Cleaning article

Abstract

To provide a cleaning article that can simply and efficiently clean a surface to be cleaned and has a satisfactory cleaning effect.SOLUTION: Provided is a cleaning article that has a pressure-accumulation type trigger spray container and a liquid cleaning composition contained within the spray container, and in which the spray container can spray the liquid cleaning composition into foam, and 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.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a cleaning article and a method for cleaning a surface to be cleaned. [Background technology]

[0002] In the sink and countertops used for washing dishes and vegetables, as well as around the kitchen such as gas ranges, inorganic dirt mainly composed of silicon and calcium, oily dirt from cooking and dishes, and a combination of these dirt adhere to the surfaces. In particular, dirt that occurs around cooking equipment is mainly oil from cooking, and since the heat source is nearby, the oil easily changes quality, making it very difficult to remove. Conventionally, powder or liquid cleansers containing abrasives, strong alkaline cleaners, etc. have been used to remove such stains. However, while the former have excellent cleaning properties, they have issues with the labor of scrubbing and the cumbersome process of rinsing and wiping, while the latter have issues with insufficient cleaning power for inorganic stains and rough hands due to the alkali. Furthermore, for cleaning kitchens, toilets, bathrooms, living rooms, and the like, trigger-type spray containers capable of spraying a detergent composition are used, and foam-discharging triggers are in widespread use from the viewpoints of preventing dripping from the object to be cleaned and increasing the time the liquid remains on the object to be cleaned to enhance the cleaning effect.

[0003] Patent Document 1 discloses an article for cleaning hard surfaces, which comprises a trigger-type spray container and a liquid detergent composition contained in the spray container, the spray container being capable of spraying the liquid detergent composition in the form of a foam, and the sprayed foam having a specific foam volume of 15 mL / g or more. Patent Document 2 discloses a cleaning article in which a liquid detergent composition is accommodated in a pressure-accumulation type foam discharge trigger spray container, and in which the foam has a specific foam volume one minute after spraying at a trigger pull speed of 6 g / s to 18 g / s of 15 mL / g to 45 mL / g, and the foam has a specific foam volume one minute after spraying at a trigger pull speed of 21 g / s to 45 g / s of 10 mL / g or less. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2017-214464 A [Patent Document 2] JP 2021-105076 A Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, the number of people, especially young people, has been prioritizing the simplification and time-saving of housework, and they want to reduce the time and effort spent on maintaining cleanliness. In addition, the number of single-person households of elderly people is increasing, and the labor of housework is becoming a heavy burden. In response to such changes in the social environment, there is a demand for a cleaning article and a cleaning method for surfaces to be cleaned that can clean objects such as hard surfaces simply and efficiently and have a satisfactory cleaning effect. The present invention provides a cleaning article and a method for cleaning a surface to be cleaned, which can clean the surface to be cleaned simply and efficiently and have a satisfactory cleaning effect. [Means for solving the problem]

[0006] The present invention relates to a cleaning article having a pressure-accumulation 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 as a foam, the sprayed foam has a specific foam volume of 15 mL / g or more, and the ratio of the specific foam volume of the foam sprayed from the spray container at 0.2 seconds / stroke to the specific foam volume of the foam sprayed from the spray container at 0.5 seconds / stroke is 0.5 or more and less than 2.0.

[0007] The present invention also relates to a method for cleaning a surface to be cleaned, which comprises contacting the surface to be cleaned with foam sprayed using the above-mentioned cleaning article. Effect of the Invention

[0008] According to the present invention, a cleaning article and a method for cleaning a surface to be cleaned are provided which can clean the surface to be cleaned simply and efficiently and have a satisfactory cleaning effect. [Brief description of the drawings]

[0009] [Figure 1] FIG. 2 is a side cross-sectional view showing a main portion of a spray container in one embodiment of the cleaning article of the present invention. [Diagram 2] This is a diagram showing the state of the spin element of the spray container shown in Figure 1 as viewed from its tip side. Of the two axial ends of the spin element, the tip of the spin element is the side closer to the nozzle part that projects foam. [Diagram 3] FIG. 2 is a side cross-sectional view showing a main portion of a spray container in another embodiment of the cleaning article of the present invention. [Figure 4] 1 is a cross-sectional view showing a foaming tube provided at the injection hole of a spray container. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The cleaning article of the present invention can always form good foam when spraying a liquid detergent composition from a trigger-type spray container, regardless of the speed at which the trigger is pulled. It is presumed that the cleaning article of the present invention can obtain sufficient foaming properties even when the trigger pulling speed differs depending on the user of the article, and is excellent in usability and foam cleansing properties.

[0011] The present invention will now be described based on preferred embodiments thereof. The cleaning article of this embodiment includes a trigger-type spray container 1 and a liquid detergent composition (not shown) contained in the spray container. The spray container used in the present invention is a trigger-type spray container. The trigger-type spray container has a configuration in which a trigger-type sprayer 3 for spraying a liquid, which is a liquid detergent composition, is attached to the mouth of a bottomed container body 2, as in the spray container 1 shown in Fig. 1. In general, the trigger 4 is pulled to discharge air from within a cylinder 9, and when the trigger 4 is returned, the liquid is sucked up through a tube 7 immersed in the liquid, filling the cylinder 9 with the liquid, and the trigger 4 is pulled again to push out the liquid from within the cylinder 9 and guide it to a vertical pipe 6, which further imparts spin to the flow of the liquid through a horizontal pipe 8 and a spin element 10, and the liquid is sprayed from a nozzle portion 11.

[0012] A more specific configuration of the spray container used in this embodiment will be described with reference to FIG. 1. The spray container 1 has a configuration in which a trigger-type sprayer 3 for spraying a liquid is attached detachably or non-detachably by screwing to the mouth of a bottomed container body 2 filled with a liquid. 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, and a vertical pipe 6 and a horizontal pipe 8 communicating with the vertical pipe 6 are formed in the sprayer body 5. A cylindrical wall portion 91 constituting a cylinder 9 is formed below the horizontal pipe 8, and a piston member 92 sliding within the cylinder 9 is disposed. The trigger 4 for pressing the piston member 92 is rotatably fitted to the side wall of the sprayer body 5. A small circle 41 shown by a dashed line in FIG. 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 constantly biased in a direction away from the mouth of the container body 2 by a biasing means (not shown) such as a leaf spring or a coil spring. In this specification, "upper" and "lower" refer to upper and lower in the vertical direction when the spray container 1 is placed on a horizontal surface.

[0013] The cylinder 9 has a first check valve 93 and a second check valve 94. The first check valve 93 allows the liquid to flow in from the flow path on the tube 7 side, while preventing the liquid from returning to the flow path when the trigger 4 is pulled, and the second check valve 94 allows the liquid to flow out to the flow path on the horizontal pipe 8 side, while preventing the liquid from returning from the flow path when the trigger 4 is released. The spin element 10 is cylindrical and has a number of grooves 10a extending in the axial direction around it as shown in FIG. 2. The tip of the spin element 10 on the nozzle portion 11 side has 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 recess 10b, so that the flow of the liquid in the recess 10b is given a spin, and the liquid to which the spin has been given is sprayed in a cone shape from the jet 11b provided in the jet nozzle forming member 11a arranged close to the tip of the spin element 10. The jet nozzle forming member 11a forms the nozzle portion 11 together with the former member 11c attached to its tip. Between the former member 11c and the jet nozzle forming member 11a, an air intake hole or groove 11d is formed, which has an inner opening on the back side of the liquid to be sprayed in a cone shape and an outer opening at the tip of the jet nozzle forming member 11a. The air taken in through this air intake hole or groove 11d is mixed with the liquid material being sprayed in a cone shape, causing the liquid detergent composition as the liquid material to turn into foam and be sprayed from the foam outlet 11e.

[0014] The sprayer 3 of the spray container 1 shown in Fig. 1 is a pressure-accumulation type sprayer. A pressure-accumulation type sprayer is configured such that even if the trigger 4 is operated, the liquid is not sprayed from the nozzle portion 11 until the liquid pressure in the cylinder 9 reaches a predetermined liquid pressure, and the liquid is sprayed when the liquid pressure in the cylinder 9 is increased to or above the predetermined liquid pressure. The sprayer 3 shown in FIG. 1 is provided with a pressure accumulator 12 so that spraying occurs only when the pressure in the cylinder 9 is increased to a predetermined liquid pressure or higher. The pressure accumulator 12 has a cylinder 13 having a cylindrical inner wall surface, and a valve member 14 arranged in the cylinder 13 and moving up and down along the central axis of the cylinder 13. The valve member 14 is constantly urged upward by a urging means 15 such as a coil spring, and when the trigger 4 is not operated, as shown in FIG. 1, a plug 14a formed at the upper end of the valve member 14 closes the outlet 13a to the downstream flow path. A plunger portion 14b whose outer periphery is in sliding contact with the inner wall surface of the cylinder 13 is connected to the lower surface of the plunger portion 14b, and a small diameter cylindrical portion 14c is connected to the lower surface of the plunger portion 14b. A flow path 14a' for liquid flowing from the small diameter cylindrical portion 14c to the periphery of the plug 14a is formed at the lower end of the plug 14a.

[0015] When the trigger 4 is operated while the cylinder 9 is filled with the liquid, the first check valve 93 is closed and the second check valve 94 is opened, and the liquid in the cylinder 9 is sent from the liquid inlet 13b into the pressure accumulating member 12. This causes the liquid pressure of the liquid in the cylinder 13 to increase. The area of ​​the upper surface of the plunger portion 14b is larger than the area of ​​the lower surface of the stopper body 14a, and due to this area difference, the liquid pressure of the liquid acts as a force to press down the valve member 14. If the operation of pulling the trigger 4 is continued, the liquid pressure in the cylinder 9 and the cylinder 13 further increases, and the force pressing down the valve member 14 becomes greater than the force pressing up the biasing means 15. This causes the valve member 14 to descend, opening the outlet 13a that was closed by the stopper body 14a, and the liquid is discharged from the nozzle portion 11. On the other hand, when the trigger 4 is pulled to the final position, the fluid pressure in the cylinders 9 and 13 decreases, and the force pushing down the valve member 14 becomes smaller than the force pushing up the valve member 14 by the biasing means 15, so that the valve member 14 rises and the outlet 13a is closed again by the plug 14a.

[0016] The cleaning article of the present invention is characterized in that the liquid detergent composition can be sprayed as a foam, and the specific foam volume of the sprayed foam is 15 mL / g or more. The specific foam volume of the sprayed foam may be, for example, the specific foam volume of the foam 1 minute after spraying from a spray container at 0.5 seconds / stroke. The specific foam volume of the sprayed foam may be, for example, both the specific foam volume of the foam 1 minute after spraying from a spray container at 0.5 seconds / stroke and the specific foam volume of the foam 1 minute after spraying from a spray container at 0.2 seconds / stroke. The specific foam volume of the foam sprayed by the cleaning article of the present invention is preferably 15 mL / g or more after 1 minute when sprayed under one or more conditions selected from 0.5 seconds / stroke and 0.2 seconds / stroke, and more preferably both the specific foam volume of the foam sprayed at 0.5 seconds / stroke after 1 minute and the specific foam volume of the foam sprayed at 0.2 seconds / stroke after 1 minute are 15 mL / g or more. Hereinafter, the same applies to the specific foam volume of the foam sprayed by the cleaning article of the present invention unless otherwise specified.

[0017] When the liquid detergent composition is foamed and sprayed, the foam specific volume of the sprayed foam is 15mL / g or more, so that the cleaning power against dirt, especially oily dirt, attached to the surface to be cleaned is improved. From the viewpoint of the convenience of being able to spray over a wide area, the foam specific volume of the sprayed foam is preferably 20mL / g or more, more preferably 25mL / g or more, and from the viewpoint of the convenience of wiping off the foam attached to the surface to be cleaned after spraying and the convenience of rinsing with water, the foam specific volume of the sprayed foam is preferably 80mL / g or less, more preferably 60mL / g or less. From the viewpoint of the cleaning power against oily dirt and the convenience, the foam specific volume of the sprayed foam is preferably 15mL / g or more and 80mL / g or less, more preferably 20mL / g or more and 60mL / g or less, and even more preferably 25mL / g or more and 60mL / g or less. The method for measuring the specific foam volume of the sprayed foam will be described later in the Examples.

[0018] Another feature of the cleaning article of the present invention is that the ratio of the specific foam volume of the foam sprayed from the spray container at 0.2 seconds / stroke to the specific foam volume of the foam sprayed from the spray container at 0.5 seconds / stroke is 0.5 or more and less than 2.0. This ratio of the specific foam volume is also called the rate of change in the specific foam volume when spraying with different trigger pull speeds. The specific foam volumes of these sprayed foams may be the specific foam volumes 1 minute after spraying from the spray container. By having the foam specific volume ratio of 0.5 or more and less than 2.0, good foam is always formed regardless of the speed at which the trigger is pulled, and convenience and efficiency are improved. From such a viewpoint, the foam specific volume ratio is 0.5 or more, preferably 0.55 or more, more preferably 0.6 or more, even more preferably 0.65 or more, and less than 2.0, preferably 1.85 or less, more preferably 1.7 or less, even more preferably 1.5 or less.

[0019] When the liquid detergent composition is foamed and sprayed, the foam specific volume of the sprayed foam is 15 mL / g or more, thereby improving adhesion to the surface to be cleaned and improving the cleaning power against oily stains adhering to the surface to be cleaned. Furthermore, since it is possible to spray over a wider area and reduce the number of times of spraying as compared with the case where the same liquid detergent composition is used, usability is improved.

[0020] In order to make the foam specific volume of the sprayed foam 15mL / g or more, it is preferable to use a spray container equipped with a pressure-accumulating sprayer as the trigger-type spray container. As a spray container equipped with a pressure-accumulating sprayer, the spray container 1 described above can be used, but is not limited thereto, and various known spray containers can be used. For example, those described in JP-A-9-122547, JP-A-9-308843, and JP-A-10-174911 can be used. Among known pressure-accumulating sprayers, those that spray liquid materials in a mist form are used by replacing the nozzle part with a nozzle part capable of discharging foam. As a nozzle part capable of discharging foam, the nozzle part 11 of the spray container 1 described above, the one described in FIG. 1 of JP-A-2004-290943, the one described in FIG. 2 of JP-A-2007-167719, and the like can also be used. In addition, from the viewpoint of improving operability for a wide range of cleaning objects, a spray container equipped with a pressure-accumulation type sprayer is preferably one that can continuously spray (continue to spray liquid without interruption) the liquid detergent composition contained in the container not only when the trigger is pulled. A pressure-accumulation type sprayer capable of continuous spray is a sprayer that can spray the liquid detergent composition continuously (independently in time) in response to the operation of the trigger when the trigger is repeatedly pulled. As such a pressure-accumulation type sprayer capable of continuous spray, those described in FIG. 1 of JP-A-2014-166624 and FIG. 1 of JP-A-2017-213497 and the like can be used.

[0021] A pressure-accumulation type spray container 16 capable of continuous spraying according to an embodiment of the present invention is shown in Fig. 3. In the explanation of the spray container 16, the same components as those in the spray container 1 shown in Fig. 1 are given the same reference numerals, and detailed explanations will be omitted. As shown in FIG. 3, a pressure-accumulation type spray container 16 capable of continuous spraying has a configuration in which a trigger-type sprayer 17 for continuously spraying the liquid material is attached to the mouth of a container body 2. The sprayer 17 includes a trigger 4, a main cylinder 18 which is pressurized in response to the pulling action of the trigger 4, a vertical supply tube section 19 to which the liquid in the main cylinder 18 is supplied, an injection tube section 21 provided between the vertical supply tube section 19 and an injection hole 20, and a storage cylinder 23 in which the liquid flowing through the injection tube section 21 can be stored through a supply hole 22. The injection hole 20 is provided with a foaming nozzle 24. An air introduction hole (not shown) is formed in the side wall of the foaming nozzle 24, and outside air taken in through this air introduction hole flows into the foaming nozzle 24 as air that foams the cleaning agent to be sprayed from the foaming nozzle 24. The main cylinder 18 is provided with a main piston 18a that can move back and forth in response to the operation of the trigger 4 to apply pressure inside the main cylinder. Storage cylinder 23 includes storage plunger 23a that is movable parallel to the axial direction of injection hole 20, and biasing means 23b that biases storage plunger 23a in the injection direction of liquid from injection hole 20. In addition, storage cylinder 23 is formed with communication hole 23c, and liquid stored in storage cylinder 23 can move to injection tube portion 21 through communication hole 23c.

[0022] When the trigger 4 of the sprayer 17 is pulled backward, the main piston 18a moves forward and backward in the main cylinder 18, pressurizing the main cylinder 18, and the liquid in the main cylinder 18 is supplied to the vertical supply cylinder 19 through the communication cylinder 25. This liquid is sprayed from the injection hole 20 through the injection 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 toward one side in the axial direction. In this way, every time the trigger 4 is pulled, the liquid is sprayed from the injection hole 20, and the storage plunger 23a moves toward one side in the axial direction to store (fill) the liquid in the storage cylinder 23. When the operation of pulling the trigger 4 is stopped, the supply of liquid into the vertical supply tube portion 19 stops, but the biasing force acting on the storage plunger 23a causes the storage plunger 23a to start moving back toward the other side in the axial direction. This causes the liquid filled in the storage cylinder 23 to be pushed out from inside the storage cylinder 23 through the communication hole 23b and the injection tube portion 21 toward the ejection hole 20, so that the liquid can be continuously ejected from the ejection hole 20. Therefore, the liquid can be ejected not only when the trigger 4 is pulled backward, but also when the trigger 4 is not operated, and thus the liquid can be continuously ejected. 4, in the case where the continuous-ejection pressure-accumulation spray container 26 is one that sprays a liquid material in mist form, a foaming cylinder 28 having an air intake hole 28a is provided in the nozzle portion 27, so that the mist collides with the foaming cylinder 28 and air is taken in to create foam. In this way, the continuous-ejection pressure-accumulation spray container 26 can be provided with the foaming cylinder 28 at the open end of the liquid ejection hole 20 in the container 26. The foaming cylinder 28 is provided integrally with the open end of the ejection hole 20 or is detachably provided.

[0023] The liquid detergent composition used in the cleaning article of the present invention is not particularly limited as long as it can spray a foam having a specific foam volume of 15 mL / g or more in combination with a spray container, but from the viewpoint of forming a foam having a specific foam volume of 15 mL / g or more or a more preferable specific foam volume as described above, and / or from the viewpoint of increasing the cleaning power of the liquid detergent composition itself against oily stains, it is preferable to use the following liquid detergent composition. The following liquid detergent compositions have high cleaning power against oily stains regardless of whether the specific foam volume is 15 mL / g or more, but by setting the specific foam volume or the ratio of the specific foam volume to a specific range, the cleaning effect on the surface to be cleaned, and further on hard surfaces, is further improved.

[0024] The reason why the cleaning article of the present invention can simply and efficiently clean the surface to be cleaned and has a satisfactory cleaning effect is not entirely clear, but is presumed to be as follows. It is believed that the liquid detergent composition contained in the container of the cleaning article of the present invention contains a combination of a specific surfactant such as component (a) and a water-soluble solvent such as component (d), which maintains the advantage of a pressure-accumulation trigger that exhibits good foaming properties under a certain pressure state, while also making it less susceptible to the effects of the specific foam volume of the foam formed due to differences in pressure application speed by using a hydrophilic polymer such as component (c) in combination. Specifically, it may be related to the foaming (fast foaming) that occurs when gas and liquid are mixed in an extremely short time. The liquid detergent composition and method for cleaning a surface to be cleaned of the present invention are not limited to the above-mentioned mechanism of action.

[0025] The liquid detergent composition used in the cleaning article 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 specific foam volume, the liquid detergent composition preferably contains an amphoteric surfactant. The amphoteric surfactant may be one or more amphoteric surfactants selected from amine oxide type amphoteric surfactants and betaine type amphoteric surfactants, and further, one or more amphoteric surfactants selected from amine oxide, sulfobetaine, and carboxybetaine. From the viewpoint of enhancing detergency, it is preferable that the surfactant contains a nonionic surfactant. From the viewpoint of adjusting the specific foam volume, the surfactant preferably includes an anionic surfactant, and more preferably the anionic surfactant is an anionic surfactant having a branched chain hydrocarbon group. From the viewpoint of achieving a good specific foam volume without being affected by the trigger pulling speed, the liquid detergent composition of the present invention preferably contains one or more compounds selected from amine oxide, sulfobetaine, carboxybetaine, alkyl (poly)glucoside, and alkyl (poly)glyceryl ether. In order to achieve a good specific foam volume without being affected by the trigger pulling speed, the liquid detergent composition of the present invention preferably contains a specific water-soluble solvent, which will be described in detail below as component (d). Examples of the water-soluble solvent include one or more selected from alcohols having 3 to 10 carbon atoms and glycol-based solvents having 2 to 14 carbon atoms. In addition, the liquid detergent composition used in the present invention may contain one or more components selected from the components (a) to (h) related to the liquid detergent composition for hard surfaces described below, and the blending amount of each component may also be the blending amount of each component described below.

[0026] The liquid detergent composition used in the present invention may be a liquid detergent composition containing the following components (a) and (d): The liquid detergent composition used in the present invention may be a liquid detergent composition containing the following components (a), (c) and (d).

[0027] As the liquid detergent composition used in the cleaning article of the present invention, it is preferable to use the "liquid detergent composition for hard surfaces" shown below. The liquid detergent composition for hard surfaces has excellent cleaning power, particularly against oily stains.

[0028] <Liquid cleaning composition for hard surfaces> The liquid cleaning 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.

[0029] <Component (a)> The component (a) is an amphoteric surfactant. From the viewpoint of achieving a good foam specific volume without being affected by the trigger pulling speed, the amphoteric surfactant is preferably one or more amphoteric surfactants selected from amine oxide type amphoteric surfactants and betaine type amphoteric surfactants, more preferably one or more amphoteric surfactants selected from amine oxide, sulfobetaine and carboxybetaine, and even more preferably one or more amphoteric surfactants selected from amine oxide and carboxybetaine.

[0030] As the amine oxide, a compound represented by the following general formula (a1) (hereinafter referred to as component (a1)) is preferable.

[0031] [ka]

[0032] [In the formula, R 1a represents a hydrocarbon group having 6 to 22 carbon atoms, preferably an alkyl or alkenyl group, more preferably an alkyl group; R 2a and R 3a each independently represents an alkyl group having 1 to 3 carbon atoms; D represents an -NHC(=O)- group or a -C(=O)NH- group; 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.

[0033] In the above general formula (a1), when q=1 and p=1, R 1a From the viewpoint of detergency and foaming property, preferably represents a hydrocarbon group having 7 or more carbon atoms, more preferably 9 or more carbon atoms, and preferably 21 or less, more preferably 17 or less, and even more preferably 15 or less carbon atoms, preferably an alkyl or alkenyl group, more preferably an alkyl group. Also, when q=0 and p=0, R 1a From the viewpoint of detergency, preferably represents a hydrocarbon group having 8 or more carbon atoms, more preferably 10 or more carbon atoms, and 22 or less, preferably 18 or less, more preferably 16 or less carbon atoms, preferably an alkyl or alkenyl group, more preferably an alkyl group. In the present invention, it is preferable that q=0 and p=0. 2a and R 3a From the viewpoint of detergency, is preferably a methyl group having one carbon atom.

[0034] Preferred specific examples of the component (a1) include: (1) Alkyl (carbon number 6 to 22) dialkyl (carbon number 1 to 3) amine oxides: capryl dimethylamine oxide, capric dimethylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, palmityl dimethylamine oxide, stearyl dimethylamine oxide, etc. (2) Amide group-containing amine oxides (compounds in which q=1 and p=1 in the general formula (a1)): caprylic acid amidopropyl dimethylamine oxide, capric acid amidopropyl dimethylamine oxide, lauric acid amidopropyl dimethylamine oxide, myristic acid amidopropyl dimethylamine oxide, palmitic acid amidopropyl dimethylamine oxide, etc. These can be used alone or in combination of two or more. From the viewpoint of reducing the influence of cleaning power and foaming property depending on the trigger pulling speed, (1) alkyl (having 6 to 22 carbon atoms) dialkyl (having 1 to 3 carbon atoms) amine oxides are more preferred.

[0035] The betaine-type amphoteric surfactant is preferably a compound represented by the following general formula (a2).

[0036] [ka]

[0037] [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 the number 0 or 1. 6a , R 7aare each independently an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms; R 8a is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group. B is -SO3 - , -OSO3 - , -COO - is a group selected from the following:

[0038] In the general formula (a2), R 4a From the viewpoint of low substrate damage, represents an alkyl or alkenyl group, preferably an alkyl group, having 7 or more, preferably 8 or more, more preferably 10 or more carbon atoms and 18 or less, preferably 16 or less, more preferably 14 or less carbon atoms. From the viewpoint of low damage to the substrate, A is preferably -COO- or -CONH-, and more preferably -CONH-. R 5a The number of carbon atoms is preferably 2 or 3. R 6a , R 7a is preferably a methyl group. From the viewpoint of low substrate damage, B is preferably -SO3 - Or -COO - and more preferably -COO - It is. r is B is -SO3 - When B is -COO, it is preferably 0. - When , it is preferably 1. R 8a The number of carbon atoms is -SO3 - When B is -COO, it is preferably 3. - When , it is preferably 1.

[0039] Specific examples of the betaine-type amphoteric surfactant include one or more selected from alkyl carboxy betaines, alkyl amido carboxy betaines, alkyl sulfo betaines, alkyl amido hydroxy sulfo betaines, and alkyl amino fatty acid salts. From the viewpoint of low substrate damage, preferred are one or more selected from alkyl amido propyl-N,N-dimethyl carboxy betaines, alkyl-N,N-dimethyl acetate betaines, N-alkyl-N,N-dimethyl-N-sulfopropyl ammonium sulfo betaines, alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl) ammonium sulfo betaines, alkanoyl amino propyl-N,N-dimethyl-N-sulfopropyl ammonium sulfo betaines, N-alkanoyl amino propyl-N,N-dimethyl-N-(2-hydroxysulfopropyl) ammonium sulfo betaines, and N-alkyl-N,N-dimethyl-N-carboxy methyl ammonium betaines, and more preferred are one or more selected from alkyl amido propyl-N,N-dimethyl carboxy betaines and alkyl-N,N-dimethyl acetate betaines. These alkyl groups have 7 or more carbon atoms, preferably 8 or more, more preferably 10 or more carbon atoms, and 18 or less, preferably 16 or less, more preferably 14 or less carbon atoms.

[0040] <(b) Component> The component (b) is a disinfectant. The component (b) is preferably at least one selected from a cationic surfactant, ethanol, and an aromatic alcohol. Examples of the cationic surfactant include a quaternary ammonium salt type surfactant.

[0041] The quaternary ammonium salt surfactant of 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).

[0042] [ka]

[0043] [In the formula, R 1b and R2b at least one selected from the group consisting of an alkyl group, an alkenyl group, or a hydroxyalkyl group having 8 to 18 carbon atoms, and the remainder each consisting of an alkyl group, a hydroxyalkyl group, or a polyoxyethylene group having 1 to 3 carbon atoms, or an average addition mole number of 10 or less; R 3b and R 4b are the same or different and each represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group having an average addition mole number of 10 or less, and X - is an anion.

[0044] [ka]

[0045] [In the formula, R 5b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, R 6b and R 7b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms; X - is an anion.

[0046] In the general formula (b1), when the quaternary ammonium salt is a mono-long chain alkyl type, R 1b is an alkyl group, an alkenyl group, or a hydroxyalkyl group having 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and even more preferably 14 or more, and 18 or less, preferably 16 or less; R 2b , R 3b and R 4b are the same or different and each is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group with an average added mole number of 10 or less. In the general formula (b1), when the quaternary ammonium salt is a di-long chain alkyl type, R 1b and R 2b are the same or different and each is an alkyl group, an alkenyl group, or a hydroxyalkyl group having 8 or more carbon atoms and 16 or less, preferably 14 or less,3b and R 4b are the same or different and each is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group with an average added mole number of 10 or less.

[0047] In the general formula (b1), X - is an anion. Examples of anions include halogen ions, such as chloride, bromide, and iodide. - Examples of the anion include alkyl sulfate ions having 1 to 3 carbon atoms, such as methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion.

[0048] Preferred examples of the compound of general formula (b1) include one or more selected from N-alkyl-N,N,N-trimethylammonium salts in which the alkyl group has 12 or more and 18 or less carbon atoms, N,N-dialkyl-N,N-dimethyl-ammonium salts in which the alkyl group has 8 or more and 14 or less carbon atoms, and N-alkyl-N,N-dimethyl-N-ethylammonium salts in which the alkyl group has 12 or more and 16 or less carbon atoms.

[0049] In general formula (b2), R 5b R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms. 5b From the viewpoint of detergency, the number of carbon atoms in R is preferably 8 or more, and preferably 18 or less, more preferably 16 or less. 5b is preferably an alkyl group or an alkenyl group, and is preferably an alkyl group.

[0050] In general formula (b2), R 6b and R 7b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms. 6b and R 7bare preferably each independently selected from alkyl groups 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.

[0051] In the general formula (b2), X - is an anion. Examples of anions include halogen ions, such as chloride, bromide, and iodide. - Examples of the anion include alkyl sulfate ions having 1 to 3 carbon atoms, such as methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion.

[0052] Specific examples of the compound of general formula (b2) include N-dodecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tridecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-dimethyl-N-benzyl ammonium salt, N-pentadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-hexadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-dodecyl-N,N-diethyl-N-benzyl ammonium salt, N-tridecyl-N,N-diethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-diethyl-N-benzyl ammonium salt, and N-hexadecyl-N,N-diethyl-N-benzyl ammonium salt, N-dodecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, N-tridecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, N-tetradecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, N-pentadecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, and N-hexadecyl-N-methyl-N-ethyl-N-benzyl ammonium salt.

[0053] From the viewpoints of bactericidal effect and compounding stability, the aromatic alcohol of the component (b) is preferably a compound represented by the following general formula (b3). R 8b O-(R 9b O) l -H (b3) [In the formula, R 8b is a hydrocarbon group having an aromatic group and a total carbon number of 6 to 10, l is an integer of 0 to 1, R 9b is an alkylene group having 2 to 4 carbon atoms, provided that the molecular weight of the compound is 106 to 250.

[0054] R 8b The total number of carbon atoms in R is the number of carbon atoms including the aromatic group. 8b From the viewpoint of bactericidal effect, the total number of carbon atoms is 6 or more, and from the viewpoint of blend stability, the total number of carbon atoms is 10 or less, preferably 9 or less, and more preferably 8 or less. 8b is an aromatic hydrocarbon group, and examples thereof include a phenyl group, a benzyl group, and a phenethyl group. In general formula (b3), 1 is preferably 1 or less, and more preferably 0, from the viewpoint of the bactericidal effect.

[0055] Specifically, from the viewpoint of bactericidal effect and compounding stability, the (b) component 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), and propylene glycol monophenyl ether (molecular weight: 152). The (b) component is preferably one or more selected from benzyl alcohol and phenoxyethanol. The (b) component 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 (b) component.

[0056] <(c) component> The component (c) is a hydrophilic polymer. The component (c) may be a polymer compound that dissolves at least 0.1 g in 100 g of water at 25° C. and has a weight average molecular weight of 10,000 or more. The inclusion of the component (c) in the liquid cleaning composition for hard surfaces of the present invention can contribute to the control of the specific foam volume of the foam formed by changing the pressurization speed.

[0057] Examples of component (c) include synthetic polymers selected from polymers having one or more groups selected from an amino group, a quaternary ammonium group, and a betaine group, polyvinyl alcohol and its derivatives, and natural polymers such as hydroxyethyl cellulose and their derivatives.

[0058] 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.

[0059] The component (c) is preferably a polymer containing a structural unit A derived from one or more monomers A selected from a monomer (c1) represented by the following general formula (c1) and a monomer (c2) represented by the following general formula (c2):

[0060] [ka]

[0061] [In the formula, R 1c , R 2c , R 3c , R 7c , R 8c , R 9c are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. 1c , Y 1c each independently represents an alkylene group having 1 to 12 carbon atoms, -COOR 12c -,-CONHR 12c -,-OCOR 12c -, -R 13c -OCO-R 12c -, where R 12c , R 13care each independently an alkylene group having 1 to 5 carbon atoms. 4c is an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, or R 1c R 2c C=C(R 3c )-X 1c -It is. 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 which may be substituted with a hydroxy group, a carboxy group, a sulfonic acid group, or a sulfate ester group, or a benzyl group; R 6c When is an alkyl group, a hydroxyalkyl group, or a benzyl group, Z - R indicates an anion. 6c If contains a carboxyl group, a sulfonic acid group, or a sulfate ester group, Z - does not exist, and R 6c These groups in the Z form anions. - Examples of the anion of R include a halogen ion, a sulfate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, an aromatic sulfonate ion which may be substituted with an alkyl group having 1 to 3 carbon atoms, and a hydroxy ion. 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 -It is. 11c is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group.

[0062] Specific preferred examples of the monomer (c1) of general formula (c1) include acryloyl (or methacryloyl) aminoalkyl (carbon number: 1 to 5)-N,N,N-trialkyl (carbon number: 1 to 3) quaternary ammonium salts, acryloyl (or methacryloyl) oxyalkyl (carbon number: 1 to 5)-N,N,N-trialkyl (carbon number: 1 to 3) quaternary ammonium salts, N-(ω-alkenyl (carbon number: 2 to 10))-N,N,N-trialkyl (carbon number: 1 to 3) quaternary ammonium salts, and N,N-di(ω-alkenyl (carbon number: 2 to 10))-N,N-dialkyl (carbon number: 1 to 3) quaternary ammonium salts, and particularly diallyldimethylammonium salt.

[0063] Specific examples of the monomer (c2) of the general formula (c2) that are preferred include acryloyl (or methacryloyl) amino alkyl (carbon number: 1 to 5)-N,N-dialkyl (carbon number: 1 to 3) amines, acryloyl (or methacryloyl) oxy alkyl (carbon number: 1 to 5)-N,N-dialkyl (carbon number: 1 to 3) amines, N-(ω-alkenyl (carbon number: 2 to 10))-N,N-dialkyl (carbon number: 1 to 3) amines, N,N-di(ω-alkenyl (carbon number: 2 to 10))-N-alkyl (carbon number: 1 to 3) amines, allylamine, diallylmethylamine, and diallylamine, and particularly preferred are allylamine, diallylmethylamine, diallylamine, acryloyl (or methacryloyl) amino propyl-N,N-dimethylamine, and acryloyl (or methacryloyl) oxy ethyl-N,N-dimethylamine. When the component (c) contains the structural unit A, the structural unit A derived from the monomer A is contained in an amount of preferably 10 mol % or more, more preferably 20 mol % or more, even more preferably 30 mol % or more, and preferably 100 mol % or less, more preferably 99 mol % or less, even more preferably 90 mol % or less, based on all structural units of the component (c).

[0064] The component (c) is preferably a polymer containing a structural unit B represented by -SO2-. Examples of a method for introducing such a structural unit B into a polymer include a method for blowing a predetermined amount of SO2 gas into a solution containing a monomer (c1) of general formula (c1) and / or a monomer (c2) of general formula (c2), and polymerizing the solution using a polymerization initiator selected from benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, dilauroyl peroxide, azobisisobutyronitrile, azobisisovalernitrile, 2,2'-azobis(2-amidinopropane), t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, persulfates, and hydrogen peroxide. A solvent can 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 can be used. The polymerization temperature varies depending on the combination of the solvent and initiator, and is preferably from -20°C to 200°C, more preferably from -10°C to 100°C. In the present invention, polymerization can also be performed by light or radiation, and polymerization can be efficiently performed by irradiating light with a wavelength of 300 nm to 450 nm.

[0065] By including structural unit B, component (c) exhibits sufficient adhesion to hard surfaces even when the polymer concentration is low, and is also less susceptible to the effects of combined use with a cationic surfactant. When the component (c) contains structural units A and B, in the component (c), the molar ratio of the structural unit B derived from monomer B to the 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, even more preferably 0.05 or more, and preferably 1 or less, more preferably 0.75 or less, even more preferably 0.5 or less, and still more preferably 0.3 or less.

[0066] In the present invention, for the purpose of further improving the antifouling effect, it is preferable that the component (c) contains a structural unit C derived from a monomer selected from the following (i) to (iv):

[0067] (i) Acrylic acid or its salts, methacrylic acid or its salts, maleic acid or its salts, maleic anhydride, styrene sulfonate, 2-acrylamido-2-methylpropane sulfonate, allyl sulfonate, vinyl sulfonate, methallyl sulfonate, sulfopropyl methacrylate, mono-ω-methacryloyloxyalkyl phosphate (having 1 to 12 carbon atoms)

[0068] (ii) An amide group-containing compound selected from acrylamide, N,N-dimethylaminopropylacrylic (or methacrylic) amide, N,N-dimethylacrylic (or methacrylic) amide, N,N-dimethylaminoethylacrylic (or methacrylic) amide, N,N-dimethylaminomethylacrylic (or methacrylic) amide, N-vinyl-2-caprolactam, and N-vinyl-2-pyrrolidone.

[0069] (iii) An ester group-containing compound selected from alkyl acrylate (or methacrylate) (having 1 to 5 carbon atoms), 2-hydroxyethyl acrylate (or methacrylate), N,N-dimethylaminoalkyl acrylate (or methacrylate) (having 1 to 5 carbon atoms), and vinyl acetate.

[0070] (iv) Olefin compounds selected from ethylene, propylene, n-butylene, isobutylene, 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, and α-methylstyrene.

[0071] Among these, in particular from the viewpoint of the antifouling effect, the constituent units derived from the monomers (i) or (ii) are preferred, among which the constituent units derived from the monomers (i) are most preferred, and among these, acrylic acid or its sodium salt or potassium salt, methacrylic acid or its sodium salt or potassium salt, and maleic acid or its sodium salt or potassium salt are preferred. Here, the counter ion of the constituent unit derived from the monomer (i) may be the cationic group portion of the polymer contained therein.

[0072] When component (c) contains structural unit C, in 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, from the viewpoint of the antifouling effect, preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.2 or more, and preferably 1.0 or less, more preferably 0.75 or less, even more preferably 0.5 or less.

[0073] In the component (c), the structural unit A, the structural unit B, and preferably the structural unit C may be present in either the main chain or the side chain of the polymer. These may be randomly polymerized, block polymerized, graft polymerized, or the like. In the present invention, it is preferable to use a polymer composed only of the structural unit A, the structural unit B, and the structural unit C.

[0074] Furthermore, the component (c) may be a natural polymer such as a polysaccharide or a cellulose derivative, or a derivative thereof. Examples of polysaccharides include karaya gum, tragacanth gum, gum arabic, acemannan, konjac mannan, acacia gum, ghatti gum, guar gum, locust bean gum, carrageenan, xanthan gum, gellan gum, pullulan, dextran, casein, gelatin, keratin, glutelin, glucagon, gluten, zein, and shellac. Among these, polysaccharides selected from xanthan gum, guar gum, and gellan gum are preferred from the viewpoint of reducing the effect of the trigger pulling speed on foamability.

[0075] Examples of cellulose derivatives include hydroxypropylmethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, methylcellulose, hydroxypropylcellulose, ethylcellulose, carboxymethylcellulose, cellulose acetate phthalate, nitrocellulose, and other cellulose ethers / esters. Among these, from the viewpoint of reducing the effect of the trigger pulling speed on foaming properties, cellulose derivatives selected from hydroxypropylmethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, methylcellulose, hydroxypropylcellulose, ethylcellulose, and carboxymethylcellulose are preferred.

[0076] From the viewpoints of blend stability and easy availability of raw materials, component (c) may be hydroxyethyl cellulose and polyvinyl alcohol. Component (c) can also be produced by reacting a compound having a cationic group with a semi-synthetic water-soluble polymer such as hydroxyethyl cellulose and soluble starch. From the viewpoints of blend stability and easy availability of raw materials, the component (c) is preferably a cationically modified polyvinyl alcohol produced by polymerizing vinyl acetate and the monomer A, or a cationically modified hydroxyethyl cellulose produced by reacting hydroxyethyl cellulose with a compound having a cationic group. An example of this cationic group is the cationic group possessed by the monomer A.

[0077] (cationic modified polyvinyl alcohol) The cation-modified polyvinyl alcohol is a polyvinyl alcohol having in its main chain or side chain a cationic group of the monomer A. The cation-modified polyvinyl alcohol is obtained by copolymerizing the raw material vinyl acetate with diallyldimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride, or the like, and saponifying the resulting copolymer by a conventional method when polymerizing the raw material vinyl acetate. Alternatively, vinyl acetate may be copolymerized with another monomer having a reactive group, and after saponification, the reactive group may be used to react with a compound containing the cationic group to cationize the polyvinyl alcohol.

[0078] (cationically modified hydroxyethyl cellulose) Cationically modified hydroxyethyl cellulose can be obtained, for example, by reacting raw cellulose with ethylene oxide to obtain hydroxyethyl cellulose, and then reacting this hydroxyethyl cellulose with a cationizing agent to cationize it.

[0079] The cellulose that can be used as the raw material cellulose includes, in addition to chemically pure cellulose, various cellulose-containing raw materials, such as woods such as various wood chips; pulps such as wood pulp produced from wood; papers such as newspapers and cardboard; plant stems and leaves such as rice straw and corn stalks; and plant shells such as rice husks, palm shells, and coconut shells.

[0080] As the cationizing agent, from the viewpoint of availability, preferred are chlorides or bromides of glycidyl trimethylammonium or glycidyl triethylammonium, chlorides such as 3-chloro-2-hydroxypropyl trimethylammonium and 3-chloro-2-hydroxypropyl triethylammonium, bromides such as 3-bromo-2-hydroxypropyl trimethylammonium and 3-bromo-2-hydroxypropyl triethylammonium, more preferred are glycidyl trimethylammonium chloride or 3-chloro-2-hydroxypropyl trimethylammonium chloride, and even more preferred is 3-chloro-2-hydroxypropyl trimethylammonium chloride. These cationizing agents may be used alone or in combination of two or more.

[0081] From the viewpoint of improving compatibility with surfactants (blend stability), the degree of cationization of component (c) is preferably 0.25 mol% or more, more preferably 0.35 mol% or more, even more preferably 0.45 mol% or more, still more preferably 0.6 mol% or more, still more preferably 0.8 mol% or more, and is preferably 5 mol% or less, more preferably 4 mol% or less, still more preferably 3 mol% or less, and still more preferably 2 mol% or less. The degree of cationization can be determined by colloid titration using potassium polyvinyl sulfate (PVSK).

[0082] The component (c) may contain a constituent unit derived from a monomer having a betaine group. Examples of the monomer having a betaine structure include N-(3-sulfopropyl)-N-(meth)acryloyloxyethyl-N,N-dimethylammonium betaine, N-(3-sulfopropyl)-N-(meth)acryloylamidopropyl-N,N-dimethylammonium betaine, N-(3-carboxymethyl)-N-(meth)acryloylamidopropyl-N,N-dimethylammonium betaine, and N-carboxymethyl-N-(meth)acryloyloxyethyl-N,N-dimethylammonium betaine.

[0083] The component (c) is preferably a polymer having a structural unit D represented by the following general formula (c3), and more preferably a copolymer containing a structural unit D represented by the following general formula (c3) and a structural unit E represented by the following general formula (c4).

[0084] [ka]

[0085] [During the ceremony, R 14c ~R 16c are the same or different, 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 -OPO3 --Y 3c - Y 2c , Y 3c : the same or different, an alkylene group having 1 to 4 carbon atoms R 18c , R 19c : the same or different, a hydrocarbon group having 1 to 4 carbon atoms X 2c :O or NR 20c and R 20c is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X 3c : Hydrogen atom, hydrocarbon group having 1 to 4 carbon atoms, R 21c SO3 - , or R 21c COO - Here, R 17c When is an alkylene group having 1 to 4 carbon atoms, X 3c is R 21c SO3 - , or R 21c COO - , R 21c is an alkylene group having 1 to 4 carbon atoms, R 17c Ga-Y 2c -OPO3 - -Y 3c -, X 3c is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

[0086] [ka]

[0087] [During the ceremony, R 22c ~R 24c are the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms X 4c : O or NH group R 25c : an alkylene group having 1 to 4 carbon atoms X 5c :N + R 26c R 27c R 28c X 6cor NR 29c R 30c and R 26c ~R 30c are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; X 6c is an anion Indicates the following.

[0088] [Structural unit D] In the general formula (c3), from the viewpoint of availability of the unsaturated monomer, polymerization property of the monomer, and enhancement of the antifouling performance of the component (c), R 14c and R 15c are each preferably a hydrogen atom. In general formula (c3), R 16c From the viewpoints of availability of the unsaturated monomer, polymerizability of the monomer, and enhancing the antifouling performance of the component (c), is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. In the general formula (c3), X 2c is preferably O from the viewpoints of availability of the unsaturated monomer, polymerizability of the monomer, and enhancing the antifouling performance of the component (c). In general formula (c3), R 17c From the viewpoint of enhancing antifouling performance, is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and still more preferably an alkylene group having 2 carbon atoms. In the general formula (c3), Y 2c , 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 general formula (c3), R 18c , R 19c From the viewpoints of availability of the unsaturated monomer, polymerizability of the monomer, and enhancing the antifouling performance of component (c), each of the groups is preferably a methyl group or an ethyl group, and more preferably a methyl group. In the general formula (c3), X 3c is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R 21c SO3 - , or R 21c COO - However, R 17cWhen is an alkylene group having 1 to 4 carbon atoms, X 3c is R 21c SO3 - , or R 21c COO - and R 17c Ga-Y 2c -OPO3 - -Y 3c -, X 3c R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. 17c Ga-Y 2c -OPO3 - -Y 3c - In order to improve the antifouling performance, X 3c R is preferably a hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group. 17c When is an alkylene group having 1 to 4 carbon atoms, from the same viewpoint, X 3c is R 21c SO3 - is preferred. Also, 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.

[0089] When component (c) contains structural unit D, in component (c), the structural unit D, relative to all structural units of component (c), is preferably 30 mol % or more, more preferably 50 mol % or more, even more preferably 70 mol % or more, still more preferably 80 mol % or more, and even more preferably 90 mol % or more, from the viewpoint of enhancing the antifouling performance of component (c), and from the same viewpoint, is preferably 99 mol % or less, more preferably 98 mol % or less, and even more preferably 95 mol % or less. Furthermore, when component (c) contains structural unit D, the content of structural unit D in component (c) is, from the viewpoint of enhancing the antifouling performance of component (c), preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, and even more preferably 90% by mass or more, and from the same viewpoint, is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 95% by mass or less.

[0090] [Structural unit E] In the general formula (c4), from the viewpoint of availability of the unsaturated monomer, polymerization property of the monomer, and enhancement of the antifouling performance of the component (c), R 22c and R 23c are each preferably a hydrogen atom. In general formula (c4), R 24c From the viewpoint of the polymerizability of the monomer and of enhancing the antifouling performance of the component (c), is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. In the general formula (c4), X 4c is preferably O from the viewpoint of the polymerizability of the monomer and from the viewpoint of enhancing the antifouling performance of the component (c). In general formula (c4), R 25c From the viewpoint of the polymerizability of the monomer and of enhancing the antifouling performance of the component (c), is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms. In the general formula (c4), X 5c From the viewpoint of enhancing the antifouling performance of the (c) component and from the viewpoint of easiness of the quaternization reaction, + R 26c R 27c R 28c X 6c or NR 29c R 30c and N + R 26c R 27c R 28c X 6c is preferred, R 26c , R 27c , R 28c From the same viewpoint, each of is preferably a methyl group or an ethyl group. In general formula (c4), R 29c , R 30c From the viewpoint of enhancing the antifouling performance of the component (c) and of the ease of the quaternization reaction, is preferably a methyl group or an ethyl group, and more preferably a methyl group. In the general formula (c4), X 6c is an anion, a halogen ion or C2H5SO4 - is preferred, C2H5SO4 - is more preferred.

[0091] When component (c) contains the structural unit E, the structural unit E in component (c), relative to all structural units of component (c), is preferably 1 mol % or more, more preferably 2 mol % or more, and even more preferably 5 mol % or more, from the viewpoint of enhancing the antifouling performance, and from the same viewpoint, is preferably 70 mol % or less, more preferably 50 mol % or less, even more preferably 30 mol % or less, still more preferably 20 mol % or less, and even more preferably 10 mol % or less.

[0092] Furthermore, when the component (c) contains the structural unit E, the content of the structural unit E in the component (c) is, from the viewpoint of enhancing the antifouling performance, preferably 1 mass% or more, more preferably 2 mass% or more, and even more preferably 5 mass% or more, and from the viewpoint of enhancing the antifouling performance of the component (c), preferably 70 mass% or less, more preferably 50 mass% or less, even more preferably 30 mass% or less, still more preferably 20 mass% or less, and even more preferably 10 mass% or less.

[0093] [Molar ratio of structural unit D to structural unit E] When component (c) contains structural units D and E, the molar ratio of structural units D to E in component (c), structural unit D / structural unit E, is, from the viewpoint of antifouling performance, preferably 30 / 70 or more, more preferably 50 / 50 or more, even more preferably 55 / 45 or more, even more preferably 60 / 40 or more, still more preferably 75 / 25 or more, and even more preferably 90 / 10 or more; and, from the viewpoint of enhancing the antifouling performance of component (c), it is preferably 99.9 / 0.1 or less, more preferably 98 / 2 or less, and even more preferably 96 / 4 or less.

[0094] [Constituent units other than constituent units D and E] The component (c) may contain a structural unit other than the structural unit D and the structural unit E, provided that the effects of the present invention are not impaired. As the structural unit other than the structural unit D and the structural unit E, a structural unit derived from an unsaturated monomer other than an unsaturated monomer having a sulfobetaine group is preferred, and a structural unit derived from a hydrophobic unsaturated monomer such as styrene is more preferred.

[0095] From the viewpoint of antifouling properties, the amount of structural units other than the structural units D and E in the component (c) is preferably 10 mol % or less, more preferably 5 mol % or less, even more preferably 1 mol % or less, still more preferably 0.5 mol % or less, and even more preferably 0.1 mol % or less, based on all structural units in the component (c). The amount of structural units other than the structural units D and E in the component (c) may be 0 mol % based on all structural units in the component (c). From the viewpoint of antifouling properties, the content of structural units other than the structural units D and E in the component (c) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less. The content of structural units other than the structural units D and E in the component (c) may be 0% by mass.

[0096] When the component (c) contains the structural unit D and the structural unit E, the total of the structural units D and E in the component (c) is, from the viewpoint of antifouling properties, preferably 90 mol % or more, more preferably 95 mol % or more, even more preferably 99 mol % or more, still more preferably 99.5 mol % or more, and even more preferably 99.9 mol % or more, based on all the structural units of the component (c). The total of the structural units D and the structural units E in the component (a) may be 100 mol % based on all the structural units of the component (c). From the viewpoint of antifouling properties, the total content of the structural units D and E in the component (c) is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, still more preferably 99.5% by mass or more, and even more preferably 99.9% by mass or more. The total content of the structural units D and E in the component (c) may be 100% by mass.

[0097] The component (c) having a betaine group may be produced by any method, specifically, the following methods (i) and (ii) are mentioned. From the viewpoint of availability of raw materials and ease of production, method (ii) is preferred. (i) A method of copolymerizing an unsaturated monomer having a betaine group and a cationic group (ii) A method in which an unsaturated monomer having an amino group and a cationic group is copolymerized, followed by quaternization with a betaining agent.

[0098] In component (c), from the viewpoints of foamability and soil resistance, the total amount of structural units derived from monomers having a group selected from an amino group, a quaternary ammonium group, and a betaine group, relative to all structural units, is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 50 mol% or more, and preferably 100 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less.

[0099] The weight average molecular weight of component (c) is, from the viewpoint of reducing the effect of the trigger pulling speed on foaming property, preferably 10,000 or more, more preferably 30,000 or more, even more preferably 50,000 or more, and still more preferably 100,000 or more, and from the same viewpoints as above, is preferably 5,000,000 or less, more preferably 3,000,000 or less, and even more preferably 2,000,000 or less. The weight average molecular weight of component (c) refers to a value determined by gel permeation chromatography (GPC). In this GPC method, pullulan can be used as a molecular weight standard. The same applies to the weight average molecular weight of component (c) below.

[0100] *GPC conditions Equipment: GPC (gel permeation chromatography) manufactured by Tosoh Corporation Column: TSKgel α-M (two columns connected in series) manufactured by Tosoh Corporation Eluent: 0.15molNa2SO4 / 1%CH3COOH / water Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2mg / mL Standard material: Pullulan standard product

[0101] When the pressure-accumulation type trigger spray container of the present invention is a pressure-accumulation type trigger spray container as shown in FIG. 1, from the viewpoint of achieving the formation of a foam with a good foam specific volume without being affected by the speed at which the trigger is pulled, and particularly suppressing a decrease in foaming ability when the trigger is pulled quickly, component (c) is preferably one or more selected from cellulose derivatives, polysaccharides and polyvinyl alcohol, more preferably one or more selected from hydroxyethyl cellulose, xanthan gum and polyvinyl alcohol, even more 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, even more preferably 50,000 or more, still more preferably 100,000 or more, even more preferably 200,000 or more, particularly preferably 300,000 or more, and preferably 5,000,000 or less, more preferably 3,000,000 or less, and even more preferably 2,000,000 or less.

[0102] When the pressure-accumulation type trigger spray container of the present invention is a pressure-accumulation type trigger spray container capable of continuously spraying liquid as shown in Figure 3, from the viewpoints of achieving the formation of a foam with a good specific foam volume without being affected by the speed at which the trigger is pulled and imparting anti-fouling properties, component (c) is preferably one or more selected from polymers containing one or more of 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, cation-modified hydroxylethyl cellulose, xanthan gum, polyvinyl alcohol, and cation-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, even more preferably 50,000 or more, still more preferably 100,000 or more, even more preferably 200,000 or more, particularly preferably 300,000 or more, and preferably 5,000,000 or less, more preferably 3,000,000 or less, and even more preferably 2,000,000 or less.

[0103] <(d) component> The liquid cleaning 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 glycol compounds having 2 to 14 carbon atoms (excluding those corresponding to component (b)) (hereinafter referred to as component (d)) from the viewpoint of improving foaming properties when sprayed. 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 glycol-based 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. Specific examples of the water-soluble organic solvents include isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, dipropylene glycol monobutyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, phenoxytriglycol, butyl diglycol (diethylene glycol monobutyl ether), and dibutylene glycol. Among these, one or more water-soluble organic solvents selected from phenoxytriglycol, butyl diglycol, propylene glycol, propylene glycol monomethyl ether, and dipropylene glycol monobutyl ether are more preferred, and one or more water-soluble organic solvents selected from butyl diglycol and dipropylene glycol monobutyl ether are particularly preferred. In addition, when the pressure-accumulation type trigger spray container of the present invention is a pressure-accumulation type trigger spray container capable of continuously spraying liquid as shown in Figure 3, by using component (d) and one or more water-soluble organic solvents selected from butyl diglycol, propylene glycol monomethyl ether, and dipropylene glycol monobutyl ether, the effect of foaming property due to the speed at which the trigger is pulled can be reduced even without containing component (c). Here, "water-soluble" 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. The method for measuring the partition coefficient between 1-octanol and water shall be in accordance with OECD Test Guideline (OECD Council Decision "C(81)30 Final Annex 1") 107.

[0104] <Composition, other ingredients, etc.> From the viewpoint of cleaning power and foaming property, the liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention contain component (a) in an amount of preferably 0.1 mass % or more, more preferably 0.3 mass % or more, even more preferably 0.5 mass % or more, still more preferably 0.8 mass % or more, and preferably 10 mass % or less, more preferably 8 mass % or less, and even more preferably 5 mass % or less.

[0105] The liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention contain the component (b) in an amount of preferably 0.005% by mass or more, more preferably 0.01% by mass or more, even more preferably 1% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2.5% by mass or less, and even more preferably 2% by mass or less, from the viewpoint of bactericidal properties. The component (b) may impair the foaming property improving effect of the component (d) depending on its type and content, so caution is required when it is contained. Note that, when bactericidal properties are not required, the component (b) is not substantially blended, that is, the liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention may contain 0% by mass of the component (b).

[0106] The liquid detergent composition and liquid detergent composition for hard surfaces of the present invention contain component (c) in an amount of preferably 0.01 mass % or more, more preferably 0.05 mass % or more, even more preferably 0.1 mass % or more, and preferably 1 mass % or less, more preferably 0.5 mass % or less, even more preferably 0.3 mass % or less, from the viewpoint of reducing the effect of the trigger pulling speed on foaming property. In addition, only when the pressure-accumulation type trigger spray container of the present invention is a pressure-accumulation type trigger spray container capable of continuously spraying liquid as shown in Figure 3, the liquid detergent composition and liquid detergent composition for hard surfaces of the present invention do not substantially need to contain component (c). In the present invention, reducing the effect of the trigger pulling speed on foamability means controlling the ratio of the specific foam volume of foam sprayed from the spray container at 0.2 seconds / stroke to the specific foam volume of foam sprayed from the spray container at 0.5 seconds / stroke to be equal to or greater than 0.5 and less than 2.0.

[0107] In the liquid detergent composition and liquid detergent composition for hard surfaces of the present invention, the mass ratio (c) / (a) of the content of component (c) to the content of component (a) is, from the viewpoint of reducing the influence of cleaning power and foaming property due to the trigger pulling speed, 0.005 or more, preferably 0.01 or more, more preferably 0.02 or more, even more preferably 0.03 or more, and from the same viewpoint, is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.1 or less.

[0108] The liquid detergent composition and liquid detergent composition for hard surfaces of the present invention contain component (d) in an amount of preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, from the viewpoint of reducing the effect of the speed at which the trigger is pulled on foaming property.

[0109] In the liquid detergent composition and liquid detergent composition for hard surfaces of the present invention, the mass ratio (d) / (a) of the content of component (d) to the content of component (a) is, from the viewpoint of detergency and reducing the influence of foaming property due to the trigger pulling speed, preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1.0 or more, and from the same viewpoint, is preferably 5.0 or less, more preferably 3.0 or less, even more preferably 2.5 or less, even more preferably 2.0 or less, and particularly preferably 1.8 or less.

[0110] When the pressure-accumulation type trigger spray container of the present invention is a container as shown in FIG. 1, from the viewpoint of reducing the influence of the cleaning power and the foaming property depending on the trigger pulling speed, in the liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention, the mass ratio (c) / (a) of the content of the component (c) to the content of the component (a) is 0.005 or more, preferably 0.01 or more, more preferably 0.02 or more, even more preferably 0.03 or more, and preferably 1 or less, more preferably 0.5 or less, even more preferably 0.1 or less, and 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, even more preferably 1.0 or more, and from the same viewpoint, preferably 5.0 or less, more preferably 3.0 or less, even more preferably 2.5 or less, even more preferably 2.0 or less.

[0111] When the pressure-accumulation type trigger spray container of the present invention is a pressure-accumulation type trigger spray container capable of continuously spraying liquid as shown in FIG. 3, from the viewpoint of reducing the influence of the foaming property depending on the trigger pulling speed, the mass ratio (c) / (a) of the content of component (c) to the content of component (a) in the liquid detergent composition and liquid detergent composition for hard surfaces of the present invention is preferably 0.5 or less, more preferably 0.2 or less, even more preferably 0.05 or less, and particularly preferably 0. And, from the viewpoint of reducing the influence of the foaming property depending on the cleaning power and the trigger pulling speed, 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, even more preferably 1.0 or more, and particularly preferably 1.3 or more, and from the same viewpoint, it is preferably 5.0 or less, more preferably 3.0 or less, even more preferably 2.5 or less, even more preferably 2.0 or less, and particularly preferably 1.8 or less.

[0112] The liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention contain water. Water can be used to make up the remainder other than the components (a), (b), (c), (d) and the optional components described below. The content of water is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and preferably 97% by mass or less, more preferably 95% by mass or less, from the viewpoints of the stability of the liquid detergent composition and the liquid detergent composition for hard surfaces and reducing the influence of the speed of pulling the trigger on the foamability. The water used is preferably ion-exchanged water, sterilized ion-exchanged water, or the like.

[0113] The liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention have a pH at 25°C of preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and preferably 12 or less, more preferably 10 or less, even more preferably 9 or less, even more preferably 8 or less. A pH adjuster can be used to adjust the liquid detergent composition of the present invention and the liquid detergent composition for hard surfaces to the above pH range. As the pH adjuster, acid agents such as inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as citric acid, lactic acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, etc., and sodium hydroxide, potassium hydroxide, ammonia and its derivatives, amine salts such as monoethanolamine, diethanolamine, triethanolamine, etc., and alkali agents such as sodium carbonate, potassium carbonate, etc. may be used alone or in combination. Further, these acid agents and alkali agents may be combined and used as a buffer system. The pH at 25 °C of the liquid detergent composition and the liquid detergent composition for hard surfaces is measured by the following method.

[0114] <pH Measurement Method> Connect a combined electrode for pH measurement (GST-5841C manufactured by Toa DKK) to a pH meter (pH / Ion Meter HM-42X manufactured by Toa DKK) and turn on the power. As the internal solution of the pH electrode, a saturated potassium chloride aqueous solution (3.33 mol / L) is used. Next, fill 100 mL beakers with pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution), respectively, and immerse them in a constant temperature bath at 25 °C for 30 minutes. Immerse the pH measurement electrode in the temperature-adjusted standard solution for 3 minutes, and perform calibration operations in the order of pH 6.86 → pH 4.01 → pH 9.18. Adjust the liquid detergent composition of the present invention or the liquid detergent composition for hard surfaces to be measured to 25 °C, immerse the electrode of the above pH meter in the liquid detergent composition of the present invention or the liquid detergent composition for hard surfaces, and measure the pH after 1 minute.

[0115] <Surfactant> The liquid detergent composition of the present invention and the liquid detergent composition for hard surfaces may contain surfactants other than the component (a) and the component (b) from the viewpoints of improving detergency and foaming properties. The surfactant other than the components (a) and (b) may be one or more surfactants selected from the group consisting of (e) a nonionic surfactant (hereinafter referred to as the component (e)) and (f) anionic surfactant (hereinafter referred to as the component (f)). From the viewpoint of improving detergency, the liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention preferably contain component (e).

[0116] <(e) component> The component (e) is a nonionic surfactant. From the viewpoint of cleaning power and foaming power, the component (e) is preferably at least one selected from the group consisting of (e1) monoalkyl glyceryl ether (hereinafter referred to as the component (e1)), (e2) polyoxyalkylene monoalkyl or alkenyl ether (hereinafter referred to as the component (e2)), (e3) alkyl polyglycoside (glycoside-type nonionic surfactant) (hereinafter referred to as the component (e3)), (e4) sorbitan-based nonionic surfactant (hereinafter referred to as the component (e4)), (e5) aliphatic alkanolamide (hereinafter referred to as the component (e5)), (e6) fatty acid monoglyceride (hereinafter referred to as the component (e6)), and (e7) sucrose fatty acid ester (hereinafter referred to as the component (e7)). Two or more of these may be used. From the viewpoint of improving cleaning power and reducing the effect of foaming property depending on the trigger pulling speed, the component (e) is preferably a nonionic surfactant in which the hydrophilic group has a sugar skeleton or a glycerin skeleton, and examples thereof include one or more types selected from the group consisting of the components (e1), (e3), (e6) and (e7), with one or more types selected from alkyl (poly)glucosides and alkyl (poly)glyceryl ethers being preferred.

[0117] 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) [In the formula, R 1erepresents an alkyl group having 6 to 18 carbon atoms, Gly represents a structural unit derived from glycerin, preferably a residue obtained by removing one hydroxyl group and one hydrogen atom from glycerin, and r represents a number of 1 to 4.

[0118] In general formula (e1), R 1e From the viewpoint of detergency, R is preferably an alkyl group having 6 or more carbon atoms, more preferably 7 or more carbon atoms, even more preferably 8 or more carbon atoms, and preferably 18 or less carbon atoms, more preferably 12 or less carbon atoms, and even more preferably 10 or less carbon atoms. Although linear alkyl groups such as hexyl, heptyl, octyl, nonyl, and decyl groups can be used, in the present invention, from the viewpoint of detergency, branched alkyl groups are preferred. 1e Specific examples of the branched alkyl group include groups selected from the group consisting of 2-ethylhexyl, sec-octyl, isononyl and isodecyl, more preferably 2-ethylhexyl or isodecyl, and particularly preferably 2-ethylhexyl.

[0119] In the general formula (e1), r is preferably 1 or more and preferably 2 or less. Compounds in which r is 1 are more preferred. Particularly preferred compounds are those in which R 1e is a 2-ethylhexyl group and r is 1. The structure represented by Gly is either a structure represented by -CH2CH(OH)CH2- in which the 1st and 3rd hydroxyl groups of glycerin are bonded, or a structure represented by -CH(CH2OH)CH2- in which the 1st and 2nd hydroxyl groups of glycerin are bonded, and varies depending on the catalyst and reaction conditions.

[0120] To obtain the compound of the general formula (e1), for example, R 1eA method of producing the glyceryl ether can be used in which an alkyl alcohol represented by -OH is reacted with an epoxy compound such as epihalohydrin or glycidol using an acid catalyst such as BF3 or an aluminum catalyst. For example, when 2-ethylhexanol is used, the resulting 2-ethylhexyl monoglyceryl ether is a mixture that may contain multiple products, as described in JP-A-2001-49291.

[0121] The (e2) component is a polyoxyalkylene monoalkyl or alkenyl ether. In the nonionic surfactant of component (e2), the number of carbon atoms in the alkyl or alkenyl group is, from the viewpoint of detergency, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and still more preferably 12 or more, and from the same viewpoint, preferably 22 or less, more preferably 18 or less, even more preferably 16 or less, and still more preferably 14 or less.

[0122] In the nonionic surfactant of component (e2), the average number of moles of oxyalkylene groups added is preferably more than 0, more preferably 1 or more, and even more preferably 3 or more, from the viewpoint of detergency, and from the same viewpoint, is preferably 50 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less. In the nonionic surfactant of component (e2), from the viewpoint of detergency, the oxyalkylene group is preferably one or more selected from an oxyethylene group, an oxypropylene group, and an oxybutylene group, and more preferably one or more selected from an oxyethylene group and an oxypropylene group.

[0123] The component (e2) can be one or more compounds selected from the compounds represented by the following general formula (e2). R 2e O[(C2H4O) l / (C3H6O) j ]H(e2) [In the formula, R 2erepresents a hydrocarbon group having 6 to 22 carbon atoms. l and j represent the average number of moles added, l represents a number from 0 to 30, j represents a number from 0 to 30, and l and j cannot be 0 at the same time. " / " represents that the oxyethylene groups and oxypropylene groups may be added randomly or in blocks, regardless of the order.

[0124] R in the above general formula (e2) 2e From the viewpoint of detergency, the number of carbon atoms is preferably 8 or more, more preferably 10 or more, and even more preferably 12 or more, and from the same viewpoint, it is preferably 18 or less, more preferably 16 or less, and even more preferably 14 or less. R 2e From the viewpoint of detergency, R is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and further preferably a secondary alkyl group. Here, the secondary alkyl group is R in the general formula (e2). 2e R that binds to O in O 2e This refers to an alkyl group in which the carbon atom is a secondary carbon atom. Specific examples of the alkyl group include various octyl groups (including 2-ethylhexyl groups), 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. Examples of alkenyl groups include various octanyl groups, various nonanyl groups, various decanyl groups, various undecanyl groups, various dodecanyl groups, various tridecanyl groups, various tetradecanyl groups, various pentadecanyl groups, various hexadecanyl groups, various heptadecanyl groups, and various octadecanyl groups (e.g., oleyl and linoleyl groups). Note that "various" refers to various isomers including n-, sec-, tert-, and iso-.

[0125] In the above general formula (e2), l and j are each independently preferably 1 or more, more preferably 2 or more, from the viewpoint of storage stability, and from the same viewpoint, are each preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less.

[0126] The component (e3) is an alkyl polyglycoside (glycoside-type nonionic surfactant). The nonionic surfactant of the component (e3) is preferably a nonionic surfactant represented by the following general formula (e3). R 3e (OR 4e ) s G t (e3) [In the formula, R 3e represents a linear or branched alkyl group, alkenyl group, or alkylphenyl group having 8 to 18 carbon atoms, preferably 12 to 14 carbon atoms, and more preferably an alkyl group; R 4e represents an alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms, s represents the average number of moles added and is a number of 0 to 5, and t represents a number whose average value is 1 to 5.

[0127] In general formula (e3), R 3e From the viewpoint of detergency, preferably represents a linear or branched alkyl group having 8 or more, preferably 10 or more, and 18 or less, preferably 14 or less, carbon atoms. In general formula (e3), from the viewpoint of storage stability, s is preferably 0 or more and preferably 2 or less, more preferably 0. From the viewpoint of storage stability, t is preferably 1.1 or more and preferably 1.5 or less, more preferably 1.4 or less. Here, t is a value measured by proton NMR method. In the general formula (e3), G may be a residue derived from one or more monosaccharides selected from glucose and fructose in terms of availability and cost. G may also be a residue derived from one or more polysaccharides selected from maltose and sucrose. G is preferably a residue derived from a monosaccharide of glucose.

[0128] (e4) Sorbitan-based nonionic surfactants, (e5) aliphatic alkanolamides, (e6) fatty acid monoglycerides, and (e7) sucrose fatty acid esters preferably have a linear or branched alkyl group having 8 to 18 carbon atoms, more preferably 12 to 14 carbon atoms.

[0129] From the viewpoint of improving detergency, the liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention contain component (e) in an amount of preferably 0.05 mass % or more, more preferably 0.1 mass % or more, even more preferably 0.2 mass % or more, and preferably 5 mass % or less, more preferably 3 mass % or less, even more preferably 2 mass % or less.

[0130] <Component (f)> The component (f) is an anionic surfactant. Examples of the component (f) include an anionic surfactant having a sulfate ester group, a phosphate ester group, a phosphonic acid group, a sulfonic acid group, or a carboxy group. From the viewpoint of detergency, the hydrocarbon group of the anionic surfactant is preferably a straight-chain or branched alkyl group, alkylene group, or aryl group having a carbon number of preferably 5 or more, more preferably 6 or more, even more preferably 7 or more, still more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, and preferably 21 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less.

[0131] The anionic surfactant is preferably one or more anionic surfactants selected from the group consisting of (f1) a sulfosuccinate ester or a salt thereof having a hydrocarbon group having from 5 to 18 carbon atoms (hereinafter referred to as component (f1)), (f2) anionic surfactants having a hydrocarbon group having from 8 to 21 carbon atoms and a sulfate ester group or a sulfonic acid group (excluding those corresponding to component (f1)) (hereinafter referred to as component (f2)), (f3) anionic surfactants having a hydrocarbon group having from 8 to 21 carbon atoms and a carboxy group (hereinafter referred to as component (f3)), and (f4) anionic surfactants having a hydrocarbon group having from 8 to 21 carbon atoms and a phosphate ester group (hereinafter referred to as component (f4)), and two or more of these may be used.

[0132] The anionic surfactant of the component (f2) may be at least one selected from alkyl sulfate salts, polyoxyalkylene alkyl ether sulfate salts, and alkanesulfonates.

[0133] Examples of salts of the anionic surfactant of component (f) include inorganic salts selected from sodium salts, ammonium salts, potassium salts, magnesium salts, etc., and organic ammonium salts selected from monoethanolammonium salts, diethanolammonium salts, triethanolammonium salts, morpholinium salts, etc.

[0134] From the viewpoint of foamability, the liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention may contain component (f) in an amount of preferably 2 mass % or less, more preferably 1 mass % or less, even more preferably 0.2 mass % or less, even more preferably 0.1 mass % or less, and for example, more than 0 mass %, but it is desirable to not essentially incorporate it. When the liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention contain component (f), the mass ratio (f) / (a) of the content of component (f) to the content of component (a) in the composition is, from the viewpoints of cleaning power and foamability, preferably 5.0 or less, more preferably 2.5 or less, even more preferably 2.0 or less, still more preferably 1.0 or less, and particularly preferably 0.5 or less.

[0135] <(g) component> From the viewpoint of blend stability, the liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention may contain a hydrotrope as component (g). As the hydrotrope, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, or their sodium, potassium, or magnesium salts are preferable, and p-toluenesulfonic acid or its salts are particularly preferable.

[0136] From the viewpoint of formulation stability, the liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention may contain component (g) in an amount of preferably 0.5 mass % or more, more preferably 1 mass % or more, even more preferably 1.5 mass % or more, and preferably 15 mass % or less, more preferably 10 mass % or less, even more preferably 5 mass % or less.

[0137] <(h) component> From the viewpoint of detergency, the liquid detergent composition and the liquid detergent 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 a salt thereof, ethylenediaminetetraacetic acid or a salt thereof, methylglycine diacetic acid or a salt thereof, and L-glutamic acid diacetic acid or a salt thereof. Examples of salts of component (h) include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, and organic amine salts such as ammonium salts, monoethanolamine salts, diethanolamine salts, and triethanolamine salts. Preferred are alkali metal salts, and more preferably sodium salts.

[0138] From the viewpoint of detergency, the liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention may contain component (h) in an amount of preferably 0.1 mass % or more, more preferably 1.0 mass % or more, even more preferably 2.0 mass % or more, and preferably 20 mass % or less, more preferably 10 mass % or less, even more preferably 6 mass % or less.

[0139] The liquid detergent compositions and liquid detergent compositions for hard surfaces of the present invention may contain optional ingredients such as enzymes, fragrances, dyes, pigments, preservatives, pH adjusters, stabilizers, cleaning aids, and the like.

[0140] The viscosity at 25°C of the liquid detergent composition and the liquid detergent composition for hard surfaces of the present invention is preferably 1 mPa·s or more, more preferably 3 mPa·s or more, even more preferably 5 mPa·s or more, and preferably 50 mPa·s or less, more preferably 20 mPa·s or less, even more preferably 15 mPa·s or less, still more preferably 12 mPa·s or less, and even more preferably 10 mPa·s or less, from the viewpoint of reducing the influence of the foaming property depending on the trigger pulling speed. The viscosity of these compositions can be adjusted by the water-soluble solvent of component (d) or the hydrotropic agent of component (g). Here, the viscosity is measured by the viscosity measurement method described below.

[0141] <Method of measuring viscosity> A Model BM B-type viscometer manufactured by TOKIMEC INC. equipped with a rotor with rotor number No. 1 is prepared. 100 mL of the liquid detergent composition or liquid detergent composition for hard surfaces of the present invention is filled into a viscosity measurement beaker, and the temperature is sufficiently adjusted in a thermostatic water bath at 25° C. The beaker containing this composition is set in the viscometer, and the value measured 60 seconds later at a rotor rotation speed of 60 r / min is measured as the viscosity of the liquid detergent composition or liquid detergent composition for hard surfaces.

[0142] The cleaning article of the present invention and the liquid detergent composition used for the cleaning article of the present invention can clean a surface to be cleaned, such as a hard surface of a textile product or a hard article. Therefore, the cleaning article of the present invention may be an article for cleaning a hard surface. The hard surface is not particularly limited, and examples thereof include glass, pottery, porcelain, enamel, tile, ceramics; metals such as aluminum, stainless steel, brass, etc.; and synthetic resins such as polyethylene, polypropylene, melamine resin, polyamide resin, ABS resin, FRP, etc. The hard surfaces to which the articles and compositions of the present invention can be applied are preferably hydrophilic hard surfaces, where "hydrophilic" in relation to the hard surface means that the static contact angle with water is less than 70°. The hard surface suitable for the present invention may be one or more hard surfaces selected from glass, pottery, porcelain, plastic, stainless steel, and silicon wafers. The surface to be cleaned in the present invention is preferably a hard surface, specifically an article having a hard surface. Examples of hard surfaces include hard surfaces of articles installed in one or more selected from kitchens, toilets, bathrooms, and living rooms. More specifically, examples of articles having hard surfaces include toilets, bathtubs, kitchen sinks, gas ranges, windowpanes, mirrors, faucets, etc.

[0143] <How to clean the surface to be cleaned> The present invention provides a method for cleaning a surface to be cleaned, which comprises contacting the surface to be cleaned with foam sprayed using the cleaning article of the present invention. The surface to be cleaned in the cleaning method of the present invention is preferably a hard surface. Furthermore, the method for cleaning a surface to be cleaned of the present invention may be a method for cleaning a hard surface, which comprises contacting the liquid cleaning composition for hard surfaces of the present invention with the hard surface and wiping off the contacted composition. The liquid detergent composition of the present invention is preferably brought into contact with the surface to be cleaned in the form of a foam using the above-mentioned cleaning article of the present invention.

[0144] In the method for cleaning a surface to be cleaned of the present invention, after contacting the hard surface with the liquid detergent composition for hard surfaces of the present invention, one or more steps selected from scrubbing the hard surface with a cleaning tool such as a sponge or a scrubbing brush, rinsing the hard surface that has been in contact with the hard surface with water, and wiping off the liquid detergent composition for hard surfaces that has been in contact with the hard surface may be performed. Examples of wiping items for wiping off the hard surface include cloth, paper, sponge, etc. The cloth may be a woven fabric or a nonwoven fabric.

[0145] The cleaning article of the present invention can be suitably used in the method for cleaning a surface to be cleaned of the present invention. The method for cleaning a surface to be cleaned of the present invention will be described in detail below by taking as an example a method for using the cleaning article of the present invention.

[0146] The method of using the cleaning article of the present invention is preferably to directly contact the liquid detergent composition foamed and sprayed from a spray container with the hard surface to be cleaned. The hard surface to be cleaned is preferably a hard surface with oily soiling, more preferably a hard surface with oily soiling containing solid grease. The cleaning article of the present invention can be suitably used as a method for cleaning hard surfaces. In a preferred method of using the cleaning article of the present invention, the liquid detergent composition foamed and sprayed using a spray container, more preferably the liquid detergent composition for hard surfaces foamed and sprayed using a spray container, is contacted with a hard surface. Specifically, the liquid detergent composition foamed and sprayed using a spray container, more preferably the liquid detergent composition for hard surfaces foamed and sprayed using a spray container, is contacted with a hard surface without dilution. After contacting with a hard surface, the composition of the liquid detergent composition may change. That is, after contacting with a hard surface, the composition of the liquid detergent composition may be diluted or concentrated.

[0147] In a preferred method of using the cleaning article of the present invention, the liquid detergent composition foamed and sprayed from a spray container, more preferably the liquid detergent composition for hard surfaces foamed and sprayed from a spray container, is brought into contact with a hard surface and then left without applying mechanical force. That is, the liquid detergent composition is brought into contact without using a flexible material such as a sponge, and left as is without applying mechanical force. According to the cleaning article of the present invention, the cleaning effect of the liquid detergent composition can be enhanced, and the cleaning effect of cleaning without applying mechanical force can be significantly improved, and the cleaning article can be left without applying mechanical force, and after leaving, the cleaning can be completed by rinsing with water.

[0148] In a preferred method of using the cleaning article of the present invention, the liquid detergent composition is sprayed in the form of a foam from a spray container, more preferably, the liquid detergent composition for hard surfaces is sprayed in the form of a foam from a spray container onto an area of ​​100 cm of the hard surface to be cleaned. 2 It is preferable to contact the substance with the aqueous solution in an amount of preferably 0.1 g or more, more preferably 0.3 g or more, even more preferably 0.4 g or more, and preferably 5 g or less, more preferably 3 g or less, even more preferably 2 g or less, relative to the amount of the aqueous solution, and further preferably spray the aqueous solution.

[0149] In a preferred method of using the cleaning article of the present invention, from the viewpoint of enhancing the cleaning power, the liquid detergent composition sprayed in the form of foam using a spray container, more preferably the liquid detergent composition for hard surfaces sprayed in the form of foam using a spray container, is left on the hard surface for preferably 10 seconds or more, more preferably 20 seconds or more, even more preferably 30 seconds or more, even more preferably 40 seconds or more, and from the same viewpoint, preferably 60 minutes or less, more preferably 30 minutes or less, even more preferably 20 minutes or less, even more preferably 10 minutes or less. In this case, the time when the liquid detergent composition first comes into contact with the hard surface may be the start of the leaving. The temperature during leaving may be room temperature, for example, 10°C or more and 30°C or less.

[0150] In short, in a preferred method of using the cleaning article of the present invention, the liquid detergent composition is sprayed in the form of a foam using a spray container, and is brought into contact with the hard surface to be cleaned for preferably at least 10 seconds, more preferably at least 20 seconds, even more preferably at least 30 seconds, and even more preferably at least 40 seconds, from the viewpoint of enhancing cleaning power, and from the same viewpoint, for preferably not more than 60 minutes, more preferably not more than 30 minutes, even more preferably not more than 20 minutes, and even more preferably not more than 10 minutes.

[0151] In the cleaning article of the present invention, the mass of the liquid detergent composition discharged as a foam in one discharge operation of the spray container is preferably 0.3 g or more, more preferably 0.4 g or more, from the viewpoint of increasing the cleaning power, and is preferably 3.0 g or less, more preferably less than 1.5 g, and even more preferably 1.2 g or less, from the viewpoint of reducing the force required to pull 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 discharged in one discharge operation can also be reduced. This makes it possible to reduce the weight of the cleaning article and improve the ease of handling, and to increase the number of times and area that can be cleaned without refilling the liquid detergent composition in the spray container. In addition, the force required to pull the trigger can also be adjusted to be small.

[0152] In the cleaning article of the present invention, the liquid detergent composition discharged as foam from the spray container in five consecutive discharge operations preferably covers an area of ​​500 cm from the viewpoint of enhancing cleaning power and operability. 2 More preferably, 750 cm 2 More preferably, 1,000 cm 2 From the viewpoint of cleaning power, it is preferably 20,000 cm 2 Less than or equal to 10,000 cm 2 More preferably, 3,000 cm 2 According to the cleaning article of the present invention, a good foam can be formed regardless of the trigger pulling speed. This makes it possible to improve the feel of use and foam cleansing properties regardless of the usage mode of the user of the article. In the cleaning article of the present invention, the area covered by the foam discharged five times in succession from the pressure-accumulation trigger spray is preferably within the above range. The foam discharged five times in succession is foam produced by continuously spraying the contents by repeatedly pulling the pressure-accumulation trigger spray or the continuous-jet trigger spray five times.

[0153] In the cleaning article of the present invention, the area covered by the liquid detergent composition ejected as a foam from the spray container in five consecutive ejection operations is the area obtained by spraying the liquid detergent composition five times in succession while moving the cleaning article 20 cm horizontally relative to the spray surface over a target surface 40 cm away from the cleaning article of the present invention, and measuring with a ruler the short and long axes of the area where the foam adheres.

[0154] The liquid detergent composition discharged as a foam from a spray container preferably has a foam thickness on the hard surface immediately after discharge of 3 mm or more, more preferably 5 mm or more, and even more preferably 8 mm or more, from the viewpoint of adhesion to the hard surface or adhesion time. The cleaning article of the present invention is preferably discharged so as to generate a foam of such thickness.

[0155] In addition, in the cleaning article of the present invention, from the viewpoint of adhering to the dirt and enhancing the cleaning power, the liquid detergent composition discharged as a foam has an adhesion time to a hard surface of preferably 20 seconds or more, more preferably 30 seconds or more, and even more preferably 1 minute or more. In addition, from the viewpoint of penetration into the dirt, it is preferably 20 minutes or less, more preferably 10 minutes or less. The adhesion time of the liquid detergent composition to a hard surface can be measured as follows. For example, a polypropylene container with a bottom (having an area of ​​200 mm x 200 mm or more) is used as a test specimen, and the corner where the bottom and wall of the container meet is sprayed once, and immediately afterwards the test specimen is stood at a right angle and the state of the foam is observed. The spray is performed with the angle between the direction of the spray container's discharge and the bottom at 45 degrees, and the distance from the foam outlet of the nozzle to the corner is 15 cm. The time from the point at which the test specimen is stood at a right angle with the bottom standing upright to the point at which the bottom of the foam moves downward (droops) 2 cm or more is measured. Adhesion is evaluated under conditions of a temperature of 20°C and a humidity of 65%.

[0156] The spray container may be entirely made of synthetic resin, or entirely or partially made of a material other than synthetic resin, such as metal or ceramic. Examples of synthetic resins that can be used include polyolefins such as polyethylene and polypropylene, polystyrene, polyethylene terephthalate (PET), polycarbonate, acrylic, polyamide, polyacetal, vinyl chloride, etc. The container body of the spray container is preferably made of synthetic resin, and can be manufactured by, for example, 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 also preferably 200 mL or more and 600 mL or less, more preferably 300 mL or more and 500 mL or less. EXAMPLES

[0157] <Examples 1 to 3 and Comparative Example 1> Liquid detergent compositions shown in Tables 1 to 3 were prepared using the components shown in Tables 1 to 3, and the following items were evaluated. The results are shown in Tables 1 to 3. Note that the mass percentages of the blended components in Tables 1 to 3 are all values ​​based on the active components.

[0158] Polymer A and polymer B of the component (c) were synthesized by the method described in Production Example 1 or 2 below. <Production Example 1> Polymer A was produced by combining and synthesizing components in a prescribed molar ratio with reference to JP-A-6-212597 and JP-B-53-10539.

[0159] <Production Example 2> Polymer B was synthesized by the methods described in steps 1 and 2 below. (Process 1) 126.30 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 1000 mL four-neck flask, and the temperature was raised to 78° C. and refluxed. 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 each added dropwise over 2 hours. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.

[0160] (Process 2) In a 1000 mL four-neck flask, 94.70 g of the obtained polymer solution, 3.15 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), and 150.00 g of water were added and heated to 50° C. 38.70 g of 1,3-propane sultone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour to carry out a reaction. After aging for 3 hours, the mixture was heated under reduced pressure at 90° C. / 20 kPa for 2 hours to distill off ethanol, and an aqueous solution containing polymer B was obtained.

[0161] In polymer B, structural unit D had the following structure in formula (c3), structural unit E had the following structure in formula (c4), and the molar ratio of structural unit D / structural unit E was 95 / 5. Structural unit D:R 14c =R 15c =H, R 16c =CH3, R 17c =C2H4,R 18c =R 19c =CH3,X 2c =O, X 3c =R 21c SO3 - , R 21c =C3H6 Unit E:R 22c =R 23c =H, R 24c =CH3,X 4c =O, R 25c =C2H4,X 5c =N + R 26c R27c R 28c X 6c , R 26c =R 27c =CH3, R 28c =C2H5,X 6c =C2H5SO4 - Polymer B had a weight average molecular weight of 63,000.

[0162] The weight average molecular weight of Polymer B was measured by gel permeation chromatography (GPC) under the following conditions. Column: Two TSKgel α-M columns (manufactured by Tosoh Corporation) were used, connected in series. Column temperature: 40℃ Eluent: 0.15molNa2SO4 / 1%CH3COOH / water Flow rate: 1.0mL / min Detector: Differential refractometer Standard material: Pullulan standard product

[0163] The weight average molecular weight of polymer B was measured by SLS (static light scattering). That is, the weight average molecular weight was calculated by measuring static light scattering under the following conditions using a light scattering photometer "DLS-7000" (manufactured by Otsuka Electronics Co., Ltd.) and preparing a Zimm-plot. The refractive index increment required for calculating 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 from 30° to 150° at 10° intervals. Temperature: 25℃ Solvent: Trifluoroethanol

[0164] <Component (a)> Lauryl dimethylamine oxide: Amphitol 20N, manufactured by Kao Corporation Lauryl amidopropyl dimethylamine oxide: Softazoline LAO-C, manufactured by Kawaken Fine Chemicals Co., Ltd. Lauryl amidopropyl betaine: Amphitol 20AB, manufactured by Kao Corporation Lauryl hydroxysulfobetaine: Amphitol 20HD, manufactured by Kao Corporation <(b) Component> Alkylbenzyldimethylammonium chloride: Sanisol B-50 (a mixture of 8 to 16 carbon atoms), 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: Fujifilm Wako Pure Chemical Industries, Ltd. Ethanol: Japan Synthetic Alcohol Co., Ltd. <(c) component> Polymer A: Diallyldimethylammonium chloride / maleic acid / SO2 = 70:25:5 (molar ratio), copolymer with weight average molecular weight of 30,000 Polymer B: the copolymer obtained in Production Example 2 HEC: Hydroxyethyl cellulose, Daicel SE850, viscosity (1%, 25°C) 2400-3000 mPa·s, molecular weight 1.56 million, manufactured by Daicel Miraize Co., Ltd. PVA: Polyvinyl alcohol, weight average molecular weight 50,000, viscosity (4%, 20°C) 20.5-24.5 mPa·s, saponification degree 87.0-89.0 mol%, Kuraray Poval 22-88, manufactured by Kuraray Co., Ltd. PVA (weight average molecular weight 70,000): Polyvinyl alcohol, weight average molecular weight 70,000, Kuraray Poval 44-88, manufactured by Kuraray Co., Ltd. PVA (weight average molecular weight 100,000): Polyvinyl alcohol, weight average molecular weight 100,000, Kuraray Poval 95-88, manufactured by Kuraray Co., Ltd. PVA (weight average molecular weight 200,000): Polyvinyl alcohol, weight average molecular weight 200,000, manufactured by Sigma-Aldrich PVA (weight average molecular weight 350,000): Polyvinyl alcohol, weight average molecular weight 350,000, Kuraray Poval 200-88KX, manufactured by Kuraray Co., Ltd. Xanthan gum (weight average molecular weight 3 million): Monart Gum OB, weight average molecular weight 3 million, MP Gokyo Food & Chemical Co., Ltd. <(d) component> -Butyl diglycol: Nippon Nyukazai Co., Ltd. Propylene glycol monomethyl ether: Nippon Nyukazai Co., Ltd. Dipropylene glycol monobutyl ether: Fujifilm Wako Pure Chemical Industries, Ltd. <(e) component> Alkyl polyglycoside: Alkyl (carbon number 12-16) polyglucose (average sugar condensation degree 1-2), product name "AG124", manufactured by Kao Corporation) 2-Ethylhexyl glyceryl ether: Penetol GE-EH, manufactured by Kao Corporation <Component (f)> Sodium di-2-ethylhexyl sulfosuccinate: Airroll CT-1L, manufactured by Toho Chemical Industry Co., Ltd. AES (alkyl ether sulfate): Emeral 270J, manufactured by Kao Corporation <(g) component> Paratoluenesulfonic acid: PTS M-7000, manufactured by Meiyu Sangyo Co., Ltd. <(h) component> Citric acid: Purified citric acid (anhydrous), manufactured by Fuso Sangyo Co., Ltd. Ethylenediaminetetraacetic acid: Chubu Cherest Co., Ltd. <Other ingredients> Sodium sulfate: Shikoku Chemical Industries Co., Ltd. ·Fragrance

[0165] <Cleanability of oil stains> 20 mg of cooking oil was applied to one side of a stainless steel substrate (Engineering Test Services, 10 cm x 10 cm x 1 mm, alkaline-cleaned), and the substrate was thoroughly dried with a hair dryer to be used as the cleaning subject for evaluation. The mass of the stainless steel substrate was measured before and after the oil was applied, and the "initial oil mass" was calculated based on the increase in mass of the stainless steel substrate before and after the oil was applied. Using a commercially available trigger-type sprayer (Kyukyutto Foam Spray (Kao Corporation), model number: TA-F), a foam of the liquid detergent composition shown in Tables 1 to 3 was sprayed (approximately 1 mL) onto an oil stain on a SUS substrate, and after leaving it for 30 seconds, a paper towel was pressed against the oil stain and gently moved back and forth five times to wipe off the stain. This operation was performed on six different oil stains on SUS substrates (three times each using two different pulling speeds, 0.5 seconds / stroke and 0.2 seconds / stroke), and the state of dirt adhesion before and after each cleaning was compared by photographing, and the photographs were visually inspected to evaluate the cleanability based on the following index. The average value of the six operations performed on the oil stains on six different SUS substrates was used to evaluate the cleanability. The results are shown in Tables 1 to 3. The higher the cleaning evaluation value, the better the ability to clean oil stains. 5: Less than 10% of the foam application area remains dirty. 4: Dirt remains on 10% to 30% of the foam application area. 3: Dirt remains on 30% to 50% of the foam application area. 2: Dirt remains on 50% to 70% of the foam application area. 1: More than 70% of the foam application area remains dirty.

[0166] <Evaluation of specific foam volume> The liquid detergent compositions in Tables 1 to 3 were filled into a spray container equipped with a pressure-accumulation sprayer (Kyukyutto Foam Spray (Kao), model number: TA-F) and a spray container equipped with a continuous-jet sprayer (Bath Magiclean Air Jet (Kao Corporation, lot number: W0262202) equipped with a nozzle tip that enables foam formation of Attack Shutto Foam Spray (Kao Corporation)) attached to the nozzle part).

[0167] <Measurement of specific foam volume> The liquid detergent composition in each spray container described in the Examples and Comparative Examples was sprayed five times in succession without intervals into a 200 mL graduated cylinder (made of glass, inner diameter 40 mm). One minute after the fifth spray, the foam volume (mL) in the graduated cylinder was visually read. The mass of the 200 mL graduated cylinder after spraying was measured using a four-digit balance (capable of measuring to two decimal places), and the difference from the mass of the graduated cylinder before spraying was taken as the foam mass (g), and the foam specific volume was calculated using the following formula. The foam specific volume was measured under conditions of a temperature of 20°C and a humidity of 65%. The amount of foam discharged by one discharge operation was calculated as the average of the foam mass (g) determined in the above-mentioned measurement of the foam specific volume, that is, the foam mass (g) / 5. Foam specific volume (mL / g) = foam volume (mL) / foam mass (g)

[0168] The specific foam volume was calculated using the sprayers in Tables 1 to 3, with the trigger pull speeds being changed to 0.5 seconds / stroke and 0.2 seconds / stroke. In addition, the ratio of the specific foam volume (2) of the foam sprayed at 0.2 seconds / stroke to the specific foam volume (1) of the foam sprayed at 0.5 seconds / stroke [specific foam volume (2) / specific foam volume (1)] was calculated and is shown in Tables 1 to 3.

[0169] <Pull speed (adjustment of evaluation conditions)> In the measurement of the specific foam volume, the time taken from the start of pulling the trigger to the end of pulling (one way) was measured, and the pulling speed (seconds / stroke) was calculated from the average value (seconds) of five times. The action from the start of pulling the trigger to the end was photographed at 1000 fps using a high-speed microscope VW-9000 (manufactured by Keyence Corporation) and a camera unit VW-600C (manufactured by Keyence Corporation), and saved as a video. The saved video was played back in slow motion using video editing software CorelVideoStudio X7, and the time taken from the start of pulling the trigger to the end of pulling was measured. Using this method, we confirmed that it was possible to experiment at two speeds: 0.5 seconds / stroke (when pulling the trigger slowly) and 0.2 seconds / stroke (when pulling the trigger quickly).

[0170] <Method of measuring viscosity> A Brookfield viscometer, Model BM, manufactured by TOKIMEC INC., equipped with a rotor with rotor number No. 1 was prepared. 100 mL of each of the liquid detergent compositions of the Examples and Comparative Examples was filled into a viscosity measurement beaker, and the temperature was thoroughly adjusted in a thermostatic water bath at 25° C. The beaker containing this composition was set in a viscometer, and the value measured 60 seconds later at a rotor rotation speed of 60 r / min was regarded as the viscosity of the liquid detergent composition.

[0171] <Evaluation of convenience (1)> Considering that a larger specific foam volume allows for a wider range of spraying, convenience (1) was evaluated as follows using the values ​​of the specific foam volume of foam formed at two different trigger pulling speeds, i.e., the specific foam volume of foam formed when the trigger was pulled slowly (0.5 seconds / stroke) and the specific foam volume of foam formed when the trigger was pulled quickly (0.2 seconds / stroke). The higher the rating number for convenience (1), the more convenient the cleaning product is. 4: At both speeds, the foam specific volume was 25 mL / g or more. 3: At both speeds, the foam specific volume was 15 mL / g or more. 2: Depending on the pulling speed, the foam specific volume was less than 15 mL / g. 1: At all pull speeds, the foam specific volume was less than 15 mL / g.

[0172] <Evaluation of efficiency (1)> Efficiency (1) was defined as an index for generating good foam independent of the pulling speed of the spray, and efficiency (1) was evaluated using the ratio of the specific foam volume (2) of foam formed when the trigger was pulled quickly (0.2 seconds / stroke) to the specific foam volume (1) of foam formed when the trigger was pulled slowly (0.5 seconds / stroke) [specific foam volume (2) / specific foam volume (1): rate of change in specific foam volume] for foam formed at two different trigger pulling speeds. The higher the efficiency (1) rating, the more efficient the cleaning product. 3: The rate of change in foam specific volume was 0.6 or more and less than 1.5. 2: The rate of change in foam specific volume was 0.5 or more and less than 0.6, or 1.5 or more and less than 2.0. 1: The rate of change in foam specific volume was less than 0.5 or greater than 2.0.

[0173] <Evaluation of simplicity (2)> The liquid detergent composition was sprayed onto a tabletop 40 cm away from the cleaning article to evaluate convenience (2). The evaluation was performed by 10 testers at two different trigger pulling speeds (0.5 seconds / stroke, 0.2 seconds / stroke), and the short and long diameters of the area where the foam was attached were measured with a ruler. The average values ​​of the 10 average areas of the foam attached at the two pulling speeds were calculated and shown in Tables 2 and 3. The larger the foam area of ​​a cleaning article, the wider the area where the foam can be sprayed, and the more convenient it is for convenience (2). In the case of the pressure-accumulation trigger, the nozzle of the cleaning article was moved horizontally at a constant speed of 20 cm relative to the surface of the desk top during one pull of the trigger. In the case of the continuous-jet trigger, the nozzle of the cleaning article was moved horizontally at a constant speed of 40 cm relative to the surface of the desk top.

[0174] <Evaluation of efficiency (2)> The efficiency (2) of the cleaning products in Tables 2 to 3 was evaluated by 10 testers who sprayed each cleaning product five times in succession as quickly as possible (no pull speed specified) and measured the specific foam volume. The specific foam volume was measured in the same manner as described above in <Measurement of specific foam volume>, and the average values ​​of 10 testers were calculated, and these average values ​​are shown in Tables 2 to 3. A cleaning article with a large specific foam volume, that is, a cleaning article that shows good foaming properties even when the trigger is pulled quickly, is an efficient cleaning article.

[0175] [Table 1]

[0176] As shown in Table 1, in Comparative Examples 1-1 to 1-3, the specific foam volume of the formed foam decreased when the trigger was pulled faster (0.2 seconds / stroke). This is thought to be because the liquid detergent composition was discharged quickly, and the formation and stabilization of the foam film could not keep up with the speed at which the air and the liquid detergent composition were mixed (hereinafter abbreviated as the air-liquid mixing speed), resulting in a high proportion of the composition that did not form a foam in the discharged liquid detergent composition, resulting in a decrease in the specific foam volume. In contrast, the liquid detergent compositions of Examples 1-1 to 1-5, which contain the (d) component and the (c) component in a predetermined ratio, were able to improve the foaming property of the composition and stabilize the film foam at the same time. That is, the liquid detergent compositions of the Examples were excellent in the quick foaming property that contributes to the foaming property and the foam stability that maintains the foam as it is. In particular, due to the contribution of the (c) component in stabilizing the film foam, it was possible to spray a foam with a predetermined foam specific volume even when the gas-liquid mixing speed was fast. This made it possible to spray a foam with a predetermined foam specific volume regardless of the difference in the trigger pulling speed, and as a result, cleaning in which good foam is brought into contact with a hard surface could be performed simply and efficiently.

[0177] [Table 2]

[0178] [Table 3] [Explanation of symbols]

[0179] 1, 16, 26 Spray canister 2 Container body 3. 17 Sprayer 4. Trigger 9 Cylinder 11e Foam outlet 18 Main Cylinder 19 Vertical supply tube 20 injection holes 21 Injection cylinder part 23 Storage Cylinder 24 Foaming nozzle (a tip that provides foaming properties) 28 Foaming tube (a tip that gives foaming properties)

Claims

1. A cleaning article comprising a pressurized trigger spray container and a liquid cleaning agent composition contained within the spray container, wherein the spray container is capable of spraying the liquid cleaning agent composition as foam, the foam specific volume of the sprayed foam is 15 mL / g or more, and the ratio of the foam specific volume of foam sprayed from the spray container at 0.2 seconds / stroke to the foam specific volume of foam sprayed from the spray container at 0.5 seconds / stroke is 0.5 or more and less than 2.

0.

2. A cleaning article according to claim 1, for cleaning hard surfaces.

3. A cleaning article according to claim 1 or 2, for cleaning the hard surface of an article provided in one or more of the following: a kitchen, toilet, bathroom, and living room.

4. The cleaning article according to claim 1 or 2, wherein the liquid cleaning agent composition contains one or more selected from amine oxide type surfactants and betaine type surfactants.

5. The cleaning article according to claim 1 or 2, wherein the liquid cleaning agent composition contains one or more selected from alkyl (poly)glucoside and alkyl (poly)glyceryl ether.

6. The cleaning article according to claim 1 or 2, wherein the liquid cleaning agent composition contains (c) a hydrophilic polymer.

7. The cleaning article according to claim 1 or 2, wherein the liquid cleaning agent composition contains (d) one or more water-soluble solvents selected from alcohols having 3 to 10 carbon atoms and glycol compounds having 2 to 14 carbon atoms.

8. The cleaning article according to claim 1 or 2, wherein the pressurized trigger spray container is capable of continuously spraying the liquid cleaning agent composition.

9. The cleaning article according to claim 8, wherein the pressurized trigger spray container is provided with a tip that imparts foaming properties to the liquid cleaning agent composition at the nozzle of the spray container.

10. The liquid detergent composition contains the following components (a), (c), and (d), wherein the weight-average molecular weight of component (c) is 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) in the composition is 0.005 or more and 1 or less, and the mass ratio (d) / (a) of the content of component (d) to the content of component (a) is 0.5 or more and 2.5 or less, the cleaning article according to claim 1 or 2. (a) Ingredients: Amphoteric surfactant (c) Component: Hydrophilic polymer (d) Components: One or more water-soluble solvents selected from alcohols with 3 to 10 carbon atoms and glycol compounds with 2 to 14 carbon atoms.

11. The pressurized trigger spray container is capable of continuously spraying the liquid detergent composition, and the spray container is equipped with a tip that imparts foaming properties to the liquid detergent composition at the spray nozzle. The cleaning article according to claim 1 or 2, wherein the liquid cleaning agent composition contains the following components (a) and (d). (a) Ingredients: Amphoteric surfactant (d) Components: One or more water-soluble solvents selected from alcohols with 3 to 10 carbon atoms and glycol compounds with 2 to 14 carbon atoms.

12. A method for cleaning a surface to be cleaned, comprising bringing foam sprayed using the cleaning article described in claim 1 or 2 into contact with the surface to be cleaned.

13. When the trigger of the aforementioned pressurized trigger spray is pulled five times in a row, the area covered by the foam on the surface to be cleaned is 500 cm². ２ The above describes the method for cleaning a surface to be cleaned according to claim 12.

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