TW202417604A - Cleaning article - Google Patents

Abstract

A cleaning article comprising: an accumulator-type trigger spray container; and a liquid cleaning composition contained in the spray container, wherein the spray container is capable of spraying the liquid cleaning composition into foam, the foam specific volume of sprayed foam is at least 15 mL/g, and the ratio of the foam specific volume of foam sprayed at 0.2 seconds/stroke from the spray container to the foam specific volume of foam sprayed at 0.5 seconds/stroke from the spray container is 0.5 or more and less than 2.0.

Description

Cleaning items

The present invention relates to a cleaning article and a cleaning method for the surface of a cleaning object.

In the sinks used for washing dishes or vegetables, or around countertops, gas stoves, etc., there are inorganic stains with silicon or calcium as the main components, oil stains from cooking or dishes, and other complex stains. In particular, the stains generated around cooking machines are mainly caused by cooking oil, which is close to the heat source, so the oil is easy to deteriorate and is very difficult to remove. Previously, for such stains, powder or liquid detergents mixed with abrasives or strong alkaline detergents were used. However, in the former case, although it has excellent cleaning performance on stains, the problem is the labor of hard scrubbing or the complexity of rinsing and wiping, and the latter has problems such as insufficient cleaning performance on inorganic stains or rough hands caused by alkali. In addition, when cleaning kitchens, toilets, bathrooms, living rooms, etc., trigger-type spray containers that can spray detergent compositions are used. From the perspective of preventing dripping from the object to be cleaned or extending the time of retention on the object to be cleaned to improve the cleaning effect, bubble spray-type triggers are becoming more and more popular.

Japanese Patent Publication No. 2017-214464 discloses a hard surface cleaning article, which includes a trigger spray container and a liquid detergent composition contained in the spray container. The spray container can spray the liquid detergent composition in the form of foam, and the foam specific volume of the sprayed foam is 15 mL/g or more. In Japanese Patent Publication No. 2021-105076, a cleaning article is disclosed, which contains a liquid cleaning agent composition in a pressure-accumulated bubble-spraying trigger spray container, and the speed of pulling the trigger is set to 6 g/s to 18 g/s, and the foam specific volume of the foam after 1 minute of spraying is 15 mL/g to 45 mL/g, and the speed of pulling the trigger is set to 21 g/s to 45 g/s, and the foam specific volume of the foam after 1 minute of spraying is 10 mL/g or less.

In recent years, young people have given priority to simplifying housework or shortening time to avoid wasting time and effort on maintaining cleanliness. In addition, the number of elderly single-person households has increased, and housework has become a greater burden. People are seeking a method for cleaning objects and surfaces of cleaning objects that can capture such changes in the social environment and can easily and efficiently clean hard surfaces and other cleaning objects with satisfactory cleaning effects. The present invention provides a method for cleaning objects and surfaces of cleaning objects that can easily and efficiently clean hard surfaces and have satisfactory cleaning effects.

The present invention relates to a cleaning article, which has a pressure storage trigger spray container and a liquid cleaning agent composition contained in the spray container, and the spray container can spray the liquid cleaning agent composition into foam, the foam specific volume of the sprayed foam is 15 mL/g or more, and the ratio of the foam specific volume of the foam sprayed from the spray container at 0.2 seconds/stroke to the foam specific volume of the foam sprayed from the spray container at 0.5 seconds/stroke is 0.5 or more and less than 2.0.

Furthermore, the present invention relates to a method for cleaning a surface of an object to be cleaned, wherein the foam sprayed by the cleaning article is brought into contact with the surface of the object to be cleaned.

According to the present invention, a cleaning article and a cleaning method for the surface of a cleaning object are provided, which can clean the surface of the cleaning object simply and efficiently and have a satisfactory cleaning effect.

When the cleaning article of the present invention sprays the liquid cleaning agent composition from the trigger spray container, good foam can be always formed regardless of the speed of pulling the trigger. It is speculated that the cleaning article of the present invention can obtain sufficient foaming properties, and the feeling of use or excellent foam cleaning properties even when the speed of pulling the trigger varies depending on the user of the article.

The present invention is described below based on its preferred embodiment. The cleaning article of this embodiment includes a trigger spray container 1 and a liquid cleaning agent composition (not shown) contained in the spray container. The spray container used in the present invention is a trigger spray container. The trigger spray container is shown in FIG. 1 as a spray container 1, which has the following structure, that is, a trigger sprayer 3 for spraying the liquid is installed at the mouth of a bottomed container body 2 filled with a liquid as a liquid detergent composition. Generally speaking, by pulling the trigger 4, the air in the cylinder 9 is discharged to the outside, and when the trigger 4 returns, the liquid is sucked up through the tube 7 immersed in the liquid, so that the cylinder 9 is filled with the liquid, and the trigger 4 is pulled again, and the liquid in the cylinder 9 is pushed out and introduced into the vertical pipe 6, and then the horizontal pipe 8 and the rotating element 10 are used to apply spin to the flow of the liquid, and the liquid is sprayed from the nozzle 11.

The more specific structure of the spray container used in the present embodiment is described with reference to FIG. 1 . The spray container 1 has the following structure: a trigger sprayer 3 for spraying liquid is detachably or non-detachably mounted on the mouth of a bottomed container body 2 filled with liquid by means of a screw connection or the like. The sprayer 3 is mainly composed of a sprayer body 5 for spraying the liquid filled in the container body 2 by pulling a trigger 4. A vertical pipeline 6 and a horizontal pipeline 8 connected to the vertical pipeline 6 are formed in the sprayer body 5. A cylindrical wall portion 91 constituting a material cylinder 9 is formed below the horizontal pipeline 8, and a piston member 92 sliding in the material cylinder 9 is provided. Moreover, the trigger 4 of the push piston member 92 is rotatably embedded in the side wall of the sprayer body 5. The small circle 41 shown by the single-point chain in Figure 1 indicates the position of the rotation axis of the trigger 4 provided on the side wall of the sprayer body 5. In addition, the trigger 4 is energized in a direction away from the mouth of the container body 2 by using an energizing device such as a leaf spring or a coil spring (not shown). In this specification, the top and the bottom are the top or the bottom in the vertical direction when the spray container 1 is placed on a horizontal surface.

The material cylinder 9 has a first check valve 93 and a second check valve 94. The first check valve 93 allows the inflow of liquid from the flow path on the side of the tube 7, and on the other hand, prevents the backflow of the liquid to the flow path when the trigger 4 is pulled. The second check valve 94 allows the outflow of liquid from the flow path on the side of the horizontal pipe 8, and on the other hand, prevents the backflow of the liquid from the flow path when the trigger 4 returns. The rotating element 10 is cylindrical, as shown in FIG. 2, and has a plurality of grooves 10a extending along its axial direction. At the front end portion arranged on the side of the nozzle portion 11, there is a cylindrical recess 10b and a groove 10c connecting the recess 10b and each groove 10a. The groove 10c is connected to a location offset from the center of the concave portion 10b, so that the flow of the liquid in the concave portion 10b is given spin, and the liquid to which the spin is given is ejected in a cone shape from the ejection port 11b provided in the ejection port forming member 11a disposed near the front end of the rotating element 10. The ejection port forming member 11a forms the ejection nozzle 11 together with the foaming member 11c mounted on the front end thereof. Between the foaming member 11c and the ejection port forming member 11a, a hole or groove 11d for air capture is formed, which has an inner opening on the back side of the liquid ejected in a cone shape and an outer opening at the front end of the ejection port forming member 11a. By mixing the air captured through the air capture hole or groove 11d with the liquid sprayed in a cone shape, the liquid detergent composition as the liquid becomes foam and is sprayed from the foam spraying port 11e.

The sprayer 3 of the spray container 1 shown in FIG1 is a pressure accumulator sprayer. The so-called pressure accumulator sprayer is constructed in such a way that even if the trigger 4 is operated, the liquid from the nozzle 11 will not be sprayed before the hydraulic pressure in the cylinder 9 reaches the specified hydraulic pressure, and the liquid will be sprayed when the hydraulic pressure in the cylinder 9 is higher than the specified hydraulic pressure. The sprayer 3 shown in FIG1 is equipped with a pressure accumulator component 12 in order to start spraying when the pressure in the cylinder 9 is higher than the specified hydraulic pressure. The pressure accumulator member 12 has a cylinder 13 with a cylindrical inner wall surface, and a valve member 14 disposed in the cylinder 13 and moving up and down along the center axis of the cylinder 13. The valve member 14 is always energized upward by an energizing device 15 such as a disc spring. When the trigger 4 is not operated, as shown in FIG1 , the bolt body 14a formed at the upper end of the valve member 14 closes the outlet 13a of the flow path toward the downstream side. Below the bolt body 14a, a plunger portion 14b is provided whose outer periphery is in sliding contact with the inner wall surface of the cylinder 13, and a small-diameter cylindrical portion 14c is provided on the lower surface of the plunger portion 14b. At the lower end of the bolt body 14a, a flow path 14a' is formed for the liquid flowing from the small-diameter cylindrical portion 14c to the periphery of the bolt body 14a.

When the cylinder 9 is filled with liquid, if the trigger 4 is operated, the first check valve 93 becomes closed, the second check valve 94 becomes open, and the liquid in the cylinder 9 is sent into the pressure accumulator 12 from the liquid inlet 13b. As a result, the hydraulic pressure of the liquid in the cylinder 13 increases. The area of the upper surface of the plunger 14b is larger than the area of the lower surface of the bolt body 14a. Due to the area difference, the hydraulic pressure of the liquid acts as a force to depress the valve member 14. Then, the operation of pulling the trigger 4 is continued, and the hydraulic pressure in the cylinder 9 and the cylinder 13 is further increased, and the force to depress the valve member 14 becomes greater than the pushing force of the energizing device 15. As a result, the valve member 14 descends, the outflow port 13a closed by the bolt 14a opens, and the liquid is ejected from the nozzle 11. On the other hand, if the trigger 4 is pulled to the final position, the hydraulic pressure in the cylinder 9 and the cylinder 13 decreases, and the force pressing down the valve member 14 becomes smaller than the pushing force of the energizing device 15, thereby the valve member 14 rises, and the outflow port 13a is closed again by the bolt 14a.

One of the features of the cleaning article of the present invention is that the liquid cleaning agent composition can be sprayed in the form of foam, and the foam specific volume of the sprayed foam is 15 mL/g or more. The foam specific volume of the sprayed foam can be, for example, the foam specific volume of the foam after 1 minute of spraying from a spray container at 0.5 seconds/stroke. In addition, the foam specific volume of the sprayed foam can also be, for example, both the foam specific volume of the foam after 1 minute of spraying from a spray container at 0.5 seconds/stroke and the foam specific volume of the foam after 1 minute of spraying from a spray container at 0.2 seconds/stroke. The foam specific volume of the foam sprayed from the cleaning article of the present invention is preferably 15 mL/g or more after 1 minute of spraying under one or more conditions selected from 0.5 seconds/stroke and 0.2 seconds/stroke, and more preferably, the foam specific volume of the foam sprayed from the cleaning article of the present invention is 15 mL/g or more after 1 minute of spraying under 0.5 seconds/stroke and the foam specific volume of the foam sprayed from the cleaning article of the present invention is 15 mL/g or more. Hereinafter, unless otherwise specified, the foam specific volume of the foam sprayed from the cleaning article of the present invention is the same.

When the liquid detergent composition is sprayed in the form of foam, the foam specific volume of the sprayed foam is 15 mL/g or more, so that the cleaning power for dirt attached to the surface of the object to be cleaned, especially oily dirt, is improved. From the perspective of the convenience of spraying in a wide range, the foam specific volume of the sprayed foam is preferably 20 mL/g or more, more preferably 25 mL/g or more, and from the perspective of the convenience related to the ease of wiping the foam attached to the surface of the object to be cleaned after spraying or the ease of washing with water, the foam specific volume of the sprayed foam is preferably 80 mL/g or less, more preferably 60 mL/g or less. From the perspective of cleaning power for oil stains and related convenience, the foam specific volume of the sprayed foam is preferably 15 mL/g to 80 mL/g, more preferably 20 mL/g to 60 mL/g, and further preferably 25 mL/g to 60 mL/g. The method for determining the foam specific volume of the sprayed foam will be described in the examples.

Furthermore, one of the characteristics of the cleaning article of the present invention is that the ratio of the foam specific volume of the foam sprayed from the spray container at 0.2 seconds/stroke to the foam specific volume of the foam sprayed from the spray container at 0.5 seconds/stroke is greater than 0.5 and less than 2.0. The foam specific volume ratio is also called the rate of change of the foam specific volume when spraying by changing the speed of pulling the trigger. The foam specific volume of the sprayed foam can be the foam specific volume after 1 minute from the spray container. By making the above-mentioned foam specific volume ratio greater than 0.5 and less than 2.0, good foam can be always formed regardless of the speed of pulling the trigger, and the simplicity and efficiency are improved. From a related perspective, the above foam specific volume ratio is 0.5 or more, preferably 0.55 or more, more preferably 0.6 or more, and more preferably 0.65 or more, and is less than 2.0, preferably 1.85 or less, more preferably 1.7 or less, and more preferably 1.5 or less.

By making the liquid detergent composition foam and spraying it, the foam specific volume of the sprayed foam is 15 mL/g or more, the adhesion to the surface of the object to be cleaned is improved, and the cleaning power for oily dirt attached to the surface of the object to be cleaned is improved. In addition, since it can be sprayed in a wider range and the number of spraying times can be reduced compared to the case of using the same liquid detergent composition, the usability is improved.

In order to make the foam specific volume of the sprayed foam be 15 mL/g or more, it is preferred to use a spray container with a pressure accumulator sprayer as a trigger spray container. As a spray container with a pressure accumulator sprayer, the above-mentioned spray container 1 can be used, but it is not limited to this, and various known ones can be used. For example, those described in Japanese Patent Laid-Open No. 9-122547, Japanese Patent Laid-Open No. 9-308843, and Japanese Patent Laid-Open No. 10-174911 can be used. Regarding the known pressure accumulator sprayer that sprays liquid in a mist form, the nozzle is replaced with a nozzle that can spray foam. As the nozzle that can spray foam, the nozzle 11 of the above-mentioned spray container 1, the nozzle described in FIG. 1 of Japanese Patent Publication No. 2004-290943, the nozzle described in FIG. 2 of Japanese Patent Publication No. 2007-167719, etc. can also be used. In addition, from the perspective of improving the operability of a wide range of cleaning objects, the spray container with an accumulator sprayer is preferably one that can continuously spray the liquid detergent composition contained in the container (the liquid is continuously sprayed without interruption) without being limited to when the trigger is pulled. The so-called continuous spraying accumulator sprayer is a sprayer that can continuously spray the liquid cleaning agent composition according to the action of the trigger (independently in time) when the trigger is pulled repeatedly. As such a continuous spraying accumulator sprayer, those described in Figure 1 of Japanese Patent Laid-Open No. 2014-166624 or Figure 1 of Japanese Patent Laid-Open No. 2017-213497 can be used.

FIG3 shows a pressure-accumulating spray container 16 capable of continuous spraying according to an embodiment of the present invention. In the description of the spray container 16, the same symbols are used for the same components as the spray container 1 shown in FIG1, and detailed descriptions are omitted. As shown in FIG3, the pressure-accumulating spray container 16 capable of continuous spraying has a structure in which a trigger sprayer 17 for continuously spraying the above-mentioned liquid is installed at the mouth of the container body 2. The sprayer 17 has a trigger 4, a main material cylinder 18 pressurized by pulling the trigger 4, a longitudinal supply cylinder 19 for supplying liquid in the main material cylinder 18, an ejection cylinder 21 provided between the longitudinal supply cylinder 19 and the ejection hole 20, and a storage cylinder 23 for storing the liquid flowing in the ejection cylinder 21 through the supply hole 22. The ejection hole 20 is provided with a foaming nozzle 24. An air inlet hole (not shown) is formed on the side wall of the foaming nozzle 24, and the external air sucked from the air inlet hole flows into the foaming nozzle 24 as air for foaming the detergent ejected from the foaming nozzle 24. The main cylinder 18 has a main piston 18a that can move in the forward and backward direction according to the action of the trigger 4 to pressurize the main cylinder. The storage cylinder 23 has a storage plunger 23a that can move parallel to the axial direction of the ejection hole 20, and an energizing device 23b that energizes the storage plunger 23a along the ejection direction of the liquid in the ejection hole 20. In addition, a connecting hole 23c is formed in the storage cylinder 23, and the liquid stored in the storage cylinder 23 can move in the ejection tube 21 through the connecting hole 23c.

When the trigger 4 of the sprayer 17 is pulled backward, the main piston 18a moves in the main cylinder 18 in the front-rear direction to pressurize the main cylinder 18, and the liquid in the main cylinder 18 is supplied to the longitudinal supply cylinder 19 through the connecting cylinder 25. The liquid is ejected from the ejection hole 20 through the ejection cylinder 21, and is also stored in the storage cylinder 23 through the supply hole 22. As the liquid is stored in the storage cylinder 23, the storage plunger 23a in the storage cylinder 23 moves to one side of the above-mentioned axial direction. In this way, each time the trigger 4 is pulled, the liquid can be ejected from the ejection hole 20, and the storage plunger 23a moves along one side of the above-mentioned axis to store (fill) the liquid in the storage cylinder 23. Moreover, if the operation of pulling the trigger 4 is stopped, the supply of the liquid in the longitudinal supply cylinder 19 stops, but the storage plunger 23a begins to move back and forth to the other side of the above-mentioned axis due to the pressure acting on the storage plunger 23a. Thereby, the liquid filled in the storage cylinder 23 is pushed out from the storage cylinder 23 through the connecting hole 23b and the ejection cylinder 21 toward the ejection hole 20 side, thereby allowing the liquid to be continuously ejected from the ejection hole 20. Therefore, liquid can be sprayed not only when the trigger 4 is pulled back, but also when the trigger 4 is not operated, and continuous spraying of liquid can be performed. Furthermore, as shown in FIG. 4 , in the case where the pressure-accumulating spray container 26 capable of continuous spraying is to spray liquid in the form of mist, by providing a foaming tube 28 having an air extraction hole 28a formed in the nozzle 27, the mist can collide with the foaming tube 28 and extract air to form foam. In this way, the pressure-accumulating spray container 26 capable of continuous spraying can be provided with a foaming tube 28 at the opening end of the ejection hole 20 of the liquid in the container 26. The bubbler tube 28 is integrally or detachably arranged with the opening end of the ejection hole 20.

The liquid detergent composition used for cleaning articles of the present invention is not particularly limited. As long as the foam with the foam specific volume of 15 mL/g or more can be sprayed by combining with a spray container, from the viewpoint of forming foam with a foam specific volume of 15 mL/g or more, or foam with the better foam specific volume, and/or increasing the cleaning power of the liquid detergent composition itself against oil stains, it is better to use the following liquid detergent composition. The following liquid detergent composition is not limited to whether the foam specific volume is 15 mL/g or more, and has a higher cleaning power against oil stains, but by making the foam specific volume or the ratio of the above foam specific volume within a specific range, the cleaning effect on the surface of the cleaning object, and then on the hard surface, is further improved.

The reason why the cleaning article of the present invention can clean the surface of the object to be cleaned simply and efficiently and has a satisfactory cleaning effect is not necessarily clear, but it is speculated as follows. It is believed that the liquid cleaning agent composition contained in the container of the cleaning article of the present invention may include a specific surfactant such as component (a) and a water-soluble solvent such as component (d), thereby maintaining the advantage of a pressure-accumulating trigger that exhibits good foaming properties under a certain pressurized state, and by further using a hydrophilic polymer such as component (c), it is not easily affected by the foam specific volume of the foam formed due to the difference in pressurization speed. Specifically, it may be related to the bubbles (fast foaming properties) when the gas and liquid are mixed in a very short time. Furthermore, the liquid cleaning agent composition and the cleaning method for the surface of the cleaning object of the present invention are not limited by the above-mentioned mechanism of action.

The liquid detergent composition used for cleaning articles of the present invention [hereinafter referred to as the liquid detergent composition of the present invention] may contain a surfactant, a water-soluble solvent and water. From the viewpoint of adjusting the foam specific volume, the liquid detergent composition preferably contains an amphoteric surfactant. As the amphoteric surfactant, one or more amphoteric surfactants selected from amine oxide type amphoteric surfactants and betaine type amphoteric surfactants can be cited, and further one or more amphoteric surfactants selected from amine oxide, sulfobetaine and carboxybetaine can be cited. In addition, from the viewpoint of improving the cleaning power, it is preferred that the surfactant contains a non-ionic surfactant. Furthermore, from the viewpoint of adjusting the foam specific volume, the surfactant preferably includes an anionic surfactant. It is more preferred that the anionic surfactant is an anionic surfactant having a branched alkyl group. From the viewpoint of achieving a good foam specific volume without being affected by the speed of pulling the trigger, the liquid detergent composition of the present invention preferably contains one or more selected from amine oxide, sulfobetaine, carboxybetaine, alkyl (poly)glucoside, and alkyl (poly)glycerol ether. Furthermore, from the viewpoint of achieving a good foam specific volume without being affected by the speed of pulling the trigger, the liquid detergent composition of the present invention preferably contains a water-soluble solvent as specified in the following (d) component. As the water-soluble solvent, for example, one or more selected from alcohols having 3 to 10 carbon atoms and diol solvents having 2 to 14 carbon atoms can be cited. In addition, the liquid cleaning agent composition used in the present invention may contain one or more components selected from the components (a) to (h) related to the liquid cleaning agent composition for hard surfaces described below, and the blending amount can also be set to the blending amount of each component described below.

The liquid detergent composition used in the present invention may be a liquid detergent composition containing the following components (a) and (d). In addition, the liquid detergent composition used in the present invention may also be a liquid detergent composition containing the following components (a), (c) and (d).

As the liquid cleaning composition used in the cleaning article of the present invention, it is preferred to use the "liquid cleaning composition for hard surfaces" shown below. The liquid cleaning composition for hard surfaces is particularly excellent in cleaning grease.

<Liquid cleaning agent composition for hard surfaces> The liquid cleaning agent composition for hard surfaces of the present invention contains (a) an amphoteric surfactant [hereinafter referred to as component (a)], (b) a bactericide [hereinafter referred to as component (b)], (c) a hydrophilic polymer [hereinafter referred to as component (c)], (d) a water-soluble solvent, and water.

<Component (a)> Component (a) is an amphoteric surfactant. As an amphoteric surfactant, from the viewpoint of achieving a good foam specific volume without being affected by the speed of pulling the trigger, it is preferably an amphoteric surfactant selected from at least one of amine oxide type amphoteric surfactants and betaine type amphoteric surfactants, more preferably an amphoteric surfactant selected from at least one of amine oxide, sulfobetaine and carboxybetaine, and further preferably an amphoteric surfactant selected from at least one of amine oxide and carboxybetaine.

The amine oxide is preferably a compound represented by the following general formula (a1) [hereinafter referred to as component (a1)].

[Chemistry 1]

[In the formula, R ^1a represents a alkyl group having 6 to 22 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, R ^2a and R ^3a each independently represent an alkyl group having 1 to 3 carbon atoms. D represents a -NHC(=O)- group or a -C(=O)NH- group, and E represents an alkylene group having 1 to 5 carbon atoms. q and p represent q=0 and p=0 or q=1 and p=1]

In the above general formula (a1), when q=1 and p=1, from the viewpoint of detergency and foaming property, R ^1a is preferably a alkyl group having 7 or more, more preferably 9 or more, and preferably 21 or less, more preferably 17 or less, and further preferably 15 or less carbon atoms, preferably an alkyl group or an alkenyl group, and further preferably an alkyl group. Furthermore, when q=0 and p=0, from the viewpoint of detergency, R ^1a is preferably a alkyl group having 8 or more, more preferably 10 or more, and 22 or less, preferably 18 or less, and further preferably 16 or less carbon atoms, preferably an alkyl group or an alkenyl group, and further preferably an alkyl group. In the present invention, q=0 and p=0 are preferred. From the viewpoint of detergency, R ^2a and R ^3a are preferably a methyl group having 1 carbon atoms.

Preferred specific examples of component (a1) include: (1) alkyl (carbon number 6 to 22) dialkyl (carbon number 1 to 3) amine oxides: octyl dimethyl amine oxide, decyl dimethyl amine oxide, lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, palmityl dimethyl amine oxide, stearyl dimethyl amine oxide, etc.; (2) amide-containing amine oxides (compounds with q=1 and p=1 in the general formula (a1)): octylamidopropyl dimethyl amine oxide, decylamidopropyl dimethyl amine oxide, laurylamidopropyl dimethyl amine oxide, myristylamidopropyl dimethyl amine oxide, palmityl dimethyl amine oxide, etc.; One or more of these may be used. From the perspective of cleaning power and reducing the effect of the trigger pulling speed on foaming properties, (1) alkyl (carbon number 6 to 22) dialkyl (carbon number 1 to 3) amine oxides are more preferred.

As the betaine type amphoteric surfactant, a compound represented by the following general formula (a2) is preferred.

[Chemistry 2]

[In the formula, R ^4a is an alkyl or alkenyl group having 7 to 18 carbon atoms, R ^5a is an alkylene group having 1 to 6 carbon atoms. A is a group selected from -COO-, -CONH-, -OCO-, -NHCO-, and -O-, and r is 0 or 1. R ^6a and R ^7a are each independently an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and R ^8a is an alkylene group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group. B is a group selected from -SO ₃ ^- , -OSO ₃ ^- , and -COO ^- ]

In the general formula (a2), from the viewpoint of low substrate damage, R ^4a is an alkyl or alkenyl group having 7 or more, preferably 8 or more, more preferably 10 or more, and 18 or less, preferably 16 or less, more preferably 14 or less carbon atoms, preferably an alkyl group. From the viewpoint of low substrate damage, A is preferably -COO- or -CONH-, more preferably -CONH-. The carbon number of R ^5a is preferably 2 or 3. R ^6a and R ^7a are preferably methyl groups. From the viewpoint of low substrate damage, B is preferably -SO ₃ ^- or -COO ^- , more preferably -COO ^- . When B is -SO ₃ ^- , r is preferably 0, and when B is -COO ^- , it is preferably 1. The carbon number of R ^8a is preferably 3 when B is -SO ₃ ^- , and is preferably 1 when B is -COO ^- .

As the betaine-type amphoteric surfactant, specifically, one or more selected from alkyl carboxy betaines, alkyl amido carboxy betaines, alkyl sulfonyl betaines, alkyl amido hydroxyl sulfonyl betaines, and alkyl amino fatty acid salts can be cited. From the viewpoint of low substrate damage, preferably selected from alkyl amidopropyl-N,N-dimethyl carboxy betaine, alkyl-N,N-dimethylacetic betaine, N-alkyl-N,N-dimethyl-N-sulfopropylammonium sulfonyl betaine, alkyl-N, At least one of N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, alkylamidopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, N-alkylamidopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, and N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaine, and more preferably at least one of alkylamidopropyl-N,N-dimethylcarboxybetaine and alkyl-N,N-dimethylacetobetaine. The carbon number of the alkyl group is 7 or more, preferably 8 or more, more preferably 10 or more, and 18 or less, preferably 16 or less, more preferably 14 or less.

<Component (b)> Component (b) is a bactericidal agent. Component (b) is preferably one or more selected from cationic surfactants, ethanol and aromatic alcohols. Examples of cationic surfactants include quaternary ammonium salt-type surfactants.

The quaternary ammonium salt type surfactant as the component (b) is preferably at least one selected from the group consisting of compounds represented by the following general formula (b1) and compounds represented by the following general formula (b2).

[Chemistry 3]

[In the formula, at least one selected from R ^1b and R ^2b represents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 to 18 carbon atoms, the rest represents an alkyl group, a hydroxyalkyl group or a polyoxyethylene group having an average molar number of addition of 10 or less carbon atoms, R ^3b and R ^4b are the same or different and represent an alkyl group, a hydroxyalkyl group or a polyoxyethylene group having an average molar number of addition of 10 or less carbon atoms, respectively, and X ^- is an anion]

[Chemistry 4]

[In the formula, R ^5b is an aliphatic alkyl group having 8 to 18 carbon atoms, R ^6b and R ^7b are independently selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms, and X ^- is an anion]

In the general formula (b1), in the case of a single-long chain alkyl type quaternary ammonium salt, R ^1b is preferably an alkyl, alkenyl or hydroxyalkyl group having 8 or more, preferably 10 or more, more preferably 12 or more, further preferably 14 or more, and 18 or less, preferably 16 or less carbon atoms, and R ^2b , R ^3b and R ^4b are the same or different and are respectively an alkyl group having 1 or more and 3 or less carbon atoms, a hydroxyalkyl group or a polyoxyethylene group having an average addition molar number of 10 or less. In the general formula (b1), in the case of a dilong chain alkyl type quaternary ammonium salt, it is preferred that R ^1b and R ^2b are the same or different and are respectively an alkyl, alkenyl or hydroxyalkyl group having 8 or more and 16 or less, preferably 14 or less carbon atoms, and R ^3b and R ^4b are the same or different and are respectively an alkyl, hydroxyalkyl group having 1 or more and 3 or less carbon atoms, or a polyoxyethylene group having an average addition molar number of 10 or less.

In the general formula (b1), ^X- is an anion. Examples of the anion include halogen ions such as chloride ions, bromide ions, and iodide ions. Examples of the anion of ^X- include alkyl sulfate ions having 1 to 3 carbon atoms, such as methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions.

Preferred compounds of the general formula (b1) include at least one selected from N-alkyl-N,N,N-trimethylammonium salts in which the alkyl group has 12 to 18 carbon atoms, N,N-dialkyl-N,N-dimethyl-ammonium salts in which the alkyl group has 8 to 14 carbon atoms, and N-alkyl-N,N-dimethyl-N-ethylammonium salts in which the alkyl group has 12 to 16 carbon atoms.

In the general formula (b2), R ^5b is an aliphatic hydrocarbon group having a carbon number of 8 or more and 18 or less. From the viewpoint of detergency, the carbon number of R ^5b is preferably 8 or more, and preferably 18 or less, and more preferably 16 or less. R ^5b is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.

In the general formula (b2), R ^6b and R ^7b are independently selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms. R ^6b and R ^7b are preferably independently selected from an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

In the general formula (b2), ^X- is an anion. Examples of the anion include halogen ions such as chloride ions, bromide ions, and iodide ions. Examples of the anion of ^X- include alkyl sulfate ions having 1 to 3 carbon atoms, such as methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions.

Specific examples of the compound of the general formula (b2) include N-dodecyl-N,N-dimethyl-N-benzylammonium salt, N-tridecyl-N,N-dimethyl-N-benzylammonium salt, N-tetradecyl-N,N-dimethyl-N-benzylammonium salt, N-pentadecyl-N,N-dimethyl-N-benzylammonium salt, N-hexadecyl-N,N-dimethyl-N-benzylammonium salt, N-dodecyl-N,N-diethyl-N-benzylammonium salt, N-tridecyl-N,N-diethyl-N-benzylammonium salt, N-tetradecyl-N,N-dimethyl-N-benzylammonium salt, -diethyl-N-benzylammonium salt, N-pentadecyl-N,N-diethyl-N-benzylammonium salt, N-hexadecyl-N,N-diethyl-N-benzylammonium salt, N-dodecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-tridecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-tetradecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-pentadecyl-N-methyl-N-ethyl-N-benzylammonium salt and N-hexadecyl-N-methyl-N-ethyl-N-benzylammonium salt.

From the viewpoint of bactericidal effect and formulation stability, the aromatic alcohol of component (b) is preferably a compound represented by the following general formula (b3). R ^8b O-(R ^9b O) _l -H (b3) [wherein, R ^8b is a alkyl group having an aromatic group and a total carbon number of 6 to 10, l is an integer of 0 to 1, and R ^9b is an alkylene group having a carbon number of 2 to 4. The molecular weight of the compound is 106 to 250]

The total carbon number of R ^8b is the carbon number including the aromatic group. The total carbon number of R ^8b is 6 or more from the viewpoint of the bactericidal effect, and is 10 or less from the viewpoint of formulation stability, preferably 9 or less, and more preferably 8 or less. R ^8b is an aromatic alkyl group, and examples thereof include phenyl, benzyl, and phenethyl. From the viewpoint of the bactericidal effect, l in the general formula (b3) is preferably 1 or less, and more preferably 0.

Specifically, from the viewpoint of bactericidal effect and formulation stability, the component (b) may be one or more selected from benzyl alcohol (molecular weight: 108), phenoxyethanol (molecular weight: 138), 2-phenylethanol (molecular weight: 122), 3-phenyl-1-propanol (molecular weight: 136), cinnamyl alcohol (molecular weight: 134), benzyl glycol (molecular weight: 152), propylene glycol monophenyl ether (molecular weight: 152). The component (b) is preferably one or more selected from benzyl alcohol and phenoxyethanol. The component (b) may be a combination of benzyl alcohol and phenoxyethanol. The liquid cleaning agent composition for hard surfaces of the present invention preferably contains one or more selected from benzyl alcohol and phenoxyethanol as the component (b).

<Component (c)> Component (c) is a hydrophilic polymer. Component (c) may be a polymer compound having a weight average molecular weight of 10,000 or more and dissolving 0.1 g or more in 100 g of water at 25°C. The liquid cleaning agent composition for hard surfaces of the present invention can help control the foam specific volume of the foam formed by utilizing the difference in the pressurization speed by including component (c).

Examples of the component (c) include polymers having one or more groups selected from an amino group, a quaternary ammonium group and a betaine group, synthetic polymers selected from polyvinyl alcohol and its derivatives, and natural polymers such as hydroxyethyl cellulose and its derivatives.

Examples of the component (c) include polymers containing structural units derived from monomers having one or more groups selected from an amino group, a quaternary ammonium group, and a betaine group.

The component (c) is preferably a polymer comprising structural units A derived from one or more monomers A selected from the group consisting of monomers (c1) represented by the following general formula (c1) and monomers (c2) represented by the following general formula (c2).

[Chemistry 5]

[In the formula, R ^1c , R ^2c , R ^3c , R ^7c , R ^8c , and R ^9c are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. X ^1c and Y ^1c are each independently a group selected from an alkylene group having 1 to 12 carbon atoms, -COOR ^12c -, -CONHR ^12c -, -OCOR ^12c -, and -R ^13c -OCO-R ^12c -. Here, R ^12c and R ^13c are each independently an alkylene group having 1 to 5 carbon atoms. R ^4c is an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, or R ^1c R ^2c C=C(R ^3c )-X ^1c -. R ^5c is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ^6c is an alkyl group having 1 to 10 carbon atoms, or a benzyl group, which may be substituted with a hydroxyl group, a carboxyl group, a sulfonic acid group, or a sulfate group. When R ^6c is an alkyl group, a hydroxyalkyl group, or a benzyl group, ^Z- represents an anion. When R ^6c includes a carboxyl group, a sulfonic acid group, or a sulfate group, ^Z- does not exist, and these groups in R ^6c become anions. Examples of the anion of ^Z- include halogen ions, sulfate ions, alkyl sulfate ions having 1 to 3 carbon atoms, aromatic sulfonic acid ions which may be substituted with an alkyl group having 1 to 3 carbon atoms, and hydroxyl ions. R ^10c is a hydrogen atom, an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, or R ^7c R ^8c C=C(R ^9c )-Y ^1c -. R ^11c is a hydrogen atom, an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms.]

As the monomer (c1) of the general formula (c1), specifically, preferred ones are acryloyl (or methacryloyl) aminoalkyl (carbon number 1 to 5)-N,N,N-trialkyl (carbon number 1 to 3) quaternary ammonium salt, acryloyl (or methacryloyl) oxyalkyl (carbon number 1 to 5)-N,N,N-trialkyl (carbon number 1 to 3) quaternary ammonium salt, N-(ω-alkenyl (carbon number 2 to 10))-N,N,N-trialkyl (carbon number 1 to 3) quaternary ammonium salt, N,N-di(ω-alkenyl (carbon number 2 to 10))-N,N-dialkyl (carbon number 1 to 3) quaternary ammonium salt, and diallyldimethylammonium salt is particularly preferred.

As the monomer (c2) of the general formula (c2), specifically, preferred ones are acryl (or methacryl) aminoalkyl (carbon number 1 to 5) -N, N-dialkyl (carbon number 1 to 3) amine, acryl (or methacryl) oxyalkyl (carbon number 1 to 5) -N, N-dialkyl (carbon number 1 to 3) amine, N- (ω-alkenyl (carbon number 2 to 10)) -N, N-dialkyl ( The preferred amines include 1 to 3 carbon atoms) amine, N,N-di(ω-alkenyl (2 to 10 carbon atoms))-N-alkyl (1 to 3 carbon atoms) amine, allylamine, diallylmethylamine, and diallylamine. Allylamine, diallylmethylamine, diallylamine, acryl (or methacryl) aminopropyl-N,N-dimethylamine, and acryl (or methacryl) oxyethyl-N,N-dimethylamine are particularly preferred. When component (c) includes structural unit A, the structural unit A derived from monomer A is preferably included in a ratio of 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, and preferably 100 mol% or less, more preferably 99 mol% or less, and further preferably 90 mol% or less relative to the total structural units of component (c).

The component (c) is preferably a polymer containing a structural unit B represented by -SO ₂ -. As a method for introducing such a structural unit B into a polymer, there can be cited the following methods: blowing a predetermined amount of SO ₂ gas into a solution containing the monomer (c1) of the general formula (c1) and/or the monomer (c2) of the general formula (c2), and using a polymerization initiator selected from benzoyl peroxide, tert-butyl hydroperoxide, isopropylbenzene hydroperoxide, dilauryl peroxide, azobisisobutylonitrile, azobisisovaleronitrile, 2,2'-azobis(2-amidinopropane), tert-butyl hydroperoxide, isopropylbenzene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, persulfate, and hydrogen peroxide to carry out polymerization. A solvent may be used during polymerization. Specifically, water, alcohols selected from methanol, ethanol, and propanol, ketones selected from acetone and methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylimidazolidinone, acetonitrile, propionitrile, toluene, xylene, and hexane may be used. The polymerization temperature varies depending on the combination of the solvent or the initiator, and is preferably from -20°C to 200°C, and more preferably from -10°C to 100°C. In addition, the polymerization may be performed by light or radiation in the present invention, and in particular, polymerization may be performed efficiently by irradiating light with a wavelength of from 300 nm to 450 nm.

By making component (c) contain structural unit B, even when the concentration of the polymer is low, sufficient adhesion to the hard surface is exhibited, and it is not easily affected by the combined use with a cationic surfactant. When component (c) contains structural unit A and structural unit B, in component (c), the molar ratio of structural unit B derived from monomer B to structural unit A derived from monomer A (structural unit B)/(structural unit A) is preferably 0.01 or more, more preferably 0.03 or more, and further preferably 0.05 or more, and is preferably 1 or less, more preferably 0.75 or less, further preferably 0.5 or less, and further preferably 0.3 or less.

In the present invention, in order to further enhance the antifouling effect, the component (c) preferably contains a structural unit C derived from a monomer selected from the following (i) to (iv).

(i) Acrylic acid or its salt, methacrylic acid or its salt, maleic acid or its salt, maleic anhydride, styrene sulfonate, 2-acrylamide-2-methylpropane sulfonate, allyl sulfonate, vinyl sulfonate, methallyl sulfonate, sulfopropyl methacrylate, mono-ω-methacryloyloxyalkyl (carbon number 1 to 12) phosphate

(ii) an amide group-containing compound selected from acrylamide, N,N-dimethylaminopropylacrylamide (methacrylamide), N,N-dimethylacrylamide (methacrylamide), N,N-dimethylaminoethylacrylamide (methacrylamide), N,N-dimethylaminomethylacrylamide (methacrylamide), N-vinyl-2-caprolactam, and N-vinyl-2-pyrrolidone

(iii) an ester group-containing compound selected from alkyl acrylate (or methacrylate) (carbon number 1 to 5), 2-hydroxyethyl acrylate (or methacrylate), N,N-dimethylaminoalkyl acrylate (or methacrylate) (carbon number 1 to 5), and vinyl acetate

(iv) an olefin compound selected from ethylene, propylene, n-butene, isobutene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene, α-methylstyrene

Among them, in particular, in terms of the antifouling effect, the structural unit derived from the monomer of (i) or (ii) is preferred, and the structural unit derived from the monomer of (i) is the most preferred. Among them, acrylic acid or its sodium or potassium salt, methacrylic acid or its sodium or potassium salt, and maleic acid or its sodium or potassium salt are preferred. Here, the counter ion of the structural unit derived from the monomer of (i) may be the cationic part of the contained polymer.

When component (c) has structural unit C, among the structural units constituting component (c), the molar ratio of structural unit C derived from monomer C to structural unit A derived from monomer A, (structural unit C)/(structural unit A), is preferably greater than 0.05, more preferably greater than 0.1, further preferably greater than 0.2, and is preferably less than 1.0, more preferably less than 0.75, and further preferably less than 0.5, in terms of antifouling effect.

The component (c) may be any one of the main chain or side chain of the structural unit A, structural unit B and preferably structural unit C present in the polymer. These may be obtained by random polymerization, block polymerization, graft polymerization, etc. In the present invention, it is preferred to use a polymer composed of only structural units A, structural units B and structural units C.

In addition, as component (c), natural polymers such as polysaccharides and cellulose derivatives or their derivatives can be cited. As polysaccharides, there can be cited: karaya gum, tragacanth gum, gum arabic, acemannan, konjac mannan, gum arabic, gum gandhi, guar gum, locust bean gum, carrageenan, santhemum gum, gellan gum, polytriglucose, dextran, casein, gelatin, keratin, gluten, glucagon, gluten, zein, and insect glue. Among them, from the viewpoint of reducing the influence on the foaming property caused by the pulling speed of the trigger, polysaccharides selected from santhemum gum, guar gum, and gellan gum are preferred.

Examples of cellulose derivatives include hydroxypropyl methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, methylcellulose, hydroxypropylcellulose, ethylcellulose, carboxymethylcellulose, cellulose acetate phthalate, nitrocellulose, and other cellulose ethers/esters. Among these, from the viewpoint of reducing the effect on foaming caused by the pulling speed of the trigger, a cellulose derivative selected from hydroxypropyl methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, methylcellulose, hydroxypropylcellulose, ethylcellulose, and carboxymethylcellulose is preferred.

From the viewpoint of formulation stability and easy raw material acquisition, component (c) may be hydroxyethyl cellulose and polyvinyl alcohol. Component (c) may also be produced by reacting hydroxyethyl cellulose and semi-synthetic water-soluble polymers such as soluble starch with a compound having a cationic group. From the viewpoint of formulation stability and easy raw material acquisition, component (c) is preferably a cationically modified polyvinyl alcohol produced by polymerizing vinyl acetate and the above-mentioned monomer A, and a cationically modified hydroxyethyl cellulose obtained by reacting hydroxyethyl cellulose with a compound having a cationic group. As the cationic group, for example, the cationic group possessed by the above-mentioned monomer A can be cited.

(Cationically modified polyvinyl alcohol) Cationically modified polyvinyl alcohol is polyvinyl alcohol having a cationic group of the above-mentioned monomer A in the main chain or the side chain. The above-mentioned cationically modified polyvinyl alcohol can be obtained by copolymerizing vinyl acetate with diallyldimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride, etc. during the polymerization of vinyl acetate as a raw material, and saponifying the obtained copolymer by a conventional method. Also, vinyl acetate can be copolymerized with monomers having other reactive groups in advance, and after saponification, the above-mentioned reactive groups can be used to react with compounds containing the above-mentioned cationic groups to cationize the polyvinyl alcohol.

(Cationically modified hydroxyethyl cellulose) Cationically modified hydroxyethyl cellulose can be obtained, for example, by reacting raw material cellulose with ethylene oxide to obtain hydroxyethyl cellulose, and then reacting the hydroxyethyl cellulose with a cationizing agent to cationize it.

As the cellulose used as the raw material cellulose, in addition to chemically pure cellulose, various wood materials such as wood chips; pulp materials such as wood pulp made from wood; paper materials such as newspapers and corrugated cardboard; plant stalks and leaves such as rice stalks and corn stalks; plant shells such as rice husks, palm shells, coconut shells, etc., which contain various cellulose materials can be used.

As the cationizing agent, from the viewpoint of the obtainability, chloride or bromide of glycidyl trimethyl ammonium or glycidyl triethyl ammonium, chlorides such as 3-chloro-2-hydroxypropyl trimethyl ammonium and 3-chloro-2-hydroxypropyl triethyl ammonium, bromides such as 3-bromo-2-hydroxypropyl trimethyl ammonium and 3-bromo-2-hydroxypropyl triethyl ammonium are preferred, glycidyl trimethyl ammonium chloride or 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is more preferred, and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is further preferred. These cationizing agents may be used alone or in combination of two or more.

The cationization degree of component (c) is preferably 0.25 mol% or more, more preferably 0.35 mol% or more, further preferably 0.45 mol% or more, further preferably 0.6 mol% or more, further preferably 0.8 mol% or more, and preferably 5 mol% or less, further preferably 4 mol% or less, further preferably 3 mol% or less, further preferably 2 mol% or less, from the viewpoint of improving compatibility with the surfactant (formulation stability).

Component (c) may include a structural unit derived from a monomer having a betaine group. Examples of the monomer having a betaine structure include N-(3-sulfopropyl)-N-(methyl)acryloyloxyethyl-N,N-dimethylammonium betaine, N-(3-sulfopropyl)-N-(methyl)acryloylaminopropyl-N,N-dimethylammonium betaine, N-(3-carboxymethyl)-N-(methyl)acryloylaminopropyl-N,N-dimethylammonium betaine, and N-carboxymethyl-N-(methyl)acryloyloxyethyl-N,N-dimethylammonium betaine.

The component (c) is preferably a polymer having a structural unit D represented by the following general formula (c3), and more preferably a copolymer comprising a structural unit D represented by the following general formula (c3) and a structural unit E represented by the following general formula (c4).

[Chemistry 6]

[In the formula, R ^14c to R ^16c : are the same or different, and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. R ^17c : an alkylene group having 1 to 4 carbon atoms, or -Y ^2c -OPO ₃ ^- -Y ^3c - Y ^2c , Y ^3c : are the same or different, and are an alkylene group having 1 to 4 carbon atoms. R ^18c , R ^19c : are the same or different, and are a alkyl group having 1 to 4 carbon atoms. X ^2c : O or NR ^20c , R ^20c is a hydrogen atom or a alkyl group having 1 to 4 carbon atoms. X ^3c : represents a hydrogen atom, a alkyl group having 1 to 4 carbon atoms, R ^21c SO ₃ ^- , or R ^21c COO ^- . wherein when R ^17c is an alkylene group having 1 to 4 carbon atoms, X ^3c is R ^21c SO ₃ ^- or R ^21c COO ^- , R ^21c is an alkylene group having 1 to 4 carbon atoms, and when R ^17c is -Y ^2c -OPO ₃ ^- -Y ^3c -, X ^3c is a hydrogen atom or a alkyl group having 1 to 4 carbon atoms]

[Chemistry 7]

[In the formula, R ^22c to R ^24c are the same or different and are hydrogen atoms or alkyl groups having 1 or 2 carbon atoms; X ^4c is O or NH; R ^25c is an alkylene group having 1 to 4 carbon atoms; X ^5c is N ^+; R ^26c R ^27c R ^28c X ^6c or NR ^29c R ^30c ; R ^26c to R ^30c are the same or different and are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms; and X ^6c represents an anion]

[Structural unit D] In the general formula (c3), from the viewpoint of the availability of unsaturated monomers, the polymerizability of monomers, and the viewpoint of improving the antifouling performance of the component (c), R ^14c and R ^15c are each preferably a hydrogen atom. In the general formula (c3), from the viewpoint of the availability of unsaturated monomers, the polymerizability of monomers, and the viewpoint of improving the antifouling performance of the component (c), R ^16c is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. In the general formula (c3), from the viewpoint of the availability of unsaturated monomers, the polymerizability of monomers, and the viewpoint of improving the antifouling performance of the component (c), X ^2c is preferably O. In the general formula (c3), from the viewpoint of improving the antifouling performance, R ^17c is preferably an alkylene group having 1 or more and 4 or less carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms. In the general formula (c3), Y ^2c and Y ^3c are each preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms. In the general formula (c3), from the viewpoint of the availability of the same unsaturated monomer, the viewpoint of the polymerizability of the monomer, and the viewpoint of improving the antifouling performance of the component (c), R ^18c and R ^19c are each preferably a methyl group and an ethyl group, and more preferably a methyl group. In the general formula (c3), ^X3c is a hydrogen atom, a alkyl group having 1 to 4 carbon ^atoms , ^R21cSO3- , or ^R21cCOO- , but when ^R17c is an alkylene group having 1 to ⁴ carbon atoms, ^X3c is _R21cSO3- ^, or ^{R21cCOO- ,} and when ^R17c is ^-Y2c - _OPO3 ^{-- Y3c-} , ^X3c is ^a hydrogen atom or a alkyl group having 1 to 4 carbon atoms. When ^R17c is ^-Y2c - _OPO3 ^-- _Y3c- , ^X3c is preferably a alkyl group having 1 to 4 carbon atoms, and more preferably a methyl ^group , from the viewpoint of improving antifouling performance. When R ^17c is an alkylene group having 1 to 4 carbon atoms, from the same viewpoint, X ^3c is preferably R ^21c SO ₃ ^- . Furthermore, R ^21c is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms.

When the component (c) includes the structural unit D, the structural unit D in the component (c) is preferably 30 mol% or more, more preferably 50 mol% or more, further preferably 70 mol% or more, further preferably 80 mol% or more, further preferably 90 mol% or more, relative to the total structural unit of the component (c), from the viewpoint of improving the antifouling performance of the component (c), and from the same viewpoint, it is preferably 99 mol% or less, more preferably 98 mol% or less, further preferably 95 mol% or less. Furthermore, when the component (c) contains the structural unit D, from the viewpoint of improving the antifouling performance of the component (c), the content of the structural unit D in the component (c) is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, and from the same viewpoint, it is preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 95% by mass or less.

[Structural unit E] In the general formula (c4), from the viewpoint of the availability of unsaturated monomers, the polymerizability of monomers, and the viewpoint of improving the antifouling performance of the component (c), R ^22c and R ^23c are each preferably a hydrogen atom. In the general formula (c4), from the viewpoint of the polymerizability of monomers and the viewpoint of improving the antifouling performance of the component (c), R ^24c is preferably a hydrogen atom or a methyl group, more preferably a methyl group. In the general formula (c4), from the viewpoint of the polymerizability of monomers and the viewpoint of improving the antifouling performance of the component (c), X ^4c is preferably O. In the general formula (c4), from the viewpoint of the polymerizability of monomers and the viewpoint of improving the antifouling performance of the component (c), R ^25c is preferably an alkylene group having 2 or 3 carbon atoms, more preferably an alkylene group having 2 carbon atoms. In the general formula (c4), from the viewpoint of improving the antifouling performance of the component (c ⁾ and the ease of the quaternary reaction ^{, X5c} is N ^{+ R26cR27cR28cX6c or NR29cR30c, preferably N+R26cR27cR28cX6c. From the same viewpoint, R26c , R27c and R28c are each preferably a methyl} group or an ethyl ^group . In the general formula (c4), from the viewpoint of improving the antifouling performance of the component (c) and the ease of the quaternary reaction, ^R29c and ^R30c are preferably a methyl group or an ethyl group, and more preferably a methyl group. In the general formula (c4), X ^6c is an anion, preferably a halogen ion or C ₂ H ₅ SO ₄ ^- , more preferably C ₂ H ₅ SO ₄ ^- .

When component (c) includes structural unit E, in component (c), the amount of structural unit E relative to the total structural units of component (c) is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 5 mol% or more, from the viewpoint of improving the antifouling performance, and, from the same viewpoint, is preferably 70 mol% or less, more preferably 50 mol% or less, further preferably 30 mol% or less, further preferably 20 mol% or less, and further preferably 10 mol% or less.

Furthermore, when the component (c) contains the structural unit E, from the viewpoint of improving the antifouling performance, the content of the structural unit E in the component (c) is preferably 1 mass % or more, more preferably 2 mass % or more, and further preferably 5 mass % or more, and from the viewpoint of improving the antifouling performance of the component (c), it is preferably 70 mass % or less, more preferably 50 mass % or less, further preferably 30 mass % or less, further preferably 20 mass % or less, and further preferably 10 mass % or less.

[Molar ratio of structural unit D to structural unit E] When component (c) includes structural unit D and structural unit E, the molar ratio of structural unit D to structural unit E in component (c) is preferably 30/70 or more, more preferably 50/50 or more, further preferably 55/45 or more, further preferably 60/40 or more, further preferably 75/25 or more, further preferably 90/10 or more, from the viewpoint of antifouling performance, in terms of structural unit D/structural unit E. Furthermore, from the viewpoint of improving the antifouling performance of component (c), it is preferably 99.9/0.1 or less, more preferably 98/2 or less, further preferably 96/4 or less.

[Structural units other than structural units D and structural units E] Component (c) may contain structural units other than structural units D and structural units E within the scope of not impairing the effects of the present invention. As structural units other than structural units D and structural units E, structural units derived from unsaturated monomers other than unsaturated monomers having sulfonyl betaine groups are preferred, and structural units derived from hydrophobic unsaturated monomers such as styrene are more preferred.

Regarding the structural units other than structural units D and structural units E in component (c), relative to the total structural units of component (c), from the perspective of antifouling properties, it is preferably 10 mol% or less, more preferably 5 mol% or less, further preferably 1 mol% or less, further preferably 0.5 mol% or less, further preferably 0.1 mol% or less. The structural units other than structural units D and structural units E in component (c) may also be 0 mol% relative to the total structural units of component (c). Regarding the content of structural units other than structural units D and structural units E in component (c), from the perspective of antifouling properties, it is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, further preferably 0.5% by mass or less, further preferably 0.1% by mass or less. The content of structural units other than structural units D and structural units E in component (c) may also be 0% by mass.

When the component (c) includes structural units D and E, the total amount of structural units D and E in the component (c) relative to the total structural units of the component (c) is preferably 90 mol% or more, more preferably 95 mol% or more, further preferably 99 mol% or more, further preferably 99.5 mol% or more, further preferably 99.9 mol% or more from the perspective of antifouling properties. The total amount of structural units D and E in the component (a) relative to the total structural units of the component (c) may also be 100 mol%. Regarding the total content of structural unit D and structural unit E in component (c), from the perspective of antifouling properties, it is preferably 90 mass% or more, more preferably 95 mass% or more, further preferably 99 mass% or more, further preferably 99.5 mass% or more, further preferably 99.9 mass% or more. The total content of structural unit D and structural unit E in component (c) may also be 100 mass%.

As a method for producing component (c) having a betaine group, any method may be adopted. Specifically, the following methods (i) and (ii) may be cited. From the viewpoint of the availability of raw materials and the ease of production, method (ii) is preferred. (i) A method of obtaining by copolymerizing a betaine group with an unsaturated monomer having a cationic group (ii) A method of obtaining by copolymerizing an amine group with an unsaturated monomer having a cationic group and then quaternizing the resultant with a betaine-forming agent

In component (c), from the viewpoint of foaming property and antifouling property, the content of the structural units derived from monomers having a group selected from an amine group, a quaternary ammonium group and a betaine group, relative to the total structural units, is preferably 10 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, and is preferably 100 mol% or less, more preferably 95 mol% or less, and further preferably 90 mol% or less.

The weight average molecular weight of component (c) is preferably 10,000 or more, more preferably 30,000 or more, further preferably 50,000 or more, further preferably 100,000 or more, from the viewpoint of reducing the effect of the trigger pulling speed on the foaming property, and from the viewpoint of the same as above, it is preferably 5,000,000 or less, more preferably 3,000,000 or less, further preferably 2,000,000 or less. In addition, the weight average molecular weight of component (c) means the value obtained by gel permeation chromatography (GPC). In the GPC method, polytriglucose can be used as a molecular weight standard. The following is the same as the weight average molecular weight of component (c).

＊GPC conditions Apparatus: GPC (Gel Permeation Chromatography) manufactured by Tosoh Corporation Column: TSKgel α-M (two connected in series) manufactured by Tosoh Corporation Eluent: 0.15 molNa ₂ SO ₄ /1%CH ₃ COOH/water Flow rate: 1.0 mL/min Column temperature: 40°C Detection: RI (Refractive Index) Sample size: 0.2 mg/mL Standard substance: Polytris-glucose standard

When the pressure-accumulating trigger spray container of the present invention is a pressure-accumulating trigger spray container as shown in FIG1 , from the viewpoint of achieving the formation of foam with a good foam specific volume without being affected by the speed of pulling the trigger, especially suppressing the reduction of foaming property when the trigger is pulled quickly, the component (c) is preferably one or more selected from cellulose derivatives, polysaccharides and polyvinyl alcohol, more preferably one or more selected from hydroxyethyl cellulose, trisaccharide and polyvinyl alcohol, further preferably one or more selected from hydroxyethyl cellulose and polyvinyl alcohol, and particularly preferably hydroxyethyl cellulose. In this case, from the same viewpoint as above, the weight average molecular weight of component (c) is preferably 10,000 or more, more preferably 30,000 or more, further preferably 50,000 or more, further preferably 100,000 or more, further preferably 200,000 or more, and particularly preferably 300,000 or more, and preferably 5,000,000 or less, further preferably 3,000,000 or less, and further preferably 2,000,000 or less.

When the pressure-accumulating trigger spray container of the present invention is a pressure-accumulating trigger spray container capable of continuously spraying liquid as shown in FIG3 , from the viewpoint of achieving the formation of foam with a good foam specific volume without being affected by the speed of pulling the trigger and imparting antifouling properties, component (c) is preferably one or more selected from polymers containing one or more structural units A to E, cellulose derivatives, polysaccharide derivatives, and polyvinyl alcohol derivatives, and more preferably one or more selected from polymers containing structural units A or D, hydroxyethyl cellulose, cationically modified hydroxyethyl cellulose, tris-glucoside, polyvinyl alcohol, and cationically modified polyvinyl alcohol. In this case, from the same viewpoint as above, the weight average molecular weight of component (c) is preferably 10,000 or more, more preferably 30,000 or more, further preferably 50,000 or more, further preferably 100,000 or more, further preferably 200,000 or more, and particularly preferably 300,000 or more, and preferably 5,000,000 or less, further preferably 3,000,000 or less, and further preferably 2,000,000 or less.

<Component (d)> From the viewpoint of improving the foaming property during spraying, the liquid cleaning agent composition for hard surfaces of the present invention may contain (d) one or more water-soluble solvents selected from alcohols having 3 to 10 carbon atoms and diol compounds having 2 to 14 carbon atoms [except for those belonging to component (b)] [hereinafter referred to as component (d)]. The component (d) is preferably one or more water-soluble organic solvents selected from alcohols having preferably 3 or more carbon atoms, more preferably 4 or more carbon atoms, and 10 or less carbon atoms, and preferably 8 or less carbon atoms, and diol compounds having 2 or more carbon atoms, preferably 3 or more carbon atoms, more preferably 4 or more carbon atoms, and 13 or less carbon atoms, preferably 12 or less carbon atoms, and more preferably 10 or less carbon atoms. As a specific example, it is more preferably one or more water-soluble organic solvents selected from isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isopentyl glycol, propylene glycol monomethyl ether, dipropylene glycol monobutyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, phenoxytriethylene glycol, diethylene glycol butyl ether (diethylene glycol monobutyl ether), and dibutylene glycol. Among them, more preferably, at least one selected from phenoxytriethylene glycol, diethylene glycol butyl ether, propylene glycol, propylene glycol monomethyl ether, and dipropylene glycol monobutyl ether, and more preferably, at least one selected from diethylene glycol butyl ether and dipropylene glycol monobutyl ether. Furthermore, when the pressure-accumulating trigger spray container of the present invention is a pressure-accumulating trigger spray container capable of continuously spraying liquid as shown in FIG. 3, by using component (d), and further using at least one selected from diethylene glycol butyl ether, propylene glycol monomethyl ether, and dipropylene glycol monobutyl ether, the effect of the trigger pulling speed on the foaming property can be reduced even if component (c) is not contained. Here, the "water solubility" in the water-soluble solvent and water-soluble organic solvent of component (d) refers to a solvent with an octanol/water partition coefficient (LogPow) of 3.5 or less. In addition, the determination method of the partition coefficient between 1-octanol and water is based on the OECD (Organisation for Economic Co-operation and Development) test guide (OECD Council Decision "C(81)30 Final Annex 1") 107.

<Composition, other ingredients, etc.> From the viewpoint of cleaning power and foaming properties, the liquid cleaning agent composition and the liquid cleaning agent composition for hard surfaces of the present invention preferably contain component (a) in an amount of 0.1 mass % or more, more preferably 0.3 mass % or more, further preferably 0.5 mass % or more, further preferably 0.8 mass % or more, and preferably 10 mass % or less, more preferably 8 mass % or less, further preferably 5 mass % or less.

From the viewpoint of bactericidal property, the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention preferably contain component (b) in an amount of 0.005 mass %, more preferably 0.01 mass %, and further preferably 1 mass %, and further preferably 5 mass %, more preferably 3 mass %, further preferably 2.5 mass %, and further preferably 2 mass %. Component (b) may impair the foaming effect of component (d) depending on its type and content, so care should be taken when containing it. Furthermore, when bactericidal property is not required, component (b) is not substantially formulated, that is, the content of component (b) in the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention may be 0 mass %.

From the perspective of reducing the effect of the trigger pulling speed on the foaming property, the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention preferably contain component (c) in an amount of 0.01 mass % or more, more preferably 0.05 mass % or more, and further preferably 0.1 mass % or more, and further preferably 1 mass % or less, more preferably 0.5 mass % or less, and further preferably 0.3 mass % or less. Furthermore, only when the pressure-accumulating trigger spray container of the present invention is a pressure-accumulating trigger spray container capable of continuously spraying liquid as shown in FIG. 3 , the liquid cleaning agent composition and the liquid cleaning agent composition for hard surfaces of the present invention may substantially not contain component (c). In the present invention, the so-called reduction of the effect on the foaming property caused by the pulling speed of the trigger means that the ratio of the foam specific volume of the foam sprayed from the above-mentioned spray container at 0.2 seconds/stroke to the foam specific volume of the foam sprayed from the above-mentioned spray container at 0.5 seconds/stroke is controlled to be greater than 0.5 and less than 2.0.

In the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention, from the viewpoint of cleaning power and reducing the influence on foaming property caused by the pulling speed of the trigger, the mass ratio (c)/(a) of the content of component (c) to the content of component (a) is 0.005 or more, preferably 0.01 or more, more preferably 0.02 or more, and further preferably 0.03 or more. Moreover, from the same viewpoint, it is preferably 1 or less, more preferably 0.5 or less, and further preferably 0.1 or less.

From the viewpoint of reducing the influence on foaming property caused by the pulling speed of the trigger, the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention preferably contain component (d) in an amount of 0.5 mass % or more, more preferably 1 mass % or more, further preferably 2 mass % or more, further preferably 3 mass % or more, and preferably 15 mass % or less, more preferably 10 mass % or less, further preferably 8 mass % or less.

In the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention, from the viewpoint of cleaning power and reducing the influence on foaming property caused by the pulling speed of the trigger, the mass ratio (d)/(a) of the content of component (d) to the content of component (a) is preferably 0.5 or more, more preferably 0.8 or more, and further preferably 1.0 or more. Moreover, from the same viewpoint, it is preferably 5.0 or less, more preferably 3.0 or less, further preferably 2.5 or less, further preferably 2.0 or less, and particularly preferably 1.8 or less.

When the pressure-accumulating trigger spray container of the present invention is a container as shown in FIG. 1 , from the viewpoint of cleaning power and reducing the influence of the pulling speed of the trigger on the foaming property, the mass ratio (c)/(a) of the content of the component (c) to the content of the component (a) in the liquid cleaning agent composition and the liquid cleaning agent composition for hard surfaces of the present invention is 0.005 or more, preferably 0.01 or more, more preferably 0.02 or more, and further preferably 0.03 or more. The mass ratio (d)/(a) of the content of the component (d) to the content of the component (a) is preferably 0.5 or more, more preferably 0.8 or more, and more preferably 1.0 or less, and from the same viewpoint, it is preferably 5.0 or less, more preferably 3.0 or less, more preferably 2.5 or less, and more preferably 2.0 or less.

In the case where the pressure-accumulating trigger spray container of the present invention is a pressure-accumulating trigger spray container capable of continuously spraying liquid as shown in FIG. 3 , from the viewpoint of reducing the influence of the pulling speed of the trigger on the foaming property, the mass ratio (c)/(a) of the content of the component (c) to the content of the component (a) in the liquid cleaning agent composition and the liquid cleaning agent composition for hard surfaces of the present invention is preferably 0.5 or less, more preferably 0.2 or less, further preferably 0.05 or less, and particularly preferably 0. From the viewpoint of cleaning power and reducing the effect of the trigger pulling speed on foaming properties, the mass ratio (d)/(a) of the content of component (d) to the content of component (a) is preferably 0.5 or more, more preferably 0.8 or more, further preferably 1.0 or more, and particularly preferably 1.3 or more. From the same viewpoint, it is preferably 5.0 or less, more preferably 3.0 or less, further preferably 2.5 or less, further preferably 2.0 or less, and particularly preferably 1.8 or less.

The liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention contain water. Water can be used as the remainder other than component (a), component (b), component (c), component (d) and any of the following components. From the perspective of the stability of the liquid cleaning composition and the liquid cleaning composition for hard surfaces, and reducing the effect of the trigger pulling speed on the foaming property, the water content is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more, and preferably 97% by mass or less, and more preferably 95% by mass or less. The water is preferably ion exchange water, sterilized ion exchange water, etc.

The pH value of the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention at 25°C is preferably 4 or more, more preferably 5 or more, and further preferably 6 or more, and is preferably 12 or less, more preferably 10 or less, further preferably 9 or less, and further preferably 8 or less. A pH adjuster can be used to adjust the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention to the above pH range. As pH adjusters, inorganic acids such as hydrochloric acid or sulfuric acid, or organic acids such as citric acid, lactic acid, succinic acid, apple acid, fumaric acid, tartaric acid, malonic acid, and maleic acid, acid agents, sodium hydroxide or potassium hydroxide, ammonia or its derivatives, amine salts such as monoethanolamine, diethanolamine, and triethanolamine, and base agents such as sodium carbonate and potassium carbonate can be used alone or in combination. In addition, these acid agents and base agents can also be combined to use as a buffer system. The pH value of the liquid detergent composition and the liquid detergent composition for hard surfaces at 25°C is measured according to the following method.

<Measurement method of pH value> Connect the pH measurement composite electrode (GST-5841C manufactured by DKK Toa) to the pH meter (pH/ion meter HM-42X manufactured by DKK Toa) and turn on the power. As the internal liquid of the pH electrode, use a saturated potassium chloride aqueous solution (3.33 mol/L). Next, fill a 100 mL beaker with a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 standard solution (neutral phosphate standard solution), and a pH 9.18 standard solution (borate standard solution) and immerse in a constant temperature bath at 25°C for 30 minutes. The electrode for pH measurement is immersed in the standard solution adjusted to a constant temperature for 3 minutes, and the calibration operation is performed in the order of pH6.86→pH4.01→pH9.18. The liquid cleaning agent composition of the present invention or the liquid cleaning agent composition for hard surfaces to be measured is adjusted to 25°C, and the electrode of the above pH meter is immersed in the liquid cleaning agent composition of the present invention or the liquid cleaning agent composition for hard surfaces, and the pH value is measured after 1 minute.

<Surfactant> From the viewpoint of improving cleaning power and foaming properties, the liquid cleaning agent composition and the liquid cleaning agent composition for hard surfaces of the present invention may contain a surfactant other than the components (a) and (b). As the surfactant other than the components (a) and (b), one or more surfactants selected from (e) nonionic surfactants [hereinafter referred to as the component (e)] and (f) anionic surfactants [hereinafter referred to as the component (f)] can be cited. From the viewpoint of improving cleaning power, the liquid cleaning agent composition and the liquid cleaning agent composition for hard surfaces of the present invention preferably contain the component (e).

<Component (e)> Component (e) is a nonionic surfactant. From the viewpoint of detergency and foaming power, component (e) is preferably selected from the group consisting of (e1) monoalkyl glyceryl ether [hereinafter referred to as component (e1)], (e2) polyoxyalkylene monoalkyl or alkenyl ether [hereinafter referred to as component (e2)], (e3) alkyl polyglycoside (glycoside type nonionic surfactant) [hereinafter referred to as component (e3)], (e4) sorbitan-based nonionic surfactant [hereinafter referred to as component (e4)], (e5) fatty alkanolamide [hereinafter referred to as component (e5)], (e6) fatty acid monoglyceride [hereinafter referred to as component (e6)], and (e7) fatty acid sucrose ester [hereinafter referred to as component (e7)], and two or more of these may be used. From the perspective of improving the cleaning power and reducing the effect of the trigger pulling speed on the foaming property, component (e) is preferably a non-ionic surfactant having a hydrophilic group with a sugar skeleton or a glycerol skeleton, for example, one or more selected from the group consisting of component (e1), component (e3), component (e6) and component (e7), preferably one or more selected from alkyl (poly) glucoside and alkyl (poly) glycerol ether.

The component (e1) is a monoalkyl glyceryl ether. Specifically, the component (e1) is preferably a compound represented by the following general formula (e1). R ^1e -O-(Gly) _r -H (e1) [wherein, R ^1e represents an alkyl group having 6 to 18 carbon atoms, Gly represents a structural unit derived from glycerol, preferably a residue obtained by removing one hydroxyl group and one hydrogen atom from glycerol, and r represents a number of 1 to 4]

In the general formula (e1), from the viewpoint of detergency, R ^1e is preferably an alkyl group having 6 or more carbon atoms, more preferably 7 or more carbon atoms, further preferably 8 or more carbon atoms, and further preferably 18 or less carbon atoms, more preferably 12 or less carbon atoms, and further preferably 10 or less carbon atoms. Straight-chain alkyl groups such as hexyl, heptyl, octyl, nonyl, and decyl can be used. However, in the present invention, from the viewpoint of detergency, branched alkyl groups are preferred. As a specific branched alkyl group for R ^1e , a group selected from 2-ethylhexyl, tert-octyl, isononyl, and isodecyl is more preferred, 2-ethylhexyl or isodecyl is more preferred, and 2-ethylhexyl is particularly preferred.

In the general formula (e1), r is preferably 1 or more and preferably 2 or less. More preferably, it is a compound in which r is 1. A particularly preferred compound is a compound in which R ^1e is 2-ethylhexyl and r is 1. The structure represented by Gly is a structure represented by -CH ₂ CH(OH)CH ₂ - in which the hydroxyl groups at the 1-position and the 3-position of glycerol are bonded, or a structure represented by -CH(CH ₂ OH)CH ₂ - in which the hydroxyl groups at the 1-position and the 2-position of glycerol are bonded, which differs depending on the catalyst or reaction conditions.

In order to obtain the compound of the general formula (e1), for example, the following method can be used, that is, using an alkyl alcohol represented by R ^1e -OH as an alcohol having 6 to 10 carbon atoms, and using an acid catalyst such as BF ₃ or an aluminum catalyst to react an epoxy compound such as epihalool or glycidol to produce the compound. For example, when 2-ethylhexanol is used, the obtained 2-ethylhexyl monoglyceryl ether is a mixture that may contain a plurality of products as described in Japanese Patent Laid-Open No. 2001-49291.

Component (e2) is a polyoxyalkylene monoalkyl or alkenyl ether. In the nonionic surfactant of component (e2), from the viewpoint of detergency, the carbon number of the alkyl or alkenyl group is preferably 6 or more, more preferably 8 or more, further preferably 10 or more, further preferably 12 or more, and from the same viewpoint, it is preferably 22 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less.

In the nonionic surfactant of component (e2), from the viewpoint of cleaning power, the average addition molar number of oxyalkylene groups is preferably greater than 0, more preferably greater than 1, and further preferably greater than 3, and from the same viewpoint, it is preferably less than 50, more preferably less than 30, further preferably less than 20, and further preferably less than 10. In the nonionic surfactant of component (e2), from the viewpoint of cleaning power, the oxyalkylene groups are preferably at least one selected from oxyethylene, oxypropylene and oxybutylene, and more preferably at least one selected from oxyethylene and oxypropylene.

The component (e2) can be selected from one or more compounds represented by the following general formula (e2). R ^2e O[(C ₂ H ₄ O) _l /(C ₃ H ₆ O) _j ]H (e2) [wherein, R ^2e represents a alkyl group having a carbon number of 6 to 22. l and j represent the average added molar number, l represents a number of 0 to 30, j represents a number of 0 to 30, and l and j are not 0 at the same time. "/" represents that oxyethyl and oxypropyl groups can be added randomly or in blocks, regardless of the order]

From the viewpoint of detergency, the carbon number of R ^2e in the general formula (e2) is preferably 8 or more, more preferably 10 or more, and further preferably 12 or more, and from the same viewpoint, it is preferably 18 or less, more preferably 16 or less, and further preferably 14 or less. From the viewpoint of detergency, R ^2e is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and further preferably a dialkyl group. Here, the dialkyl group refers to an alkyl group in which the carbon atom of R ^2e bonded to O in R ^2e O in the general formula (e2) forms a dialkyl group. As the alkyl group, specifically, various octyl groups (including 2-ethylhexyl), various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups (lauryl groups), various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, and various octadecyl groups can be exemplified. As the alkenyl group, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, and various octadecyl groups (e.g., oleyl and linoleyl groups) can be exemplified. Furthermore, "various" means various isomers including normal, second, third, and iso.

From the viewpoint of storage stability, l and j in the general formula (e2) are each independently preferably 1 or more, more preferably 2 or more, and from the same viewpoint, preferably 20 or less, more preferably 10 or less, and further preferably 5 or less.

The component (e3) is an alkyl polyglycoside (glycoside-type non-ionic surfactant). The non-ionic surfactant of the component (e3) is preferably a non-ionic surfactant represented by the following general formula (e3). R ^3e (OR ^4e ) _s G _t (e3) [wherein, R ^3e represents a linear or branched alkyl, alkenyl or alkylphenyl group having 8 to 18 carbon atoms, preferably 12 to 14 carbon atoms, preferably an alkyl group, R ^4e represents an alkylene group having 2 to 4 carbon atoms, and G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms. s represents the average addition molar number, and is a number from 0 to 5. t represents a number whose average value is from 1 to 5]

In the general formula (e3), from the viewpoint of detergency, R ^3e is preferably a linear or branched alkyl group having 8 or more, preferably 10 or more, and 18 or less, and preferably 14 or less carbon atoms. In the general formula (e3), from the viewpoint of storage stability, s is preferably 0 or more, and preferably 2 or less, and more preferably 0. From the viewpoint of storage stability, t is preferably 1.1 or more, and preferably 1.5 or less, and more preferably 1.4 or less. In addition, t is a measured value obtained by a proton NMR method. In the general formula (e3), from the viewpoint of availability and cost, G can be, for example, a residue derived from one or more monosaccharides selected from glucose and fructose. Furthermore, G may be a residue derived from one or more polysaccharides selected from maltose and sucrose. G is preferably a residue derived from a monosaccharide such as glucose.

(e4) sorbitan-based nonionic surfactants, (e5) aliphatic alkanolamides, (e6) fatty acid monoglycerides, and (e7) fatty acid sucrose esters preferably have a linear or branched alkyl group having preferably 8 to 18 carbon atoms, more preferably 12 to 14 carbon atoms.

From the viewpoint of improving the cleaning power, the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention preferably contain component (e) in an amount of 0.05 mass % or more, more preferably 0.1 mass % or more, further preferably 0.2 mass % or more, and preferably 5 mass % or less, more preferably 3 mass % or less, further preferably 2 mass % or less.

<Component (f)> Component (f) is an anionic surfactant. Component (f) may be an anionic surfactant having a sulfate group, a phosphate group, a phosphonic acid group, a sulfonic acid group or a carboxyl group. From the viewpoint of cleaning power, the alkyl group possessed by the anionic surfactant is preferably a linear or branched alkyl group, an alkylene group or an aryl group having a carbon number of preferably 5 or more, more preferably 6 or more, further preferably 7 or more, further preferably 8 or more, further preferably 10 or more, further preferably 12 or more, and preferably 21 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less.

The anionic surfactant is preferably one or more selected from the group consisting of (f1) a sulfosuccinate or a salt thereof having a carbon number of 5 to 18 (hereinafter referred to as component (f1)), (f2) an anionic surfactant having a carbon number of 8 to 21 and a sulfate group or a sulfonic acid group (excluding those belonging to component (f1)), (f3) an anionic surfactant having a carbon number of 8 to 21 and a carboxyl group (hereinafter referred to as component (f3)), and (f4) an anionic surfactant having a carbon number of 8 to 21 and a phosphate group (hereinafter referred to as component (f4), and two or more of these may be used.

Examples of the anionic surfactant as the component (f2) include at least one selected from alkyl sulfates, polyoxyalkylene alkyl ether sulfates and alkane sulfonates.

Examples of the salt of the anionic surfactant as component (f) include inorganic salts selected from sodium salts, ammonium salts, potassium salts, magnesium salts, and organic ammonium salts selected from monoethoxide ammonium salts, diethoxide ammonium salts, triethoxide ammonium salts, morpholinium salts, and the like.

From the viewpoint of foaming property, the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention may contain component (f) in an amount of preferably 2% by mass or less, more preferably 1% by mass or less, further preferably 0.2% by mass or less, further preferably 0.1% by mass or less, and for example, more than 0% by mass, and it is desirable that the component (f) is substantially not blended. In the case where the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention contain component (f), in the composition, from the viewpoint of cleaning power and foaming property, the mass ratio (f)/(a) of the content of component (f) to the content of component (a) is preferably 5.0 or less, more preferably 2.5 or less, further preferably 2.0 or less, further preferably 1.0 or less, and particularly preferably 0.5 or less.

<Component (g)> From the viewpoint of formulation stability, the liquid cleaning agent composition and the liquid cleaning agent composition for hard surfaces of the present invention may contain a hydrophilic agent as component (g). As the hydrophilic agent, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid or their sodium, potassium or magnesium salts are preferred, and p-toluenesulfonic acid or its salt is particularly preferred.

From the viewpoint of formulation stability, the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention preferably contain the component (g) in an amount of 0.5 mass % or more, more preferably 1 mass % or more, further preferably 1.5 mass % or more, and preferably 15 mass % or less, more preferably 10 mass % or less, further preferably 5 mass % or less.

<Component (h)> From the viewpoint of cleaning power, the liquid cleaning agent composition and the liquid cleaning agent composition for hard surfaces of the present invention may contain a chelating agent as component (h). Examples of the chelating agent include: citric acid or its salts, ethylenediaminetetraacetic acid or its salts, methylglycine diacetic acid or its salts, L-glutamine diacetic acid or its salts, etc. Examples of the salt of component (h) include: alkali metal salts such as sodium salts and potassium salts, alkali earth metal salts such as magnesium salts, ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts and other organic amine salts, preferably alkali metal salts, more preferably sodium salts.

From the viewpoint of cleaning power, the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention preferably contain component (h) in an amount of 0.1 mass % or more, more preferably 1.0 mass % or more, further preferably 2.0 mass % or more, and preferably 20 mass % or less, more preferably 10 mass % or less, further preferably 6 mass % or less.

The liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention may contain any ingredients such as enzymes, fragrances, dyes, pigments, preservatives, pH adjusters, stabilizers, cleaning aids, etc.

From the viewpoint of reducing the effect of the trigger pulling speed on the foaming property, the viscosity of the liquid cleaning composition and the liquid cleaning composition for hard surfaces of the present invention at 25°C is preferably 1 mPa·s or more, more preferably 3 mPa·s or more, and further preferably 5 mPa·s or more, and further preferably 50 mPa·s or less, more preferably 20 mPa·s or less, further preferably 15 mPa·s or less, further preferably 12 mPa·s or less, and further preferably 10 mPa·s or less. The viscosity of the compositions can be adjusted by using the water-soluble solvent of the component (d) or the water-soluble auxiliary agent of the component (g). Here, the viscosity is measured by the following viscosity measurement method.

<Viscosity measurement method> Prepare a B-type viscometer model BM manufactured by TOKIMEC INC. with a rotor No. 1 installed. Fill 100 mL of the liquid detergent composition or liquid detergent composition for hard surfaces of the present invention into a viscosity measurement beaker and fully adjust the temperature in a constant temperature water bath at 25°C. Place the beaker containing the composition in the viscometer, set the rotor speed to 60 r/min, and measure the value after 60 seconds. Set this value as the viscosity of the liquid detergent composition or liquid detergent composition for hard surfaces for measurement.

The cleaning article of the present invention and the liquid cleaning agent composition used in the cleaning article of the present invention can clean the surface of the cleaning object, such as the hard surface of fiber products or hard objects. Therefore, the cleaning article of the present invention can be a hard surface cleaning article. There is no particular limitation on the hard surface, and examples thereof include: glass, pottery, porcelain, enamel, tile, ceramics; metals such as aluminum, stainless steel, and brass; synthetic resins such as polyethylene, polypropylene, melamine resin, polyamide resin, ABS (acrylonitrile-butadiene-styrene) resin, and FRP (Fiber Reinforced Plastic). As the hard surface of the article and composition to which the present invention can be applied, a hydrophilic hard surface is preferred. Here, "hydrophilicity" of the hard surface means that the static contact angle with water is less than 70°. Suitable hard surfaces in the present invention can be exemplified by one or more hard surfaces selected from glass, pottery, porcelain, plastic, stainless steel and silicon wafers. The surface of the cleaning object of the present invention is preferably a hard surface, specifically, an article with a hard surface. As a hard surface, for example: the hard surface of an article equipped in one or more places in the kitchen, toilet, bathroom and living room can be cited. More specifically, items with hard surfaces include toilets, bathtubs, kitchen sinks, gas stoves, window glass, mirrors, faucets, etc.

<Cleaning method for the surface of a cleaning object> The present invention provides a cleaning method for the surface of a cleaning object, which allows the foam sprayed by the cleaning article of the present invention to contact the surface of the cleaning object. The surface of the cleaning method of the present invention is preferably a hard surface. In addition, the cleaning method of the surface of the cleaning object of the present invention can be a cleaning method for the surface of a hard surface by bringing the liquid cleaning agent composition of the present invention into contact with the hard surface and wiping the contacted composition. The liquid cleaning agent composition of the present invention is preferably brought into contact with the surface of the cleaning object in the form of foam using the cleaning article of the present invention.

In the cleaning method of the surface of the cleaning object of the present invention, after the liquid cleaning agent composition for hard surfaces of the present invention is brought into contact with the hard surface, one or more of the following steps may be performed: scrubbing the hard surface with a cleaning tool such as a sponge or a bristle brush, washing the hard surface in contact with the hard surface with water, and wiping the liquid cleaning agent composition for hard surfaces in contact with the hard surface. Examples of wiping articles for wiping the hard surface include cloth, paper, sponge, etc. The cloth may be a woven cloth or a non-woven cloth.

In the method for cleaning the surface of the object to be cleaned of the present invention, the cleaning article of the present invention can be appropriately used. Hereinafter, regarding the method for cleaning the surface of the object to be cleaned of the present invention, the method of using the cleaning article of the present invention is exemplified and described in detail.

The preferred method of using the cleaning article of the present invention is to directly contact a liquid cleaning agent composition sprayed into foam using a spray container with a hard surface as a cleaning object. In addition, the hard surface as the cleaning object is preferably a hard surface with oil stains attached, and further preferably a hard surface with oil stains containing solid grease attached. The cleaning article of the present invention can be appropriately implemented as a cleaning method for hard surfaces. In the preferred method of using the cleaning article of the present invention, a liquid cleaning agent composition sprayed into foam using a spray container, and more preferably a liquid cleaning agent composition for hard surfaces sprayed into foam using a spray container, is brought into contact with a hard surface. Specifically, a liquid detergent composition sprayed into foam using a spray container, more preferably a liquid detergent composition for hard surfaces sprayed into foam using a spray container, is brought into contact with a hard surface without dilution. After contacting the hard surface, the composition of the liquid detergent composition may change. That is, after contacting the hard surface, the composition of the liquid detergent composition may be diluted or concentrated.

Furthermore, in a preferred method of using the cleaning article of the present invention, a liquid cleaning agent composition sprayed into foam using a spray container, or more preferably a liquid cleaning agent composition for hard surfaces sprayed into foam using a spray container, is brought into contact with a hard surface and then placed without applying mechanical force. In other words, the contact is made without using flexible materials such as sponges, and the article is placed directly without applying mechanical force. The cleaning article of the present invention can improve the cleaning effect of the liquid cleaning agent composition, can greatly improve the cleaning effect of cleaning without applying mechanical force, can be placed without applying mechanical force, and can be rinsed with water to complete the cleaning after being placed.

In a preferred method of using the cleaning article of the present invention, the liquid cleaning composition sprayed into foam using a spray container, more preferably the liquid cleaning composition for hard surfaces sprayed into foam using a spray container, is ^brought into contact with the hard surface of the cleaning object at a ratio of preferably 0.1 g or more, more preferably 0.3 g or more, further preferably 0.4 g or more, and preferably 5 g or less, more preferably 3 g or less, further preferably 2 g or less, with respect to an area of 100 cm 2, and preferably sprayed.

In the preferred method of using the cleaning article of the present invention, from the perspective of improving the cleaning power, after the liquid cleaning agent composition sprayed into foam by a spray container, or more preferably the liquid cleaning agent composition for hard surfaces sprayed into foam by a spray container, contacts the hard surface, it is preferably left for more than 10 seconds, more preferably more than 20 seconds, further preferably more than 30 seconds, further preferably more than 40 seconds, and from the same perspective, it is preferably left for less than 60 minutes, more preferably less than 30 minutes, further preferably less than 20 minutes, further preferably less than 10 minutes. In this case, the time point when the liquid cleaning agent composition first contacts the hard surface can be set as the start of placement. Furthermore, the temperature during storage may be room temperature, for example, 10° C. to 30° C.

In summary, in the preferred method of using the cleaning article of the present invention, from the perspective of improving the cleaning power, the liquid cleaning agent composition sprayed into foam using a spray container is preferably in contact with the hard surface as the cleaning object for more than 10 seconds, more preferably more than 20 seconds, further preferably more than 30 seconds, further preferably more than 40 seconds, and, from the same perspective, it is preferably less than 60 minutes, more preferably less than 30 minutes, further preferably less than 20 minutes, and further preferably less than 10 minutes.

The mass of the liquid detergent composition sprayed in the form of foam in one spraying operation of the cleaning article of the present invention is preferably 0.3 g or more, more preferably 0.4 g or more, from the viewpoint of improving the cleaning power, and is preferably 3.0 g or less, more preferably less than 1.5 g, and further preferably 1.2 g or less from the viewpoint of reducing the force of pulling the trigger. According to the cleaning article of the present invention, since the foam specific volume of the sprayed foam is high, the amount of the liquid detergent composition sprayed in one spraying operation can also be reduced. Thus, the cleaning articles can be made lighter and the operability can be improved, or the number of times or area that can be cleaned can be increased without replenishing the liquid detergent composition in the spray container. In addition, the force of pulling the trigger can be adjusted to be smaller.

Regarding the coverage of the liquid detergent composition sprayed in the form of foam from the spray container in 5 consecutive spraying operations of the cleaning article of the present invention, from the perspective of improving cleaning power and operability, it is preferably 500 ^cm2 or more, more preferably 750 ^cm2 or more, and further preferably 1,000 ^cm2 or more. Moreover, from the perspective of cleaning power, it is preferably 20,000 ^cm2 or less, more preferably 10,000 ^cm2 or less, and further preferably 3,000 ^cm2 or less. According to the cleaning article of the present invention, good foam can be formed without depending on the pulling speed of the trigger. Thereby, the feeling of use or foam cleaning performance can be improved without depending on the usage pattern of the user using the above-mentioned article. In the cleaning article of the present invention, the coverage of the foam sprayed 5 times continuously from the pressure-accumulating trigger spray is preferably within the above range. The foam sprayed 5 times continuously is obtained by repeatedly pulling the pressure-accumulating trigger spray or the continuous spray trigger spray 5 times to continuously spray the contents. Sprayer

In the cleaning article of the present invention, the coverage range of the liquid detergent composition sprayed in the form of foam from the spray container in 5 consecutive spraying operations is the area obtained by measuring the short diameter and long diameter of the range with foam attached with a ruler on the surface of the object 40 cm away from the cleaning article of the present invention relative to the spraying surface, and spraying the liquid detergent composition 5 times continuously.

In terms of the close contact or close contact time of the liquid detergent composition sprayed in the form of foam using a spray container with a hard surface, the thickness of the foam on the hard surface just after spraying is preferably 3 mm or more, more preferably 5 mm or more, and further preferably 8 mm or more. The cleaning article of the present invention is preferably sprayed with the liquid detergent composition in a manner that produces foam of such thickness.

Furthermore, from the viewpoint of improving the cleaning power by adhering closely to the stains, the liquid detergent composition sprayed in the form of foam on the cleaning article of the present invention preferably has a close contact time with the hard surface of more than 20 seconds, more preferably more than 30 seconds, and further preferably more than 1 minute. Furthermore, from the viewpoint of the permeability to the stains, it is preferably less than 20 minutes, more preferably less than 10 minutes. The close contact time of the liquid detergent composition on the hard surface can be measured as follows. For example, a bottomed container made of polypropylene (having an area of more than 200 mm×200 mm) is used as a test piece, and the corner at the junction of the bottom and the wall of the container is sprayed once, and then the test piece is immediately raised at a right angle to observe the state of the foam. The spraying direction of the spray container is set at an angle of 45 degrees to the bottom, and the distance from the foam outlet of the nozzle to the corner is set to 15 cm. The time from the point when the test piece is placed upright at a right angle with the bottom upright until the lower end of the foam moves downward (droops) by more than 2 cm is measured. The evaluation of adhesion is carried out at a temperature of 20°C and a humidity of 65%.

The spray container may be made entirely of synthetic resin, or may be made entirely or partially of materials other than synthetic resins such as metal or ceramics. As synthetic resins, for example, polyolefins such as polyethylene and polypropylene, polystyrene, polyethylene terephthalate (PET), polycarbonate, acrylic resin, polyamide, polyacetal, vinyl chloride, etc. may be used. The container body of the spray container is preferably formed of synthetic resin, and may be manufactured, for example, by blow molding. The capacity of the container body of the spray container is preferably 200 mL or more, more preferably 300 mL or more, and preferably 600 mL or less, more preferably 500 mL or less, and preferably 200 mL or more and 600 mL or less, more preferably 300 mL or more and 500 mL or less.

<Aspects of the present invention> The following are examples of aspects of the present invention. In these aspects, the descriptions related to a cleaning article having a pressure-accumulating trigger spray container and a liquid detergent composition contained in the spray container, and a cleaning method for a surface of a cleaning object in which foam sprayed using the cleaning article contacts the surface of the cleaning object can be modified as needed and applied.

<1> A cleaning article, comprising a pressure-accumulating trigger spray container and a liquid detergent composition contained in the spray container, wherein the spray container is capable of spraying the liquid detergent composition into foam, the foam specific volume of the sprayed foam is 15 mL/g or more, and the ratio of the foam specific volume of the foam sprayed from the spray container at 0.2 seconds/stroke to the foam specific volume of the foam sprayed from the spray container at 0.5 seconds/stroke is 0.5 or more and less than 2.0.

<2> The cleaning article as described in <1>, wherein the liquid cleaning agent composition is made into foam and sprayed, and the foam specific volume of the sprayed foam is preferably 15 mL/g to 80 mL/g, more preferably 20 mL/g to 60 mL/g, and further preferably 25 mL/g to 60 mL/g.

<3> The cleaning article as described in <1> or <2>, wherein the ratio of the foam specific volume of the foam sprayed from the above-mentioned spray container at 0.2 seconds/stroke to the foam specific volume of the foam sprayed from the above-mentioned spray container at 0.5 seconds/stroke is 0.5 or more, preferably 0.55 or more, more preferably 0.6 or more, and further preferably 0.65 or more, and is less than 2.0, preferably 1.85 or less, more preferably 1.7 or less, and further preferably 1.5 or less.

<4> Any cleaning article listed in any of <1> to <3>, which is used for cleaning hard surfaces.

<5> A cleaning article as described in any one of <1> to <4>, wherein the liquid cleaning agent composition contains one or more selected from amine oxide, sulfobetaine, carboxybetaine, alkyl (poly)glucoside, and alkyl (poly)glyceryl ether.

<6> A cleaning article as described in any one of <1> to <5>, wherein the liquid cleaning agent composition contains (d) one or more selected from alcohols having 3 to 10 carbon atoms and diol solvents having 2 to 14 carbon atoms.

<7> A cleaning article as described in any one of <1> to <6>, wherein the liquid cleaning agent composition contains (a) an amphoteric surfactant and (d) a water-soluble solvent.

<8> A cleaning article as described in any one of <1> to <6>, wherein the liquid cleaning agent composition contains (a) an amphoteric surfactant, (c) a hydrophilic polymer and (d) a water-soluble solvent.

<9> A cleaning article as described in any one of <1> to <8>, wherein the liquid cleaning agent composition contains (a) an amphoteric surfactant [hereinafter referred to as component (a)], wherein the amphoteric surfactant of component (a) is preferably at least one selected from amine oxide type amphoteric surfactants and betaine type amphoteric surfactants, more preferably at least one selected from amine oxide, sulfobetaine and carboxybetaine, and further preferably at least one selected from amine oxide and carboxybetaine.

<10> The cleaning article as described in <9>, wherein the amine oxide is a compound represented by the following general formula (a1) [hereinafter referred to as component (a1)].

[Chemistry 8] [In the formula, R ^1a represents a alkyl group having 6 to 22 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, R ^2a and R ^3a each independently represent an alkyl group having 1 to 3 carbon atoms. D represents a -NHC(=O)- group or a -C(=O)NH- group, and E represents an alkylene group having 1 to 5 carbon atoms. q and p represent q=0 and p=0 or q=1 and p=1]

<11> The cleaning article as described in <10>, wherein the component (a1) is an alkyl (carbon number 6 to 22) dialkyl (carbon number 1 to 3) amine oxide: octyl dimethyl amine oxide, decyl dimethyl amine oxide, lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, palmityl dimethyl amine oxide, stearyl dimethyl amine oxide.

<12> The cleaning article as described in <10>, wherein the component (a1) is a compound containing amido-type amine oxide (a compound in which q=1 and p=1 in the general formula (a1)): octylamidopropyl dimethylamine oxide, decylamidopropyl dimethylamine oxide, laurylamidopropyl dimethylamine oxide, myristylamidopropyl dimethylamine oxide, palmitylamidopropyl dimethylamine oxide.

<13> The cleaning article as described in <9>, wherein the above-mentioned betaine-type amphoteric surfactant is a compound represented by the following general formula (a2) [hereinafter referred to as component (a2)].

[Chemistry 9] [In the formula, R ^4a is an alkyl or alkenyl group having 7 to 18 carbon atoms, R ^5a is an alkylene group having 1 to 6 carbon atoms. A is a group selected from -COO-, -CONH-, -OCO-, -NHCO-, and -O-, and r is 0 or 1. R ^6a and R ^7a are each independently an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and R ^8a is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group. B is a group selected from -SO ₃ ^- , -OSO ₃ ^- , and -COO ^- ]

<14> The cleaning article as described in <13>, wherein the above-mentioned betaine-type amphoteric surfactant is one or more selected from alkylamidopropyl-N,N-dimethylcarboxybetaine, wherein the carbon number of the alkyl group is 7 or more, preferably 8 or more, more preferably 10 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, and alkyl-N,N-dimethylacetatebetaine.

<15> A cleaning article as described in any one of <1> to <14>, wherein the liquid cleaning agent composition contains (b) a disinfectant [hereinafter referred to as component (b)], and component (b) contains one or more selected from benzyl alcohol and phenoxyethanol.

<16> A cleaning article as described in any one of <1> to <15>, wherein the liquid cleaning agent composition contains (c) a hydrophilic polymer [hereinafter referred to as component (c)].

<17> The cleaning article as described in <16>, wherein the component (c) is a polymer comprising structural units A derived from one or more monomers A selected from monomers (c1) represented by the following general formula (c1) and monomers (c2) represented by the following general formula (c2).

[Chemistry 10]

[In the formula, R ^1c , R ^2c , R ^3c , R ^7c , R ^8c , and R ^9c are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. X ^1c and Y ^1c are each independently a group selected from an alkylene group having 1 to 12 carbon atoms, -COOR ^12c -, -CONHR ^12c -, -OCOR ^12c -, and -R ^13c -OCO-R ^12c -. Here, R ^12c and R ^13c are each independently an alkylene group having 1 to 5 carbon atoms. R ^4c is an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, or R ^1c R ^2c C=C(R ^3c )-X ^1c -. R ^5c is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ^6c is an alkyl group having 1 to 10 carbon atoms, or a benzyl group, which may be substituted with a hydroxyl group, a carboxyl group, a sulfonic acid group, or a sulfate group. When R ^6c is an alkyl group, a hydroxyalkyl group, or a benzyl group, ^Z- represents an anion. When R ^6c includes a carboxyl group, a sulfonic acid group, or a sulfate group, ^Z- does not exist, and these groups in R ^6c become anions. Examples of the anion of ^Z- include halogen ions, sulfate ions, alkyl sulfate ions having 1 to 3 carbon atoms, aromatic sulfonic acid ions which may be substituted with an alkyl group having 1 to 3 carbon atoms, and hydroxyl ions. R ^10c is a hydrogen atom, an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, or R ^7c R ^8c C=C(R ^9c )-Y ^1c -. R ^11c is a hydrogen atom, an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms.]

<18> The cleaning article as described in <16>, wherein component (c) is a natural polymer such as a polysaccharide or a cellulose derivative or a derivative thereof.

<19> The cleaning article as described in <18>, wherein the cellulose derivative is a cellulose derivative selected from hydroxypropyl methylcellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, ethyl cellulose, and carboxymethyl cellulose.

<20> The cleaning article as described in <16>, wherein component (c) is hydroxyethyl cellulose and polyvinyl alcohol.

<21> The cleaning article as described in <16>, wherein the component (c) is preferably a polymer having a structural unit D represented by the following general formula (c3), and more preferably a copolymer comprising a structural unit D represented by the following general formula (c3) and a structural unit E represented by the following general formula (c4).

[Chemistry 11]

[In the formula, R ^14c to R ^16c : are the same or different, and are a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. R ^17c : an alkylene group having 1 to 4 carbon atoms, or -Y ^2c -OPO ₃ ^- -Y ^3c - Y ^2c , Y ^3c : are the same or different, and are an alkylene group having 1 to 4 carbon atoms. R ^18c , R ^19c : are the same or different, and are a alkyl group having 1 to 4 carbon atoms. X ^2c : O or NR ^20c , R ^20c is a hydrogen atom or a alkyl group having 1 to 4 carbon atoms. X ^3c : represents a hydrogen atom, a alkyl group having 1 to 4 carbon atoms, R ^21c SO ₃ ^- , or R ^21c COO ^- . wherein when R ^17c is an alkylene group having 1 to 4 carbon atoms, X ^3c is R ^21c SO ₃ ^- or R ^21c COO ^- , R ^21c is an alkylene group having 1 to 4 carbon atoms, and when R ^17c is -Y ^2c -OPO ₃ ^- -Y ^3c -, X ^3c is a hydrogen atom or a alkyl group having 1 to 4 carbon atoms]

[Chemistry 12]

[In the formula, R ^22c to R ^24c are the same or different and are hydrogen atoms or alkyl groups having 1 or 2 carbon atoms; X ^4c is O or NH; R ^25c is an alkylene group having 1 to 4 carbon atoms; X ^5c is N ^+; R ^26c R ^27c R ^28c X ^6c or NR ^29c R ^30c ; R ^26c to R ^30c are the same or different and are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms; and X ^6c represents an anion]

<22> The cleaning article as described in <16>, wherein the weight average molecular weight of component (c) is preferably 10,000 or more, more preferably 30,000 or more, further preferably 50,000 or more, further preferably 100,000 or more, and preferably 5,000,000 or less, further preferably 3,000,000 or less, further preferably 2,000,000 or less.

<23> A cleaning article as described in any one of <1> to <16>, wherein the liquid cleaning agent composition contains (c) a hydrophilic polymer [hereinafter referred to as component (c)], and component (c) is preferably one or more selected from cellulose derivatives, polysaccharides, and polyvinyl alcohol, more preferably one or more selected from hydroxyethyl cellulose, tris-glucoside, and polyvinyl alcohol, and further preferably one or more selected from hydroxyethyl cellulose and polyvinyl alcohol.

<24> A cleaning article as described in any one of <1> to <16>, wherein the liquid cleaning agent composition contains (c) a hydrophilic polymer [hereinafter referred to as component (c)], and when the pressure-accumulating trigger spray container is a pressure-accumulating trigger spray container capable of continuous spraying, component (c) is preferably selected from one or more polymers containing one or more structural units A to E, cellulose derivatives, polysaccharide derivatives, and polyvinyl alcohol derivatives, and more preferably selected from one or more polymers containing structural units A or D, hydroxyethyl cellulose, cationically modified hydroxyethyl cellulose, tris-glucoside, polyvinyl alcohol, and cationically modified polyvinyl alcohol.

<25> A cleaning article as described in any one of <1> to <24>, wherein the liquid cleaning agent composition contains (d) one or more water-soluble solvents selected from alcohols having a carbon number of 3 to 10 and diol compounds having a carbon number of 2 to 14 [hereinafter referred to as component (d)], and component (d) is preferably selected from isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, isopentyl glycol, propylene glycol monohydrate ...ethylene glycol monohydrate, propylene glycol monohydrate, ethylene glycol monohydrate, propylene glycol monohydrate, ethylene glycol monohydrate, propylene glycol monohydrate, ethylene glycol monohydrate, propylene glycol monohydrate, ethylene glycol monohydrate One or more selected from methyl ether, dipropylene glycol monobutyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, phenoxy triethylene glycol, diethylene glycol butyl ether (diethylene glycol monobutyl ether), and dibutylene glycol, more preferably one or more selected from phenoxy triethylene glycol, diethylene glycol butyl ether, propylene glycol, propylene glycol monomethyl ether, and dipropylene glycol monobutyl ether, and particularly preferably one or more selected from diethylene glycol butyl ether and dipropylene glycol monobutyl ether.

<26> A cleaning article as described in any one of <1> to <25>, wherein the liquid cleaning agent composition contains (a) an amphoteric surfactant [hereinafter referred to as component (a)] and (c) a hydrophilic polymer [hereinafter referred to as component (c)], The mass ratio (c)/(a) of the content of component (c) to the content of component (a) in the liquid cleaning agent composition is 0.005 or more, preferably 0.01 or more, more preferably 0.02 or more, further preferably 0.03 or more, and preferably 1 or less, more preferably 0.5 or less, further preferably 0.1 or less.

<27> The cleaning article as described in any one of <1> to <26>, wherein the liquid cleaning agent composition contains (a) an amphoteric surfactant [hereinafter referred to as component (a)] and (d) one or more water-soluble solvents selected from alcohols having a carbon number of 3 to 10 and diol compounds having a carbon number of 2 to 14 [hereinafter referred to as component (d)], The mass ratio (d)/(a) of the content of component (d) to the content of component (a) in the liquid cleaning agent composition is preferably 0.5 or more, more preferably 0.8 or more, further preferably 1.0 or more, and preferably 5.0 or less, more preferably 3.0 or less, further preferably 2.5 or less, further preferably 2.0 or less, and particularly preferably 1.8 or less.

<28> A cleaning article as described in any one of <1> to <27>, wherein the liquid cleaning agent composition contains (a) an amphoteric surfactant [hereinafter referred to as component (a)], (d) one or more water-soluble solvents selected from alcohols having a carbon number of 3 to 10 and diol compounds having a carbon number of 2 to 14 [hereinafter referred to as component (d)], and (c) a hydrophilic polymer [hereinafter referred to as component (c)], and the mass ratio of the content of component (c) to the content of component (a) in the liquid cleaning agent composition is (c) /(a) is 0.005 or more, preferably 0.01 or more, more preferably 0.02 or more, and more preferably 0.03 or more, and preferably 1 or less, more preferably 0.5 or less, and more preferably 0.1 or less, and the mass ratio (d)/(a) of the content of component (d) to the content of component (a) is preferably 0.5 or more, more preferably 0.8 or more, and more preferably 1.0 or more, and preferably 5.0 or less, more preferably 3.0 or less, and more preferably 2.5 or less, and more preferably 2.0 or less.

<29> A cleaning article as described in any one of <1> to <28>, wherein the liquid cleaning agent composition contains (a) an amphoteric surfactant [hereinafter referred to as component (a)], (d) one or more water-soluble solvents selected from alcohols having a carbon number of 3 to 10 and diol compounds having a carbon number of 2 to 14 [hereinafter referred to as component (d)], and (c) a hydrophilic polymer [hereinafter referred to as component (c)], and when the pressure-accumulating trigger spray container is a pressure-accumulating trigger spray container capable of continuous spraying, the liquid cleaning agent composition , the mass ratio (c)/(a) of the content of component (c) to the content of component (a) is preferably 0.5 or less, more preferably 0.2 or less, further preferably 0.05 or less, and particularly preferably 0, and the mass ratio (d)/(a) of the content of component (d) to the content of component (a) is preferably 0.5 or more, more preferably 0.8 or more, further preferably 1.0 or more, particularly preferably 1.3 or more, and preferably 5.0 or less, more preferably 3.0 or less, further preferably 2.5 or less, further preferably 2.0 or less, and particularly preferably 1.8 or less.

<30> For cleaning articles as described in any one of <1> to <29>, when the liquid cleaning agent composition contains (a) an amphoteric surfactant [hereinafter referred to as component (a)] and (f) anionic surfactant [hereinafter referred to as component (f)], the mass ratio (f)/(a) of the content of component (f) to the content of component (a) in the composition is preferably 5.0 or less, more preferably 2.5 or less, further preferably 2.0 or less, further preferably 1.0 or less, and particularly preferably 0.5 or less.

<31> A cleaning article as described in any one of <1> to <30>, wherein the viscosity of the liquid cleaning agent composition at 25°C is preferably 1 mPa·s or more, more preferably 3 mPa·s or more, and further preferably 5 mPa·s or more, and further preferably 50 mPa·s or less, more preferably 20 mPa·s or less, further preferably 15 mPa·s or less, further preferably 12 mPa·s or less, and further preferably 10 mPa·s or less.

<32> A method for cleaning the surface of an object to be cleaned, wherein the foam sprayed by using any cleaning article described in any one of <1> to <31> is brought into contact with the surface of the object to be cleaned.

<33> A method for cleaning the surface of a cleaning object as described in <32>, wherein the coverage area of the liquid detergent composition sprayed in the form of foam from the spray container of the above-mentioned cleaning object in 5 consecutive spraying operations is preferably 500 ^cm2 or more, more preferably 750 ^cm2 or more, and further preferably 1,000 ^cm2 or more, and is preferably 20,000 ^cm2 or less, more preferably 10,000 ^cm2 or less, and further preferably 3,000 ^cm2 or less.

Examples <Examples 1 to 3 and Comparative Example 1> Using the components listed in Tables 1 to 3, the liquid detergent compositions shown in Tables 1 to 3 were prepared and evaluated for the following items. The results are shown in Tables 1 to 3. In addition, the mass % of the formulated components in Tables 1 to 3 are all values based on the active ingredients.

The polymer A and polymer B of component (c) are synthesized according to the method described in the following Production Example 1 or 2. <Production Example 1> Polymer A is synthesized in a manner to achieve a prescribed molar ratio by referring to Japanese Patent Laid-Open No. 6-212597 and Japanese Patent Publication No. 53-10539.

<Production Example 2> Polymer B was synthesized by the method described in the following steps 1 and 2. (Step 1) 126.30 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a 4-necked flask with an internal capacity of 1000 mL, and the temperature was raised to 78°C to reflux. At this time, a solution containing 181.12 g of 2-(dimethylamino)ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 23.60 g of 2-(dimethylamino)ethyl methacrylate diethyl sulfate (manufactured by Kao Corporation/90% aqueous solution), and 53.20 g of ethanol, and a solution containing 5.83 g of 2,2'-azobis(2-methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) and 10.00 g of ethanol were added dropwise over 2 hours. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.

(Step 2) In a 1000 mL 4-necked flask, add 94.70 g of the obtained polymer solution, 3.15 g of sodium bicarbonate (manufactured by Wako Pure Chemical Industries, Ltd.), and 150.00 g of water, and raise the temperature to 50°C. At this time, 38.70 g of 1,3-propane sultone (manufactured by Tokyo Chemical Industry Co., Ltd.) is added dropwise over 1 hour to react. After aging for 3 hours, ethanol is distilled off by heating under reduced pressure at 90°C/20 kPa for 2 hours to obtain an aqueous solution containing polymer B.

The structural unit D of polymer B in formula (c3) has the following structure, the structural unit E in formula (c4) has the following structure, and the molar ratio of structural unit D/structural unit E is 95/5. Structural unit D: R ^14c =R ^15c =H, R ^16c =CH ₃ , R ^17c =C ₂ H ₄ , R ^18c =R ^19c =CH ₃ , X ^2c =O, X ^3c =R ^21c SO ₃ ^- , R ^21c =C ₃ H ₆ Structural unit E: R ^22c =R ^23c =H, R ^24c =CH ₃ , X ^4c =O, R ^25c =C ₂ H ₄ , X ^5c =N ⁺ R ^26c R ^27c R ^28c X ^6c , R ^26c =R ^27c =CH ₃ , R ^28c =C ₂ H ₅ , X ^6c =C ₂ H ₅ SO ₄ ^-The weight average molecular weight of polymer B is 63,000.

The weight average molecular weight of polymer B was measured by gel permeation chromatography (GPC) under the following conditions. Column: Two TSKgel α-M (manufactured by Tosoh Co., Ltd.) were connected in series. Column temperature: 40°C Solvent: 0.15 mol Na ₂ SO ₄ /1% CH ₃ COOH/water Flow rate: 1.0 mL/min Detector: Differential refractometer Standard substance: Polytriglucose standard

In addition, the weight average molecular weight of polymer B was measured using SLS (static light scattering method). That is, by using a light scattering photometer "DLS-7000" (manufactured by Otsuka Electronics Co., Ltd.), static light scattering was measured under the following conditions, and Zimm-plot was prepared for calculation. In addition, the refractive index increment required for the calculation of the molecular weight was measured using a differential refractometer "DRM3000" (manufactured by Otsuka Electronics Co., Ltd.). Wavelength: 632.8 nm (helium-neon laser) Scattering angle: measured every 10° from 30° to 150°. Temperature: 25°C Solvent: trifluoroethanol

<(a) Ingredients> ・Lauryl dimethylamine oxide: Amphitol 20N, manufactured by Kao Corporation ・Lauryl amidopropyl dimethylamine oxide: SOFTAZOLINE LAO-C, manufactured by Kawaken Seika Chemical Co., Ltd. ・Lauryl amidopropyl betaine: Amphitol 20AB, manufactured by Kao Corporation ・Lauryl hydroxysulfobetaine: Amphitol 20HD, manufactured by Kao Corporation <(b) Ingredients> ・Alkylbenzyl dimethyl ammonium chloride: SANISOL B-50 (mixture of carbon numbers 8 to 16), manufactured by Kao Corporation ・Dodecyltrimethylammonium chloride (C12TMAC): manufactured by Tokyo Chemical Industry Co., Ltd. ・Stearyltrimethylammonium chloride (C18TMAC): manufactured by Tokyo Chemical Industry Co., Ltd. ・Benzyl alcohol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・Ethanol: manufactured by Nippon Synthetic Alcohol Co., Ltd. <(c) Components> ・Polymer A: copolymer of diallyldimethylammonium chloride/maleic acid/SO ₂ = 70:25:5 (molar ratio), weight average molecular weight 30,000 ・Polymer B: copolymer obtained in the above-mentioned Production Example 2 ・HEC: hydroxyethyl cellulose, DAICEL SE850, viscosity (1%, 25℃) 2400-3000 mPa・s, molecular weight 1.56 million, DAICEL PVA manufactured by Miraizu Co., Ltd.: Polyvinyl alcohol, weight average molecular weight 50,000, viscosity (4%, 20°C) 20.5 to 24.5 mPa・s, saponification degree 87.0 to 89.0 mol%, KURARAY POVAL 22-88, PVA manufactured by Kuraray Co., Ltd. (weight average molecular weight 70,000): Polyvinyl alcohol, weight average molecular weight 70,000, KURARAY POVAL 44-88, PVA manufactured by Kuraray Co., Ltd. (weight average molecular weight 100,000): Polyvinyl alcohol, weight average molecular weight 100,000, KURARAY POVAL 95-88, PVA manufactured by Kuraray Co., Ltd. (weight average molecular weight 200,000): Polyvinyl alcohol, weight average molecular weight 200,000, PVA manufactured by Sigma-Aldrich (weight average molecular weight 350,000): Polyvinyl alcohol, weight average molecular weight 350,000, KURARAY POVAL 200-88KX, manufactured by Kuraray Co., Ltd. Monat Gum (weight average molecular weight 3 million): Monat Gum OB, weight average molecular weight 3 million, manufactured by MP Gokyo Food & Chemical Co., Ltd. <(d) Ingredients> ・Diethylene glycol butyl ether: manufactured by Nippon Emulsifier Co., Ltd. ・Propylene glycol monomethyl ether: manufactured by Nippon Emulsifier Co., Ltd. ・Dipropylene glycol monobutyl ether: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. <(e) Ingredients> ・Alkyl polyglycoside: Alkyl (carbon number 12 to 16) polyglucose (average sugar condensation degree 1 to 2), product name "AG124", manufactured by Kao Co., Ltd.) ・2-Ethylhexylglyceryl ether: Penetol GE-EH, manufactured by Kao Co., Ltd. <(f) Ingredients> ・Di-2-ethylhexyl sodium sulfosuccinate: Airrol CT-1L, manufactured by Toho Chemical Industry Co., Ltd. ・AES (alkyl ether sulfate): Emal 270J, manufactured by Kao Corporation <(g) ingredient> ・p-Toluenesulfonic acid: PTSM-7000, manufactured by Meiyou Industry Co., Ltd. <(h) ingredient> ・Citric acid: Refined citric acid (anhydride), manufactured by Fuso Industry Co., Ltd. ・Ethylenediaminetetraacetic acid: manufactured by Chubu Chelest Co., Ltd. <Other ingredients> ・Sodium sulfate: manufactured by Shikoku Chemical Industry Co., Ltd. ・Fragrance

<Oil cleaning performance> 20 mg of cooking oil was applied to the entire surface of one side of a SUS (Steel Use Stainless, Japanese stainless steel standard) substrate (manufactured by Engineering Test Service, 10 cm×10 cm×1 mm, alkali washed), and it was fully dried in a dryer and used as the evaluation cleaning object. The mass of the SUS substrate before and after the oil was applied was measured, and the "initial oil mass" was calculated based on the mass increase of the SUS substrate before and after the oil was applied. Using a commercially available trigger sprayer (Kyukyutto Foam Sprayer (manufactured by Kao Corporation), model number: TA-F), the liquid detergent compositions in Tables 1 to 3 were sprayed in a foamy state (approximately 1 mL) onto the oil stains on the SUS substrate. After leaving it for 30 seconds, kitchen paper was pressed on the oil stains and the stains were wiped off by applying a light force back and forth 5 times. This operation was performed on the oil stains on 6 different SUS substrates (using two trigger speeds of 0.5 seconds/stroke and 0.2 seconds/stroke for 3 times each). The stain adhesion status before and after cleaning was compared by taking photos, and the cleaning performance was evaluated visually based on the following indicators. In the evaluation of cleaning performance, the average value of 6 operations on oil stains on 6 different SUS substrates was used. The results are shown in Tables 1 to 3. The higher the value of the cleaning performance evaluation, the better the cleaning performance of oil stains. 5: The stain residue is less than 10% relative to the foam coating area. 4: The stain residue is more than 10% and less than 30% relative to the foam coating area. 3: The stain residue is more than 30% and less than 50% relative to the foam coating area. 2: The stain residue is more than 50% and less than 70% relative to the foam coating area. 1: Relative to the foam coating area, the stains remain more than 70%.

<Evaluation of Foam Specific Volume> The liquid detergent compositions in Tables 1 to 3 were filled into a spray container with a pressure-accumulating sprayer (Kyukyutto Foam Spray (Kao), Model No.: TA-F) and a spray container with a continuous sprayer (Bath Magic Rin Air Jet (Kao Co., Ltd., Batch No.: W0262202) with a nozzle tip of Attack Shutto Foam Spray (Kao Co., Ltd.) installed on the nozzle).

<Determination of Foam Specific Volume> Using each spray container described in the embodiment and comparative example, the liquid detergent composition inside was sprayed continuously 5 times without interval in a 200 mL measuring cylinder (made of glass, inner diameter 40 mm). After the 5th spray, the volume of foam in the measuring cylinder was visually read (mL) 1 minute later. In addition, the mass of the 200 mL measuring cylinder after spraying was measured using a 4-digit balance (which can measure to 2 decimal places), and the difference from the mass of the measuring cylinder before spraying was set as the mass of the foam (g), and the foam specific volume was calculated according to the following formula. The foam specific volume was measured at a temperature of 20°C and a humidity of 65%. In addition, the amount of foam sprayed by one spraying operation is the average of the mass (g) of foam obtained in the above-mentioned foam specific volume measurement, that is, the mass (g) of foam/5. Foam specific volume (mL/g) = Foam volume (mL)/foam mass (g)

The foam specific volume was calculated using the sprayers in Tables 1 to 3 under the conditions of changing the trigger pulling speed to 0.5 seconds/stroke and 0.2 seconds/stroke, respectively. In addition, the ratio of the foam specific volume (2) of the foam sprayed at 0.2 seconds/stroke to the foam specific volume (1) of the foam sprayed at 0.5 seconds/stroke [foam specific volume (2)/foam specific volume (1)] was calculated and shown in Tables 1 to 3.

<Pulling speed (adjustment of evaluation conditions)> In the above foam specific volume measurement, the time taken from the start of the trigger pulling to the end of the pulling (one-way) was measured, and the pulling speed (seconds/stroke) was calculated based on the average value (seconds) of 5 times. In addition, the action of pulling the trigger from the start to the end of the pulling was filmed at 1000fps using High-speed Microscope VW-9000 (manufactured by Keyence Co., Ltd.) and Camera Unit VW-600C (manufactured by Keyence Co., Ltd.), and saved as an image. The saved image was played back slowly using the video editing software CorelVideo Studio X7, and the time taken from the start of the trigger pulling to the end of the pulling was measured. In this method, it was confirmed that the experiment can be conducted using two speeds: 0.5 seconds/stroke (when the trigger is pulled slowly) and 0.2 seconds/stroke (when the trigger is pulled quickly).

<Viscosity measurement method> Prepare a B-type viscometer model BM manufactured by TOKIMEC INC. with a rotor No. 1 installed. 100 mL of the liquid detergent composition of the embodiment and the comparative example is filled in a viscosity measurement beaker and the temperature is fully adjusted in a constant temperature water bath at 25°C. The beaker containing the composition is placed in the viscometer, the rotor speed is set to 60 r/min, and the value after 60 seconds is measured, and this value is set as the viscosity of the liquid detergent composition.

<Evaluation of Convenience (1)> Considering that a foam with a larger specific volume can be sprayed in a wider range, the foam generated at two trigger pull speeds, namely, the foam specific volume of the foam generated when the trigger is pulled slowly (0.5 seconds/stroke) and the foam specific volume of the foam generated when the trigger is pulled quickly (0.2 seconds/stroke), was used to evaluate the convenience (1) as follows. The larger the evaluation number of the convenience (1), the more convenient the cleaning item is. 4: The foam specific volume is 25 mL/g or more at both speeds. 3: The foam specific volume is 15 mL/g or more at both speeds. 2: The foam specific volume does not reach 15 mL/g depending on the pull speed. 1: The foam specific volume does not reach 15 mL/g at any pull speed.

<Evaluation of efficiency (1)> The index of generating good foam without depending on the trigger speed of spraying is defined as efficiency (1). The efficiency (1) is evaluated using the ratio of the foam specific volume (2) of the foam formed when the trigger is pulled quickly (0.2 seconds/stroke) to the foam specific volume (1) of the foam formed when the trigger is pulled slowly (0.5 seconds/stroke) [foam specific volume (2)/foam specific volume (1): foam specific volume change rate]. The larger the evaluation number of efficiency (1), the more efficient the cleaning item is. 3: The foam specific volume change rate is 0.6 or more and less than 1.5. 2: The change rate of the foam specific volume is 0.5 or more and less than 0.6, or 1.5 or more and less than 2.0. 1: The change rate of the foam specific volume is less than 0.5, or 2.0 or more.

<Evaluation of Convenience (2)> The liquid detergent composition was sprayed on the tabletop 40 cm away from the cleaning items to evaluate the convenience (2). The evaluation was conducted by 10 testers at two different trigger pull speeds (0.5 seconds/stroke and 0.2 seconds/stroke). The short and long diameters of the area with foam were measured with a ruler. The average of the area with foam at the two pull speeds was calculated and shown in Tables 2 and 3. The wider the foam area of the cleaning items, the wider the range of foam spraying, and the better the convenience (2). Furthermore, in the case of a pressure-accumulating trigger, during the action of pulling the trigger once, the spray port of the cleaning items moves horizontally 20 cm relative to the sprayed surface of the table top at a constant speed. In addition, in the case of a continuous spray trigger, the spray port of the cleaning items moves horizontally 40 cm relative to the sprayed surface of the table top at a constant speed.

<Evaluation of efficiency (2)> The evaluation of the efficiency (2) of the cleaning items in Tables 2 and 3 was conducted by having 10 testers spray their respective cleaning items 5 times continuously as quickly as possible (※no specified trigger speed) and measure the foam specific volume. The foam specific volume was measured by the same method as described in the above <Measurement of foam specific volume>, and the average value of the 10 testers was calculated and shown in Tables 2 and 3. The cleaning items with larger foam specific volume, that is, the cleaning items that showed good foaming properties even when the trigger was pulled quickly, were the cleaning items with good efficiency.

[Table 1] Embodiment Comparison Example 1-1 1-2 1-3 1-4 1-5 1-1 1-2 1-3 Cleaning items Types of Sprayers Continuous spray Accumulator Accumulator Accumulator Accumulator Accumulator Accumulator Accumulator Liquid cleaning agent composition Composition (mass%) (a) Lauryl Dimethylamine Oxide 0.6 1.0 Laurylamidopropyl dimethylamine oxide 0.2 Laurylamidopropyl betaine 3 3 3 3 1.7 Lauryl Hydroxyl Sulfobetaine 3.15 (b) Alkylbenzyldimethylammonium chloride 0.1 0.1 Dodecyltrimethylammonium chloride (C12TMAC) 0.15 Stearyl trimethyl ammonium chloride (C18TMAC) 0.05 Benzyl alcohol 2 2 2 2 Ethanol 2.0 3.0 (c) Polymer A 0.1 Polymer B 0.1 HEC 0.02 0.05 0.10 0 PVA 0.1 (d) Diethylene glycol butyl ether 5 5 5 5 5 8.78 Propylene glycol monomethyl ether 2.0 3.0 (e) Alkyl polyglycoside 0.3 2-Ethylhexylglyceryl ether 0.3 1.5 (f) Di-2-ethylhexyl sodium sulfosuccinate 1.35 (g) p-Toluenesulfonic acid monohydrate 4.72 (h) Citric Acid 40 Ethylenediaminetetraacetic acid 3 3 3 3 Sodium sulfate 1 1 1 1 spices 0.1 02 0.2 0.2 0.2 0.2 0.0 0.2 water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Total 100 100 100 100 100 100 100 100 25℃ viscosity (mPa・s) 1.5 1.7 3.6 4.5 7.3 2.9 2.7 2.0 (c)/(a)(mass ratio) 0.13 0.10 0.01 002 0.03 0 0 0.06 (d)/(a)(mass ratio) 2.5 5.0 1.7 1.7 1.7 1.7 2.8 1.8 Foam specific volume (1) (swing speed: 0.5 sec/stroke) (mL/g) 16 39 53 62 40 49 40 twenty two Foam specific volume (2) (swing speed: 0.2 seconds/stroke) (mL/g) 17 25 40 50 54 16 14 7 Foam specific volume (2)/Foam specific volume (1) 1.06 0.64 0.75 0.81 1.35 0.33 0.35 0.32 Reviews Simplicity(1) 3 4 4 4 4 3 2 2 Efficiency (1) 3 2 3 3 3 1 1 1 Detergency of oil stains 4.7 4.5 4.3 4.5 4.5 4.0 4.2 3.8

As shown in Table 1, in Comparative Examples 1-1 to 1-3, if the trigger is pulled faster (0.2 seconds/stroke), the foam specific volume of the foam formed is reduced. This is considered to be because the liquid detergent composition is sprayed quickly, and the formation and stabilization of the foam film are not carried out in time relative to the mixing speed of air and the liquid detergent composition (hereinafter referred to as the gas-liquid mixing speed), so the ratio of the composition that does not become foam in the spray of the sprayed liquid detergent composition becomes higher, resulting in a decrease in the foam specific volume. In contrast, the liquid detergent composition of Examples 1-1 to 1-5 can take into account both the improvement of the foamability of the composition and the stability of the film foam by including component (d) and component (c) at a prescribed ratio. That is, the liquid detergent composition of the embodiment has excellent rapid foaming properties that contribute to foaming properties, and excellent foam stability that directly maintains foam. In particular, even when the gas-liquid mixing speed is faster due to the stabilization effect of the (c) component on the film foam, foam of a specified foam specific volume can be sprayed. In this way, regardless of the difference in the speed of pulling the trigger, foam of a specified foam specific volume can be sprayed, and as a result, cleaning of hard surfaces with good foam contact can be performed simply and efficiently.

[Table 2] Embodiment 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 Cleaning items Types of Sprayers Accumulator Accumulator Accumulator Accumulator Accumulator Accumulator Accumulator Accumulator Accumulator Accumulator Liquid cleaning agent composition Composition (mass%) (a) Lauryl Dimethylamine Oxide 2.97 2.94 2.91 2.80 2.0 2.5 Laurylamidopropyl dimethylamine oxide 3.0 3.0 3.0 3.0 (c) HEC 0.03 0.06 0.09 0.20 PVA (weight average molecular weight 70,000) 0.3 PVA (weight average molecular weight 100,000) 0.3 PVA (weight average molecular weight 200,000) 0.3 PVA (weight average molecular weight 350,000) 0.3 Sanxian glue (weight average molecular weight 3 million) 0.1 0.1 (d) Diethylene glycol butyl ether 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Propylene glycol monomethyl ether Dipropylene glycol monobutyl ether 5.0 5.0 (f) AES(Alkyl Ether Sulfate) 1.0 0.5 water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Total 100 100 100 100 100 100 100 100 100 100 25℃ viscosity (mPa・s) 2.0 2.8 4.6 23.4 1.4 1.4 1.4 1.4 23.1 32.2 (c)/(a)(mass ratio) 0.010 0.020 0.031 0.071 0.100 0.100 0.100 0.100 0.050 0.040 (d)/(a)(mass ratio) 1.68 1.70 1.72 1.79 1.67 1.67 1.67 1.67 2.50 2.00 Foam specific volume (1) (swing speed: 0.5 sec/stroke) (mL/g) 50 58 57 16 27 35 40 57 18 26 Foam specific volume (2) (swing speed: 0.2 seconds/stroke) (mL/g) 42 44 51 25 15 19 twenty one 35 15 20 Foam specific volume (2)/Foam specific volume (1) 0.83 0.76 0.90 1.61 0.54 0.55 0.52 0.61 0.85 0.76 Reviews Simplicity (2) (cm ² ) 1275 1430 1280 840 855 930 980 1375 805 810 Efficiency (2) (mL/g) 41 43 51 28 15 19 19 30 10 19 Detergency of oil stains 4.5 4.5 4.4 4.4 4.3 4.2 4.2 4.4 4.0 4.1

[table 3] Embodiment 3-1 3-2 3-3 3-4 3-5 Cleaning items Types of Sprayers Continuous spray Continuous spray Continuous spray Continuous spray Continuous spray Liquid cleaning agent composition Composition (mass%) (a) Lauryl Dimethylamine Oxide 2.0 3.0 Laurylamidopropyl dimethylamine oxide 2.0 3.0 Lauryl Hydroxyl Sulfobetaine 2.0 (d) Diethylene glycol butyl ether 5.0 5.0 Propylene glycol monomethyl ether Dipropylene glycol monobutyl ether 5.0 5.0 5.0 (e) Alkyl polyglycoside 3.0 3.0 3.0 2-Ethylhexylglyceryl ether 3.0 3.0 water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Total 100 100 100 100 100 25℃ viscosity (mPa・s) 2.5 2.2 1.5 4.5 3.5 (d)/(a)(mass ratio) 2.5 2.5 2.5 1.7 1.7 Foam specific volume (1) (swing speed: 0.5 sec/stroke) (mL/g) 25 19 26 twenty two 45 Foam specific volume (2) (swing speed: 0.2 seconds/stroke) (mL/g) 26 17 25 twenty three 47 Foam specific volume (2)/Foam specific volume (1) 1.04 0.91 0.95 1.04 1.05 Reviews Simplicity (2) (cm ² ) 1038 900 1038 1000 1570 Efficiency (2) (mL/g) 26 17 twenty three twenty four 47 Detergency of oil stains 4.3 4.4 4.3 4.5 4.6

1: Spray container 2: Container body 3: Sprayer 4: Trigger 5: Sprayer body 6: Vertical pipeline 7: Pipe 8: Horizontal pipeline 9: Cylinder 10: Rotating element 10a: Groove 10b: Concave 10c: Groove 11: Nozzle 11a: Spray port forming component 11b: Spray port 11c: Foaming component 11d: Hole or groove for air capture 11e: Foam spray port 12: Pressure accumulator component 13: Cylinder 13a: Outflow port 13b: Liquid inlet 14: Valve component 14a: Plug 14a': Liquid flow path 14b: plunger part 14c: small diameter cylindrical part 15: energy device 16: spray container 17: sprayer 18: main material cylinder 18a: main piston 19: vertical supply cylinder 20: spray hole 21: injection cylinder 22: supply hole 23: storage cylinder 23a: storage plunger 23b: energy device 23c: connecting hole 24: foaming nozzle (pointed mouth for foaming) 25: connecting cylinder 26: spray container 27: nozzle part 28: foaming cylinder (pointed mouth for foaming) 28a: air extraction hole 41: small circle 91: Cylindrical wall 92: Piston component 93: First check valve 94: Second check valve

FIG. 1 is a side sectional view of the main part of the spray container in one embodiment of the cleaning article of the present invention. FIG. 2 is a view showing the state of the rotating element of the spray container shown in FIG. 1 observed from its front end side. The front end of the rotating element is the side of the axial ends of the rotating element close to the nozzle portion for spraying foam. FIG. 3 is a side sectional view of the main part of the spray container in another embodiment of the cleaning article of the present invention. FIG. 4 is a cross-sectional view of the foaming cylinder provided in the spray hole of the spray container.

1: Spray container

2: Container body

3:Sprayer

4: Trigger

5: Sprayer body

6: Vertical pipeline

7: Tube

8: Horizontal pipeline

9: Material tank

10: Rotating element

11: Nozzle

11a: Injection nozzle forming component

11b: Nozzle

11c: Foam components

11d: Holes or slots for air capture

11e: Foam spray outlet

12: Pressure accumulator components

13: Material tank

13a: Outflow port

13b: Liquid inlet

14: Valve components

14a: Plug body

14a': Liquid flow path

14b: Plunger part

14c: Small diameter cylindrical part

15: Energy-enabling devices

21: Injection tube

41: Xiaoyuan

91: Cylindrical wall

92: Piston component

93: No. 1 check valve

94: No. 2 check valve

Claims (13)

A cleaning article, comprising a pressure-accumulating trigger spray container and a liquid cleaning agent composition contained in the spray container, wherein the spray container is capable of spraying the liquid cleaning agent composition into foam, the foam specific volume of the sprayed foam being 15 mL/g or more, and the ratio of the foam specific volume of the foam sprayed from the spray container at 0.2 seconds/stroke to the foam specific volume of the foam sprayed from the spray container at 0.5 seconds/stroke is 0.5 or more and less than 2.0. For example, the cleaning items in claim 1 are used for cleaning hard surfaces. For cleaning items in claim 1 or 2, the items shall be selected from the hard surface cleaning of items provided in at least one of the kitchen, toilet, bathroom and living room. The cleaning article according to any one of claims 1 to 3, wherein the liquid cleaning agent composition contains at least one selected from amine oxide type surfactants and betaine type surfactants. The cleaning article according to any one of claims 1 to 4, wherein the liquid cleaning agent composition contains at least one selected from alkyl (poly) glucoside and alkyl (poly) glycerol ether. The cleaning article according to any one of claims 1 to 5, wherein the liquid cleaning composition contains (c) a hydrophilic polymer. The cleaning article of any one of claims 1 to 6, wherein the liquid cleaning agent composition contains (d) one or more water-soluble solvents selected from alcohols having 3 to 10 carbon atoms and diol compounds having 2 to 14 carbon atoms. A cleaning article as claimed in any one of claims 1 to 7, wherein the pressure-accumulated trigger spray container can continuously spray the liquid cleaning agent composition. As for the cleaning article of claim 8, the above-mentioned pressure-accumulated trigger spray container has a pointed mouth, and the pointed mouth at the spray hole of the above-mentioned liquid cleaning agent composition in the spray container imparts foaming properties to the liquid cleaning agent composition. A cleaning article as claimed in any one of claims 1 to 9, wherein the liquid cleaning agent composition comprises the following components (a), (c) and (d), the weight average molecular weight of component (c) being 100,000 or more and 2,000,000 or less, the mass ratio (c)/(a) of the content of component (c) to the content of component (a) being 0.005 or more and 1 or less, the mass ratio (d)/(a) of the content of component (d) to the content of component (a) being 0.5 or more and 2.5 or less, Component (a): amphoteric surfactant Component (c): hydrophilic polymer Component (d): one or more water-soluble solvents selected from alcohols having 3 or more and 10 or less carbon atoms and diol compounds having 2 or more and 14 or less carbon atoms. A cleaning article as claimed in any one of claims 1 to 9, wherein the pressure-accumulating trigger spray container is capable of continuously spraying the liquid cleaning composition and has a pointed mouth, wherein the pointed mouth imparts foaming properties to the liquid cleaning composition at the spray hole of the liquid cleaning composition of the spray container. The liquid cleaning composition contains the following components (a) and (d), (a) component: amphoteric surfactant (d) component: one or more water-soluble solvents selected from alcohols having 3 to 10 carbon atoms and diol compounds having 2 to 14 carbon atoms. A method for cleaning the surface of an object to be cleaned, wherein the foam sprayed from the cleaning article of any one of claims 1 to 11 is brought into contact with the surface of the object to be cleaned. A method for cleaning the surface of an object to be cleaned as claimed in claim 12, wherein the range of the surface of the object to be cleaned covered by the foam when the trigger of the above-mentioned storage trigger spray is pulled continuously for 5 times is more than 500 ^cm2 .