa * s, it is unpreferable.
[0013]
In the present invention, the viscosity of the cleaning agent measured at 25 ° C. using a HaakeRS-100 viscometer is 3000 sec.^-1In the high shear rate region of 100 mPa · s or less, 0.5 sec^-1In the low shear rate range of 100 to 1 × 10^FivemPa · s is desirable. Here, 3000sec^-1Is the shear rate of 0.5 sec.^-1From 3000sec^-1Up to 3000 seconds when going up in 10 minutes^-1It is the viscosity when reaching. Similarly, 0.5 sec^-1Is the shear rate of 3000 sec.^-1From 0.5 sec^-1On the return trip when descending in 10 minutes until 0.5 sec^-1It is the viscosity when reaching.
The above 3000 sec^-1The lower limit of the viscosity in the high shear rate region is not particularly limited, but a preferable lower limit is 1 mPa · s, and a more preferable lower limit is 0.1 mPa · s.
Also, the above 3000 sec^-1A more preferable upper limit of the viscosity in the high shear rate region is 50 mPa · s, and a more preferable upper limit is 10 mPa · s.
0.5sec^-1More preferable lower limit of the viscosity in the low shear rate region (standing) is 5 × 10²mPa · s, more preferred lower limit is 1 × 10^ThreemPa · s.
[0014]
3000sec above^-1The upper limit value of the viscosity in the high shear rate region is a value selected so that the discharge of the cleaning agent from the discharge device such as a trigger sprayer is not difficult.
In addition, the above 0.5 sec^-1The lower limit value of the viscosity in the low shear rate region (standing) is a value selected so that the adhesion staying property on the wall surface or the like is not lowered.
0.5sec^-1It is preferable to select the upper limit value of the viscosity in the low shear rate region (stationary) so that the continuous pumping of the cleaning agent from the container body to the discharge device is not difficult.
[0015]
In the present invention, the cleaning agent preferably has a string-like micelle structure. In this case, it is possible to obtain a highly thixotropic cleaning agent in which the viscosity decreases rapidly when the shear rate increases, and the viscosity increases rapidly when the shear rate decreases. That is, when hysteresis is drawn by changing the shear rate, a large difference is obtained between when the shear rate is increased (outward path) and when the shear rate is decreased (return path).
This is thought to be because, in the case of string-like micelles, the structure is gently entangled, so that it can be rapidly aligned (decrease in viscosity) or entangled again (increase in viscosity) as the shear stress increases and decreases. It is done.
It should be noted that thixotropic properties cannot be obtained by increasing the viscosity in the case of a spherical micelle structure composed of a general surfactant. In addition, thixotropy is formed by polymers and clay minerals, and the force to form a network (interaction between particles) is strong. In a very short time, it is difficult to unravel this force and the viscosity does not easily drop.
As described above, since the string-like micelle structure is adopted, a sudden change in viscosity can be obtained. Therefore, the viscosity is increased to the extent that uniform discharge is possible in response to a sudden increase in shear stress during discharge. Can be reduced. In addition, when the shear stress reaches the surface of the object to be cleaned and suddenly decreases, the viscosity increases instantaneously, so that good adhesion retention is obtained.
[0016]
  In the present invention, the cleaning agent is a chlorine-based cleaning agent containing (1) an alkali metal hypochlorite, (2) an alkali agent, and (3) a surfactant.Ru. As described above, since the cleaning agent of the present invention has thixotropic properties, it adheres to the surface of the object to be cleaned in a state in which a large number of bubbles overlap each other like when a cleaning agent having a low viscosity is originally foamed. There is no end to it. Therefore, the cleaning agent component in contact with the surface of the object to be cleaned is likely to come into contact with the air, and the generation of hypochlorous acid having bleaching activity is easily promoted. Therefore, a high detergency can be exhibited.
[0017]
  In the present invention, as the foaming mechanism, a configuration having a foaming cylinder provided on the flight path of the cleaning agentAdopt. In addition, it is desirable that the foam-forming cylinder is arranged so as to have a central axis that is substantially the same as the central axis in the flight direction of the cleaning agent. In this case, since the cleaning agent entrains air inside the foaming cylinder while colliding with the inner wall of the foaming cylinder, the foam can be effectively contained. FoamingTubeThe minimum inner wall diameter is 2-8mmTheThis is because if the minimum diameter is larger than 8 mm, the cleaning agent does not easily collide with the inner wall of the foam-forming cylinder, and the cleaning agent cannot contain sufficient bubbles. On the other hand, if the minimum diameter is less than 2 mm, it is difficult to produce, and clogging is likely to occur, and the pattern does not spread in an appropriate pattern. Moreover, when providing a bubble making cylinder, it is desirable that the uneven | corrugated surface part is formed in the inner wall surface. Thereby, a bubble can be included more effectively.
[0018]
In the present invention, a configuration having a mesh screen provided on the cleaning agent flight path can also be suitably employed as the foaming mechanism. It is desirable that the screen is disposed substantially orthogonal to the central axis of the cleaning agent in the flight direction.
In this case, the cleaning agent that flies may be configured not to come into contact with surrounding members until reaching the screen, but the configuration in which the screen and the foam cylinder are combined, in particular, near the outlet of the foam cylinder. It is preferable to adopt a configuration provided in In this case, since the cleaning agent entrains air inside the foaming tube while colliding with the inner wall of the foaming tube, and further entrains air on the screen surface even when passing through the screen, it can contain bubbles more effectively.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the detergent product of the present invention will be described. First, the cleaning agent used in this embodiment will be described. The cleaning agent of this embodiment is a chlorine bleach containing (1) alkali metal hypochlorite, (2) alkali agent, and (3) surfactant.
Examples of the alkali metal hypochlorite (1) include sodium hypochlorite and potassium hypochlorite, with sodium hypochlorite being particularly preferred. Although content in particular of alkali metal hypochlorite is not restrict | limited, Usually, it is 0.1-10 mass% of the whole composition, Preferably it is the range of 1-5 mass%. If the content of the alkali metal hypochlorite is less than 0.1% by mass, the bleaching power is insufficient. On the other hand, even if it exceeds 10% by mass, the bleaching power is not particularly improved.
[0020]
(2) Although it does not restrict | limit especially as an alkali agent of a component, Caustic alkali, a silicate, etc. are mentioned. As the caustic alkali, sodium hydroxide, potassium hydroxide and the like are used, and as the silicate, sodium metasilicate and the like are used. Of these, sodium hydroxide is preferably used. The content of the alkali agent is not particularly limited, but is usually in the range of 0.1 to 5% by mass, preferably 0.5 to 3% by mass of the entire composition. When the content of the alkali agent is less than 0.1% by mass, the stability of the alkali metal hypochlorite decreases, and it tends to deteriorate over time. On the other hand, if the amount exceeds 5% by mass, the effect on the mucous membrane of the skin and eyes can be considered, and the effect of blending cannot be exhibited.
[0021]
(3) Although it does not restrict | limit especially as a surfactant of a component, Surfactant generally used for washing | cleaning uses, such as anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant, is mentioned. It is done. Among these, it is preferable to use at least one selected from (a) an alkali metal salt of a fatty acid, (b) an amine oxide, and (c) an alkylbenzene sulfonate, and the components (a) to (c) are used. Most preferably, it is used as a surfactant mixture.
[0022]
The above preferred surfactant and surfactant mixture will be described in more detail.
Although it does not restrict | limit especially as an alkali metal salt of the fatty acid which is (a) component, The alkali metal salt of the fatty acid containing a C8-C20 linear or branched unsaturated is suitable. Examples of alkali metal salts of fatty acids containing suitable unsaturation include, for example, coconut fatty acid (derived from coconut oil) containing an average of about 12 carbons, and tallow fatty acid (derived from tallow fats) containing an average of about 18 carbon atoms. ), Sodium salts such as oleic acid and linoleic acid, and potassium salts. These alkali metal salts of unsaturated fatty acids may be used alone, for example, a mixture of unsaturated fatty acids such as oleic acid and linoleic acid and saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, etc. A sodium salt, potassium salt, or the like may be used. The proportion of the unsaturated fatty acid salt is preferably 2% by mass or more, particularly 7% by mass or more in the component (a). If the ratio of the unsaturated fatty acid is too small, the viscosity of the system is lowered, and as a result, the adhesion retention is deteriorated.
[0023]
Although content in particular of (a) component in the cleaning agent of this embodiment is not restrict | limited, It is 0.01-3 mass% of the whole composition, Preferably it is the range of 0.1-2 mass%. When the content of the component (a) is less than 0.01% by mass, the adhesion retention is poor, and when it exceeds 3% by mass, the stability of the system is deteriorated.
[0024]
The amine oxide of component (b) is not particularly limited, but is preferably a tertiary amine oxide, and is represented by the general formula R₁R₂R_ThreeA tertiary amine oxide represented by N → O is more preferable. In the above general formula, R₁Examples of the alkyl group having 8 to 20 carbon atoms include octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, and mixtures of alkyl groups having different carbon numbers derived from natural products. In these, the dodecyl group and the alkyl group derived from coconut oil are preferable. R₂, R_ThreeIs an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable. Specific examples of the tertiary amine oxide include coconut dimethylamine oxide and lauryl dimethylamine oxide.
[0025]
Although content in particular of (b) component in the cleaning agent of this embodiment is not restrict | limited, It is 0.01-5 mass% of the whole composition, Preferably it is the range of 0.1-3 mass%. When the content of the component (b) is less than 0.01% by mass, the adhesion retention is poor, and when it exceeds 5% by mass, the stability of the alkali metal hypochlorite is deteriorated over time.
[0026]
Although it does not restrict | limit especially as alkylbenzenesulfonate of (c) component, Carbon number of the alkyl group substituted to a benzene ring is 8-20, Preferably it is 12-14, and a linear thing is suitable.
The content of the component (c) in the cleaning agent of the present embodiment is not particularly limited, but is 0.01 to 0.5% by mass, preferably 0.05 to 0.3% by mass of the entire composition. . When the content of the component (c) is less than 0.01% by mass, the adhesion retention is poor, and when it exceeds 0.5% by mass, the stability of the system is deteriorated.
[0027]
The cleaning agent of the present embodiment has the above components (1) to (3) as essential components, but as other builder for improving cleaning performance, aromatic sulfonates such as toluene sulfonate and xylene sulfonate, It is also possible to mix arbitrary components such as a solvent, a pigment, and a fragrance. The blending amount of these optional components can be a normal amount as long as the effects of the present invention are not hindered. The bleaching detergent composition of the present invention can be prepared by a conventional method by adding a balanced amount of water to the above essential components and other optional components.
[0028]
The cleaning agent of this embodiment has a viscosity at 25 ° C. of 20 mPa · s or more, preferably 50 mPa · s or more, more preferably 100 mPa · s or more.
Further, the cleaning agent of the present embodiment exhibits a thixotropic property of quasi-viscous flow. That is, the cleaning agent of this embodiment has a viscosity of 3000 sec measured with a Haake RS-100 viscometer at 25 ° C.^-1In the high shear rate range of 0.1 to 100 mPa · s, preferably 0.1 to 50 mPa · s, more preferably 0.1 to 10 mPa · s, and 0.5 sec.^-1In the low shear rate range (stationary)^FivemPa · s, preferably 5 × 10²~ 1x10^FivemPa · s, more preferably 1 × 10^Three~ 1x10^FiveIt is set to mPa · s.
[0029]
The cleaning agent of this embodiment has a string-like micelle structure made of a surfactant as shown in FIG. 5 so as to exhibit the above-described excellent thixotropy.
The size of the micelle aggregate can be directly measured by the light scattering method. When the micelle size is not so large, there is no angle dependency of light scattering. This is true for most surfactant spherical micelles. At this time, if the molecular weight of the micelle is defined, the Debye equation is established.
The molecular weight and dry radius of the giant micelle can be obtained from the angular dependence of the Debye plot. It increases in parallel with the molecular weight. If giant micelles are represented by rigid rods, the radius of inertia R is proportional to the molecular weight M, but actually has a lower dependence, and their relationship is R for many surfactants. ~ M^0.6The proportional relationship is shown. This indicates that the giant micelle is rod-shaped but not rigid but flexible, and its degree is close to that of a random coil. Such a huge micelle is generally called a string-like micelle. It is known that string-like micelles are formed by growing ionic micelles by adding salt.
As shown in FIG. 5, string-like micelles form a gently entangled structure, and the viscosity changes abruptly in response to a sudden change in shear stress.
[0030]
Next, the discharge container of this embodiment is demonstrated based on figures. In the present embodiment, a case will be described in which a trigger type discharge container using a trigger pump as a discharge device is filled with a cleaning agent to obtain a cleaning product.
FIG. 1 is a schematic configuration diagram showing a cleaning product according to an embodiment of the present invention. The cleaning product of this embodiment includes a discharge container 1 and a cleaning agent 70. The discharge container 1 has a neck portion 13a, a container body 13 filled with the cleaning agent 70, and an upper portion of the neck portion 13a. It is comprised from the trigger pump 20 (discharge device) attached to. The cleaning agent 70 is the cleaning agent of the present embodiment described above.
[0031]
The trigger pump 20 is inserted into the injection cylinder 14, the piston part 12 incorporated in the injection cylinder 14, the trigger lever 11 that drives the piston part 12, and the container body 13, and on the upstream side of the piston part 12. The liquid feeding tube 17 is connected to the distal end side of the injection cylinder 14 and the injection nozzle 15 is connected to the downstream side of the piston portion 12. The foaming mechanism is provided in the injection nozzle 15.
Although detailed illustration of the piston portion 12 is omitted, the piston portion 12 is schematically composed of a cylinder and a piston 12a, an intake valve on the upstream side of the cylinder, and an ejection valve on the downstream side of the cylinder. The trigger lever 11 operates the biston 12a. By doing so, the cleaning agent 70 introduced from the liquid feeding tube 17 is fed to the spray nozzle 15 at a high pressure.
[0032]
A foaming mechanism for causing the cleaning agent 70 to contain foam is provided in the spray nozzle 15. The injection nozzle 15 can select any one of a bubble mode, a straight mode, and a closed mode. When the foam mode is selected, bubbles are generated in the cleaning agent 70 by the foam-forming mechanism (the foam-forming cylinder 39 and the screen 42) in the injection nozzle 15, and the cleaning agent 70 containing the bubbles is injected. The liquid is sprayed toward the object to be cleaned.
Further, when the straight mode is selected, the jetting liquid of the cleaning agent 70 that does not contain bubbles is sprayed as it is. When the closed mode is selected, the trigger lever 11 can be pulled. It is designed not to be jetted.
Hereinafter, the configuration and operation of the injection nozzle 15 will be described in detail for each mode.
[0033]
FIG. 2 is a longitudinal sectional view showing the injection nozzle 15 in the bubble mode.
In FIG. 2, reference numeral 31 denotes a cleaning agent guide body fitted and fixed inside the end portion 12 b on the downstream side of the piston portion 12 at the tip end portion of the injection cylinder 14. The distal end portion of the cleaning agent guide body 31 is a plug body 32 in which shallow grooves 60 and 60 are formed in the busbar direction at a plurality of circumferential positions.
[0034]
Reference numeral 28 denotes a nozzle body, which is rotatably fitted to the end 12b of the piston portion 12 in a substantially cylindrical fitting wall 25. A shielding wall 26 is formed on the downstream end face of the fitting wall 25, and a nozzle hole 27 is formed in the center in the vicinity of the distal end portion of the plug 32. A gap between the nozzle hole 27 and the plug 32 is a spin region 63.
Further, the nozzle body 28 is formed with an inner cylinder portion 33 from the shielding wall 26 toward the upstream side, and the protruding end portion 61 of the inner cylinder portion 33 has inner grooves 24 in a plurality of circumferential directions in the direction of the bus. , 24 are formed. In the case of the bubble mode of FIG. 2, the positions of the inner grooves 24, 24 and the shallow grooves 60, 60 coincide with each other in the circumferential direction, and the inner cylinder portion 33 and the cleaning agent guide body formed by connecting these grooves. A space between the piston portion 31 and the spin region 63 forms a flow path 62 that leads from the piston portion 12 to the nozzle hole 27.
[0035]
Further, the peripheral wall 50 of the nozzle body 28 has a protruding wall 51 on the downstream side, and a mounting cylinder 41 integrally formed with the screen 42 and the foam-forming cylinder 39 is fitted and fixed to the protruding wall 51. . The foam-forming cylinder 39 is arranged coaxially with the mounting cylinder 41 with the downstream end face aligned. Further, the foam-forming cylinder 39 is formed to have a smaller diameter and shorter than the mounting cylinder 41, and a gap 34 is formed between the foam-forming cylinder 39 and the shielding wall 26. Further, the screen 42 is positioned on the downstream end face of the foam-forming cylinder 39 and the mounting cylinder 41, and the position of the foam-forming cylinder 39 with respect to the mounting cylinder 41 is maintained by the screen 42.
A liquid dripping prevention mechanism 80 is formed on the downstream side of the shielding wall 26 so as to protrude toward the foam-forming cylinder 39.
Ring-shaped protrusions 40a are formed in various patterns on the inner wall 40 of the foam tube 39 in various patterns, as will be described in detail in the following embodiments. The screen 42 is formed with a plurality of mesh holes 43... In various patterns, as will be described in detail in the following embodiments.
A path from the mesh holes 43 to the gap 34 via the bubble-forming cylinder 39 and the mounting cylinder 41 is an air introduction path 52 into the bubble-forming cylinder 39.
[0036]
As described above, in the foam mode shown in FIG. 2, the positions of the inner grooves 24, 24 and the shallow grooves 60, 60 coincide with each other in the circumferential direction, and the inner cylinder portion 33 formed by communicating these grooves and the cleaning agent. A gap between the guide body 31 and the spin region 63 forms a flow path 62 that leads from the piston portion 12 to the nozzle hole 27. In this case, the flow path 62 is narrow at the position of the shallow grooves 60, 60 and has a sharp bend at the position where the spin region 63 is entered.
Therefore, when the cleaning agent 70 whose pressure has been increased by the piston portion 12 is supplied, the high-pressure cleaning agent 70 rapidly flows from the periphery of the spin region 63 toward the center and is rotated at a high speed.
Then, it is ejected from the nozzle hole 27 in a conical flow shape, and reaches the screen 42 without colliding with the inner wall 40 of the foam-forming cylinder 39. Further, while colliding with the screen 42, the mesh hole of the injection port 39a. 43 and 43 are discharged as the injection liquid F.
[0037]
In this way, in the process in which the cleaning agent 70 passes through the nozzle hole 27 via the flow path 62, the viscosity decreases due to shearing stress from each member of the nozzle 15, so that the injection is performed without requiring a strong gripping force of the user. it can. In addition, the nozzles 27 are uniformly ejected without causing spots like when a high viscosity cleaning agent is forcibly discharged. On the other hand, since the moderate viscosity is maintained, the air G can be appropriately taken in as fine bubbles in the process of colliding with the inner wall 40 and the screen 42 of the foam-forming cylinder 39.
[0038]
Then, when the spray liquid F reaches the object to be cleaned, the shear stress suddenly decreases and the high viscosity is immediately recovered. In this way, the high viscosity is recovered, and the apparent specific gravity is lowered due to the taken-in bubbles, so that the jet liquid F has high adhesion retention. Moreover, since it inject | emitted uniformly from the nozzle hole 27, it can adhere to a washing | cleaning target object also uniformly.
[0039]
Furthermore, unlike when a cleaning agent having a low viscosity is originally foamed, a large amount of foam does not adhere to the surface of the object to be cleaned in a state where many layers are overlapped. Therefore, as shown in FIG.6 (b), the cleaning agent component L can carry out surface contact, including the bubble B in the washing | cleaning target object S, and can enlarge a contact area. It can evenly adhere to dirt and exert its detergency evenly.
Furthermore, the cleaning agent component L in contact with the surface of the cleaning object S is likely to come into contact with the air, and the generation of hypochlorous acid having bleaching activity is easily promoted. Therefore, a high detergency can be exhibited.
As described above, when the foam mode is selected in the cleaning product of the present embodiment, the spray liquid F is uniformly attached to the object to be cleaned without requiring a strong gripping force of the user, and the state is stably maintained. In addition, since the bleaching activity of the cleaning agent 70 itself is improved, effective cleaning can be performed.
[0040]
FIG. 3 is a longitudinal sectional view showing the injection nozzle 15 in the straight mode.
3, the same components as those in FIG. 2 are denoted by the same reference numerals, and detailed description thereof is omitted. Switching from the foam mode shown in FIG. 2 to the straight mode shown in FIG. 3 is performed by rotating the nozzle body 28 by 120 degrees. However, for convenience of explanation, in FIG. Is shown in a state rotated 120 degrees.
As shown in FIG. 3, a plurality of deep grooves 66, 66 are formed in the plug body 32 from the front end face in a circumferential direction at a plurality of locations in the busbar direction over a certain section.
[0041]
In the case of the straight mode of FIG. 3, the positions of the inner grooves 24, 24 and the deep grooves 66, 66 coincide with each other in the circumferential direction, and the inner cylinder portion 33 and the cleaning agent guide body 31 formed by connecting these grooves The air gap between them and the spin region 63 form a flow path 62 that leads from the piston portion 12 to the nozzle hole 27. In this case, the flow path 62 is wide at the positions of the deep grooves 66 and 66 and has a gentle bend at the position where the spin area 63 is entered.
Therefore, when the cleaning agent 70 whose pressure has been increased by the piston portion 12 is supplied, the high-pressure cleaning agent 70 gently flows into the spin region 63, and a small diffusion angle is applied from the nozzle hole 27 without applying much rotational force. Injected into a conical flow. Then, it reaches the screen 42 with almost no collision with the inner wall 40 of the foam tube 39. Moreover, since it collides at a low speed also when colliding with the screen 42 compared with the case of bubble mode, as a result, it discharges as the injection liquid F from the net holes 43 and 43, containing few bubbles.
[0042]
FIG. 4 is a longitudinal sectional view showing the injection nozzle 15 in the closed mode.
4, the same components as those in FIG. 2 are denoted by the same reference numerals, and detailed description thereof is omitted. Switching from the bubble mode shown in FIG. 2 to the straight mode shown in FIG. 4 is performed by rotating the nozzle body 28 by 120 degrees on the opposite side to that in FIG. 3, but for convenience of explanation, FIG. FIG. 4 shows a state where the cleaning agent guide body 31 side is rotated 120 degrees.
[0043]
In the closed mode of FIG. 4, a location where neither the shallow groove 60 nor the deep groove 66 of the plug body 32 is formed is located in the circumferential direction to be communicated with the inner grooves 24, 24. The nozzle hole 27 is closed by 32 without being reached.
Therefore, even when the cleaning agent 70 whose pressure has been increased by the piston portion 12 is supplied, the cleaning agent 70 is not ejected from the nozzle 15.
[0044]
In the present embodiment, the foam-forming cylinder 39 and the like are formed separately from the nozzle body 28, but may be formed integrally with the nozzle body 28. For example, it may be formed continuously with the inner cylinder portion 33 while securing the air introduction path 52.
In this embodiment, a trigger type discharge container using a trigger pump is filled with a cleaning agent to obtain a cleaning product, but a former pump dispenser can also be used.
[0045]
【Example】
Hereinafter, in the said embodiment, performance evaluation was performed about the Example and comparative example which changed the property of the foaming cylinder 39, the screen 42, and the cleaning agent 70 variously. The viscosity measurement method as the properties of the cleaning agent 70, and the ejection performance, the adhesion retention rate, and the bleaching power as the performance evaluation indexes were determined by the following methods.
[0046]
<Measurement method of viscosity>
The cleaning agent 70 adjusted to 25 ° C. was measured using a B-type viscometer (manufactured by TOKIMEC; DVL-B2), and the value after 1 minute was measured at a rotational speed of 60 rpm and a third rotor.
[0047]
<Measurement method of viscosity>
Various bleaching detergent compositions adjusted to 25 ° C. were measured using a B-type viscometer (manufactured by TOKIMEC; DVL-B2), and the value after 1 minute was measured at a rotational speed of 60 rpm and a third rotor.
[0048]
<Ejection evaluation method>
Using a trigger-type sprayer, sensory evaluation was performed according to the following evaluation criteria by five panelists on the discharge performance when a total of five strokes were made to the central portion of the spray panel standing vertically from a position where the distance became 20 cm.
[0049]
Evaluation criteria;
5 (dots): A liquid having fine bubbles uniformly adheres in a perfect circle.
4: The liquid with fine bubbles is uniformly attached in a substantially circular shape.
3: The liquid with fine bubbles adheres substantially uniformly in a substantially circular shape.
2: The liquid with rough bubbles is adhered almost uniformly in a distorted circle.
1: The liquid with rough bubbles adheres to the spots in a distorted circular shape.
[0050]
<Measurement method of adhesion retention>
In the same manner as the method for evaluating the dischargeability, various bleaching detergents are sprayed on the central portion of the spray panel using a trigger sprayer, and the weight of the panel is measured after 1 minute. This test was performed three times, and the adhesion retention rate was calculated by the following formula.
[Expression 1]

[0051]
<Measurement of bleaching power>
Black mold (Cladosporium cladosporioides) cultured and deposited unglazed tile [INAX: SPKC-1060] was used as a model plate. L value = 30-40). The model mold plate was placed vertically, and various bleaching compositions were sprayed from a distance of 10 cm onto the center of the one-stroke (about 0.8 g) plate using a trigger sprayer. After being left for 3 minutes, washed with water and air-dried, the lightness (L value) was measured using a color difference meter [manufactured by MINOLTA; CR-200].
[0052]
(About the inner diameter of the foam tube)
In order to evaluate the appropriate inner diameter of the foam-forming cylinder 39, first, Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated without the protrusion 40a and the screen 42. As shown in Table 1, good results were obtained in terms of dischargeability, adhesion retention rate, and bleaching power in the range of 2 to 8 mm in inner diameter.
[0053]
[Table 1]

[0054]
Next, evaluation of Examples 6 to 8 provided with the protrusions 40a was performed in the range of the inner diameter of the foam-forming cylinder 3 evaluated as appropriate in the above. As shown in Table 2, good results were obtained with respect to ejection properties, adhesion retention rate, and bleaching power.
In the following, the shapes (a) and (b) of the protrusions refer to the longitudinal cross-sectional shapes (a) and (b) shown in FIG. 7, respectively. Further, the position of the ridge indicates the length from the nozzle hole 27 side end of the foam-forming tube 39 to the nearest ridge, and the “back” is 4.0 mm in length. In this case, “intermediate” means that the length is 4.5 mm, and “exit” means that the length is 5.0 mm. Moreover, when there are a plurality of protrusions, each pitch is 0.7 mm.
[0055]
[Table 2]

[0056]
Next, in the range of the inner diameter of the foam-forming cylinder 3 evaluated as appropriate in the above, evaluation of Examples 9 to 12 in which the protrusions 40a are not provided and the screen 42 (mesh shape: (a)) is provided. Went. As a result, as shown in Table 3, in all cases, good results were obtained with respect to dischargeability, adhesion retention rate, and bleaching power. In addition, in the above and the following, the shapes (a) to (g) of the mesh indicate the shapes (a) to (g) shown in FIG.
[0057]
[Table 3]

[0058]
Next, in order to evaluate the influence of the viscosity of the cleaning agent 70, Examples 13 to 15 and Comparative Examples 3 to 4 were evaluated. As shown in Table 4, when the viscosity was 20 or more, good results were obtained with respect to dischargeability, adhesion retention rate, and bleaching power. On the other hand, at a viscosity of 5 or less, even when the protrusions 40a and the screen 42 were provided to form bubbles, the adhesion retention rate was extremely inferior.
[0059]
[Table 4]

[0060]
Next, Examples 16 to 24 were evaluated in order to evaluate the influence of the number, shape, and position of the protrusions 40a. As shown in Table 5, good results were obtained in all cases. However, in Example 24, the adhesion retention rate was slightly lower. This is considered to be because when the protrusion 40a is formed in the vicinity of the outlet, the cleaning agent 70 hardly collides and sufficient bubbles are not formed.
[0061]
[Table 5]

[0062]
Next, in order to evaluate the influence of the mesh shape of the screen 70, Examples 25-31 were evaluated. As shown in Table 6, good results were obtained in all cases. In addition, as a tendency, the improvement of adhesion retention was seen, so that the mesh was fine. This is probably because the finer the mesh, the easier it is to form bubbles.
[0063]
[Table 6]

[0064]
【The invention's effect】
  The cleaning product of the present invention isVomitIn the discharge container, (1) alkali metal hypochlorite; 0.1 to 10% by mass, (2) alkali agent; 0.1 to 5% by mass, (3) (a)Includes linear or branched unsaturation with 8-20 carbon atomsAn alkali metal salt of a fatty acid, (b) an amine oxide, and (c)The alkyl group has 12 to 14 carbon atomsA surfactant mixture containing an alkylbenzene sulfonate; contains 0.1 to 10% by mass, and therefore has thixotropic properties.And a viscosity measured at 25 ° C. and a rotation speed of 60 rpm using a B-type viscometer is 20 mPa · s to 1500 mPa · s.Since the cleaning agent is stored, the cleaning agent can be discharged well and uniformly without any resistance from the nozzle when discharging from the discharge device.
  That is, since the cleaning agent has thixotropic properties, there is no difficulty in discharging from the discharge device, preventing a decrease in adhesion retention, and it is difficult to continuously pump the cleaning agent from the container body to the discharge device. Can be prevented. Also,The discharge device includes a nozzle hole provided in the injection nozzle, a spin area provided upstream of the nozzle hole, and a foam-forming cylinder provided on a flight path of the cleaning agent injected from the nozzle hole. It shall be equipped with a foaming mechanism,By setting the upper limit of the inner diameter of the foam-forming cylinder to 8 mm, it is possible to ensure that the cleaning agent collides with the inner wall of the foam-forming cylinder and to discharge sufficient detergent, and clogging by setting the lower limit to 2 mm. Can be prevented, and an appropriate discharge pattern of the cleaning agent can be obtained.
  In addition, since the cleaning agent having the above-mentioned characteristics is used in the discharge device having the foam-forming mechanism, the discharged cleaning composition can uniformly cover the soiled object on the vertical surface and the inclined surface, and adhere and stay. Excellent in bleaching and bleaching properties.
  Therefore, according to the cleaning product of the present invention, it is not necessary to apply the cleaning agent to the same place over and over, the feeling of wrist fatigue can be reduced, the waste of the cleaning agent is eliminated, and a very good cleaning effect is obtained. Since it is obtained, it is particularly suitably used for bleaching hard surfaces such as bathrooms, kitchens and toilets and removing mold.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram showing a cleaning product according to an embodiment of the present invention.
FIG. 2 is a longitudinal sectional view showing a spray nozzle in a foam mode of the cleaning product of FIG.
3 is a longitudinal sectional view showing an injection nozzle in the straight mode of the cleaning product of FIG. 1. FIG.
4 is a longitudinal sectional view showing an injection nozzle in a closed mode of the cleaning product of FIG. 1. FIG.
FIG. 5 is a conceptual diagram of a micelle structure.
6A and 6B are explanatory diagrams showing the state of attachment of the cleaning agent to the object to be cleaned, where FIG. 6A shows the state of attachment when a conventional cleaning product is used, and FIG. 6B shows the foam mode of the present embodiment. It is the adhesion situation when used.
FIG. 7 is a diagram showing ridge patterns (a) and (b) used in Examples.
FIG. 8 is a plan view showing screen mesh patterns (a) to (g) used in the examples.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Discharge container, 11 ... Trigger lever, 12 ... Piston part, 13 ... Container main body, 13a ... Neck part, 14 ... Injection cylinder, 17 ... Liquid feeding tube, 15 .... Injection nozzle, 20 ... trigger pump, 27 ... nozzle hole, 28 ... nozzle body, 31 ... cleaning agent guide body, 32 ... plug body, 33 ... inner cylinder 39 ... Foam tube, 39a ... injection port, 40 ... inner wall, 40a ... ridge, 41 ... mounting tube, 42 ... screen, 43 ... net hole, 50 ... Peripheral wall, 52 ... Air introduction path, 60 ... Shallow groove, 66 ... Deep groove, 70 ... Cleaning agent

Claims (8)

A discharge container having a container main body for storing the cleaning agent, a trigger type discharge device using a trigger pump for discharging the cleaning agent stored in the container main body, and the cleaning agent stored in the container main body; A detergent product comprising:
The cleaning agent contained in the container body is
(1) alkali metal hypochlorite: 0.1 to 10% by mass,
(2) Alkaline agent: 0.1 to 5% by mass,
(3) (a) Alkali metal salt of fatty acid containing linear or branched unsaturated having 8 to 20 carbon atoms , (b) amine oxide, and (c) alkyl group having 12 to 14 carbon atoms Surfactant mixture containing alkylbenzene sulfonate; 0.1 to 10% by mass, and the viscosity of the cleaning agent measured at 25 ° C. and a rotational speed of 60 rpm using a B-type viscometer is 20 mPa · s to 1500 mPa · s,
The discharge device has a nozzle hole provided in an injection nozzle, a spin region provided upstream of the nozzle hole, and a minimum inner wall diameter provided on a flying path of a cleaning agent injected from the nozzle hole. The foaming cylinder has a diameter of 2 to 8 mm, and the cleaning agent flows in from the periphery of the spin region while rotating toward the central portion communicating with the nozzle hole of the spin region, and then rotates from the nozzle hole. The detergent product is configured to be ejected in a conical flow shape and then discharged while colliding with the inner wall of the foam-forming cylinder . The said washing | cleaning agent contains 0.1-2 mass% of alkali metal salt of the fatty acid containing (a) C8-C20 linear or branched unsaturated. Cleaning product. The said cleaning agent contains 0.1-3 mass% of (b) amine oxide, The cleaning product of Claim 1 or 2 characterized by the above-mentioned. The said cleaning agent contains 0.05-0.3 mass% of alkylbenzene sulfonates with 12-14 carbon atoms of (c) alkyl group, The cleaning agent as described in any one of Claims 1-3 characterized by the above-mentioned. Cleaning products. 5. A cleaning product according to any one of claims 1 to 4, wherein an uneven surface portion is formed on an inner wall surface of the foam-forming cylinder. The detergent product according to any one of claims 1 to 4, wherein a ring-shaped protrusion is formed on an inner wall surface of the foam-forming cylinder. The detergent product according to any one of claims 1 to 4, wherein two or more ring-shaped protrusions are formed on an inner wall surface of the foam-forming cylinder. Furthermore, it has a mesh-like screen provided in the downstream end surface of the said foaming cylinder, The cleaning agent product as described in any one of Claims 1-7 characterized by the above-mentioned.

Images