Liquid toilet cleaning agent composition

Abstract

To provide a liquid detergent composition for toilet having excellent wiping property and washing power and excellent spreading property of flowing water in view of the circumstance where in a flush toilet, when water is flushed into a toilet bowl, water is required to spread over a wide area on the surface of the toilet bowl (excellent spreading property of flowing water), and by spreading water over a wide area on the surface of the toilet bowl, dirt adhering to the toilet bowl can be washed further satisfactorily.SOLUTION: The composition comprises a component (A): a surfactant, a component (B): a specific compound and a component (C): a polymer having a repeating unit (c1) derived from a monomer having a quaternary ammonium group. The mass ratio represented by the component (A) / the component (C) is preferably 0.2 to 12.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid cleaning composition for toilets.

Background Art

[0002] As a method for cleaning toilet seats, floors, walls, etc., there is a method of foaming or atomizing a liquid cleaning composition and spraying it onto the object to be cleaned, and then wiping off the sprayed liquid cleaning composition. For the liquid cleaning composition used in such a cleaning method, in addition to detergency, it is required to be easy to wipe off (good wiping property). For example, Patent Document 1 proposes a liquid cleaning composition for toilets containing a specific surfactant and a specific solvent in a specific mass ratio.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] By the way, in a flush toilet, when water is poured into the toilet bowl, it is required that the water spreads over a wide area on the surface of the toilet bowl (excellent spreading property of running water). By spreading water over a wide area on the surface of the toilet bowl, the dirt adhering to the toilet bowl can be washed better. Therefore, the present invention provides a liquid cleaning composition for toilets that is excellent in wiping property, detergency, and spreading property of running water.

Means for Solving the Problems

[0005] The present invention has the following aspects. <1> (A) component: a surfactant, and (B) component: a compound represented by the following formula (b1), and (C) Component: A polymer having repeating units (c1) derived from a monomer having a quaternary ammonium group, A liquid toilet cleaning agent composition containing [a specific ingredient]. [ka] [In formula (b1), R 1 [where m is an alkylene group with 2 or 3 carbon atoms, and m is a number from 1 to 6] <2> The mass ratio expressed as component (A) / component (C) is 0.2 to 12. <1> A liquid toilet cleaning agent composition as described above. <3> The content of component (A) is 0.5 to 5% by mass, The content of component (B) is 0.2 to 4.5% by mass, The content of component (C) is 0.2 to 4% by mass. <1> or <2> A liquid toilet cleaning agent composition as described above. <4> The repeating unit (c1) is at least one selected from the repeating unit (c1-1) derived from diallyldimethylammonium salt and the repeating unit (c1-2) derived from methacrylamidopropyltrialkylammonium salt. <1> ~ <3> A liquid toilet cleaning agent composition as described in any of the following. [Effects of the Invention]

[0006] The liquid toilet cleaning agent composition of the present invention exhibits excellent wiping properties and cleaning power, as well as excellent water spreadability. [Modes for carrying out the invention]

[0007] (Liquid cleaning agent composition for toilets) The liquid toilet cleaning agent composition of the present invention (hereinafter sometimes simply referred to as "liquid cleaning agent composition") contains components (A) to (C).

[0008] <(A) component> Component (A) is a surfactant. The liquid detergent composition has excellent cleaning power and wiping properties due to the inclusion of component (A). Examples of component (A) include amphoteric surfactants, anionic surfactants, nonionic surfactants, amine oxide-type surfactants, and cationic surfactants. Among these, amphoteric surfactants are preferred as component (A). Using amphoteric surfactants can further enhance cleaning power and wipeability.

[0009] <<Amphoteric surfactants>> There are no particular restrictions on the amphoteric surfactant, and it can be appropriately selected depending on the purpose. Examples include betaine-based amphoteric surfactants and amino acid-based amphoteric surfactants. Among these, betaine-based amphoteric surfactants are preferred. Examples of betaine-based amphoteric surfactants include carbobetaine-based amphoteric surfactants, amidebetaine-based amphoteric surfactants, sulfobetaine-based (hydroxysulfobetaine-based, amidesulfobetaine-based) amphoteric surfactants, imidazolinium betaine-based amphoteric surfactants, phosphobetaine-based amphoteric surfactants, and aminopropionic acid-based amphoteric surfactants. Carbobetaine-based amphoteric surfactants and amidebetaine-based amphoteric surfactants are preferred as betaine-based amphoteric surfactants, with amidebetaine-based amphoteric surfactants being more preferred.

[0010] (1) Examples of carbobetaine-based amphoteric surfactants include dimethylaminoacetic acid betaine laurate, myristyldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine. (2) Examples of amidobetaine-based amphoteric surfactants include coconut oil fatty acid amidopropyl betaine (cocamidopropyl betaine), lauric acid amidopropyl betaine, and isostearamidopropyl betaine. (3) Examples of sulfobetaine-based amphoteric surfactants include coconut oil fatty acid dimethylaminohydroxysulfobetaine, lauryldimethylaminohydroxysulfobetaine, lauryl hydroxysulfobetaine, coconut oil fatty acid dimethylsulfopropylbetaine, lauryl sulfobetaine, stearyl sulfobetaine, myristyl sulfobetaine, etc. (4) Examples of imidazolinium betaine-based amphoteric surfactants include coconut oil alkyl-N-hydroxyethylimidazolinium betaine, coconut oil alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, etc. (5) Examples of phosphobetaine-based amphoteric surfactants include lauryl hydroxyphosphobetaine, etc. (6) Examples of aminopropionic acid-based amphoteric surfactants include sodium laurylaminodipropionate, triethanolamine laurylaminodipropionate, etc. (7) Examples of amino acid-based amphoteric surfactants include laurylaminofatty acid salts, stearylaminofatty acid salts, myristylaminofatty acid salts, etc. As the amphoteric surfactant, lauric acid amidopropyl betaine, lauryldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine are preferred, and lauric acid amidopropyl betaine and lauryldimethylaminoacetic acid betaine are particularly preferred from the perspective of wiping properties. Examples of the counter ions of the salt include ions of alkali metal salts, ions of ammonium salts, ions of alkanolamine salts, etc. Among these, ions of alkali metal salts are preferred, and sodium ions and potassium ions are more preferred.

[0011] Amphoteric surfactants are commercially available. Examples of lauramidopropyl betaine include "Enacol L-30B" manufactured by Lion Specialty Chemicals Co., Ltd. Examples of coconut fatty acid amide propyl betaine include "TEGO BETAIN CK-OK" manufactured by Degussa. Examples of palm kernel oil fatty acid amide propyl betaine include "Ampholex PB-1" manufactured by Miyoshi Oil & Fat Co., Ltd. Examples of lauryldimethylaminoacetic acid betaine include "Lebon LD-36" manufactured by Sanyo Chemical Industries, Ltd. and "Obazoline LB-SF" manufactured by Toho Chemical Industry Co., Ltd. Examples of stearyldimethylaminoacetic acid betaine include "Anitol 86B" manufactured by Kao Corporation.

[0012] With respect to the total mass of component (A), the content of the amphoteric surfactant is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 100% by mass. When the content of the amphoteric surfactant is at least the above lower limit value, the detergency can be further enhanced and the wiping property can be further enhanced.

[0013] ≪Anionic Surfactant≫ Examples of the anionic surfactant include the following. (1) Linear or branched alkylbenzene sulfonates (LAS or ABS) having an alkyl group with 8 to 18 carbon atoms. (2) Alkane sulfonates having 10 to 20 carbon atoms. (3) α-Olefin sulfonates (AOS) having 10 to 20 carbon atoms. (4) Alkyl sulfates or alkenyl sulfates (AS) having 10 to 20 carbon atoms. (5) Any of alkylene oxides having 2 to 4 carbon atoms, or linear or branched alkyl (or alkenyl) ether sulfates (AES) having an alkyl (or alkenyl) group with 10 to 20 carbon atoms to which ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) are added in an average amount of 0.5 to 10 moles. (6) Alkyl (or alkenyl) phenyl ether sulfates having a linear or branched alkyl (or alkenyl) group with 10 to 20 carbon atoms, obtained by adding an average of 3 to 30 moles of any alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1). (7) Alkyl (or alkenyl) ether carboxylates having a linear or branched alkyl (or alkenyl) group with 10 to 20 carbon atoms, obtained by adding an average of 0.5 to 10 moles of any alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1). (8) Alkyl polyhydric alcohol ether sulfates such as alkylglyceryl ether sulfonic acid having 10 to 20 carbon atoms. (9) Long-chain monoalkyl, dialkyl, or sesquialkyl phosphates. (10) Polyoxyethylene monoalkyl, dialkyl, or sesquialkyl phosphates. (11) Higher fatty acid salts (soaps) with 10 to 20 carbon atoms. Examples of constituent salts include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; alkanolamine salts such as monoethanolamine salt (monoethanolammonium), diethanolamine salt (diethanolammonium), and triethanolamine salt (triethanolammonium); and ammonium salts, with sodium salts and potassium salts being preferred.

[0014] Nonionic surfactants Examples of nonionic surfactants include the following: (1) Polyoxyalkylene alkyl ether. (2) Polyoxyalkylene alkyl (or alkenyl) phenyl ethers. (3) Alkyl fatty acid ester alkoxylates obtained by adding alkylene oxide between the ester bonds of long-chain fatty acid alkyl esters. (4) Polyoxyalkylene sorbitan fatty acid ester. (5) Polyoxyalkylene sorbitol fatty acid ester. (6) Polyoxyalkylene fatty acid esters. (7) Polyoxyalkylene hydrogenated castor oil. (8) Glycerin fatty acid ester. (9) Alkyl polyglycoside.

[0015] As a nonionic surfactant, one which is an aliphatic alcohol to which an alkylene oxide has been added is preferred. Examples of aliphatic alcohols include primary alcohols and secondary alcohols. The alkyl group of the aliphatic alcohol may have a branched chain. The number of carbon atoms in the aliphatic alcohol is preferably 6 to 22, and more preferably 8 to 18. The number of carbon atoms in the alkylene oxide is preferably 2 to 4. The average number of moles of added alkylene oxide is preferably 3 to 30 moles. Preferred nonionic surfactants are polyoxyalkylene alkyl ethers obtained by adding 5 to 9 moles (average number of moles added) of ethylene oxide to an aliphatic alcohol having a branched alkyl group with 12 to 18 carbon atoms, and alkyl polyglucosides having 12 to 16 carbon atoms.

[0016] Semi-polar surfactants Examples of semi-polar surfactants include amine oxide type surfactants. Examples of amine oxide-type surfactants include alkylamine oxides and amidoamine oxides. Examples of alkylamine oxides include dodecyldimethylamine oxide, myristyldimethylamine oxide, and coconut alkyldimethylamine oxide. Examples of amidoamine oxides include coconut oil fatty acid amidopropylamine oxide and lauric acid amidopropylamine oxide. Among these, dodecyldimethylamine oxide (AX) is preferred as a semipolar surfactant.

[0017] The content of component (A) is preferably 0.5 to 5% by mass, more preferably 0.5 to 3.5% by mass, and more preferably 0.5 to 3% by mass, relative to the total mass of the liquid detergent composition. If the content of component (A) is within the above range, the wiping ability can be further improved.

[0018] <(B) component> Component (B) is a compound represented by the following formula (b1). By including component (B), which is a so-called glycol-based solvent, the cleaning power of the liquid detergent composition can be enhanced.

[0019] [ka]

[0020] [In formula (b1), R 1 [where m is an alkylene group with 2 or 3 carbon atoms, and m is a number from 1 to 6]

[0021] R 1 This is either an ethylene group or a propylene group, or both. 1 It is preferable that it contains an ethylene group. m is a number between 1 and 6, with 1 to 3 being preferred. Examples of component (B) include monoethylene glycol monophenyl ether, triethylene glycol monophenyl ether, monopropylene glycol monophenyl ether, and tripropylene glycol monophenyl ether. Among these, monoethylene glycol monophenyl ether is preferred as component (B) from the viewpoint of improving cleaning power.

[0022] (B) The content of component (B) is preferably 0.2 to 4.5% by mass, and more preferably 1 to 4.5% by mass, relative to the total mass of the liquid detergent composition. If the content of component (B) is above the lower limit, the cleaning power can be further enhanced. If the content of component (B) is below the upper limit, the wiping ability can be further enhanced.

[0023] The mass ratio (A / B ratio) of component (A) / component (B) is preferably 0.3 to 9, more preferably 0.5 to 5, and even more preferably 0.5 to 3.5. When the A / B ratio is above the lower limit, the wiping ability can be further enhanced. When the A / B ratio is below the upper limit, the cleaning power can be further enhanced.

[0024] <(C) component> Component (C) is a polymer having repeating units (c1) derived from a monomer having a quaternary ammonium group. The inclusion of component (C) enhances the spreadability of the liquid detergent composition.

[0025] Examples of repeating units (c1) include repeating units (c1-1) derived from diallyldimethylammonium salt and repeating units (c1-2) derived from methacrylamidopropyltrialkylammonium salt. Examples of monomer salts include chlorides. The repeating unit (c1) is preferably at least one selected from repeating unit (c1-1) and repeating unit (c1-2).

[0026] In component (C), the amount of repeating units (c1) is preferably 20 to 100 mol%, and more preferably 40 to 100 mol%, relative to the total number of moles of repeating units constituting component (C). When the mole fraction of repeating units (c1) is within the above range, the spreadability of the flowing water can be enhanced.

[0027] Component (C) may have repeating units other than the repeating unit (c1) (arbitrary repeating units). As an optional repeating unit, repeating unit (c2) is preferred. That is, as component (C), a copolymer having repeating unit (c1) and repeating unit (c2) (sometimes referred to as "c1c2 polymer") is preferred. By using a c1c2 polymer as component (C), the spreadability of the flowing water can be further enhanced.

[0028] The repeating unit (c2) is selected from at least one of the following: a repeating unit (c2-1) derived from acrylic acid, a repeating unit (c2-2) derived from acrylamide, and a repeating unit (c2-3) derived from methyl acrylate. Among these, a copolymer containing the repeating unit (c2-2) is preferred as the c1c2 polymer. These repeating units (c2) may be a single type or a combination of two or more types.

[0029] (C) When component is a c1c2 polymer, the molar ratio of repeating units (c2) to repeating units (c1) (c2 / c1 ratio) is preferably greater than 0 and 4 or less, more preferably greater than 0 and 3.5 or less, and even more preferably between 0.05 and 3. If the c2 / c1 ratio is above the lower limit, the sprayability is improved and workability is further enhanced. If the c2 / c1 ratio is below the upper limit, the spread of the flowing water is further enhanced.

[0030] In a c1c2 polymer, the sum of repeating units (c1) and (c2) is preferably 100 mol%.

[0031] (C) Examples of components include diallyldimethylammonium chloride (DADMAC) polymer (DADMAC polymer), acrylic acid / diallyldimethylammonium chloride / acrylamide copolymer, DADMAC / sulfur dioxide copolymer, maleic acid / DADMAC / sulfur dioxide copolymer, acrylic acid / methacryloylaminopropyltrimethylammonium chloride (MAPTAC) / acrylamide copolymer, etc.

[0032] Examples of acrylic acid-DADMAC-acrylamide copolymers include the compound represented by the following formula (c11) (compound c11).

[0033] [ka]

[0034] In equation (c11), n, l, and z are numbers that represent the number of repetitions in the repeating unit, respectively. Compound (c11) may be a random copolymer or a block copolymer.

[0035] Examples of DADMAC-sulfur dioxide copolymers include the compound represented by the following formula (c12) (compound c12).

[0036] [ka]

[0037] In equation (c12), k is a number representing the number of repetitions in the repeating unit. Compound (C12) may be a random copolymer or a block copolymer.

[0038] Examples of maleic acid-DADMAC-sulfur dioxide copolymers include the compound represented by the following formula (c13) (compound c13).

[0039] [ka]

[0040] In equation (c13), w, x, and y are numbers that represent the number of repetitions in the repeating unit, respectively. Compound (c13) may be a random copolymer or a block copolymer.

[0041] Examples of acrylic acid / methacrylamidopropyl-trimethylammonium chloride (MAPTAC) / acrylamide copolymers include the compound represented by the following formula (c14) (compound c14).

[0042] [ka]

[0043] In equation (c14), p, q, r, and s are numbers that represent the number of repetitions in the repeating unit, respectively. Compound (c14) may be a random copolymer or a block copolymer.

[0044] Examples of DADMAC polymers include Merquat100 Polymer (trade name, weight-average molecular weight 190,000, manufactured by Lubrizol).

[0045] Examples of compound (c11) include Merquat295 Polymer (trade name, weight-average molecular weight 190,000, manufactured by Lubrizol) and Merquat740 Polymer (trade name, weight-average molecular weight 120,000, manufactured by Lubrizol).

[0046] Examples of compound (c12) include PAS-A-1 (trade name, weight-average molecular weight 5,000, manufactured by Nitto Boseki Medical Co., Ltd.).

[0047] Examples of compound (c13) include PAS-84 (trade name, weight-average molecular weight 20,000, manufactured by Nitto Boseki Medical Co., Ltd.).

[0048] Examples of compounds (c14) include Merquat2003 (trade name, weight-average molecular weight 1.2 million, manufactured by Lubrizol).

[0049] The weight-average molecular weight of component (C) is preferably 3,000 to 2,000,000, more preferably 4,000 to 1,500,000, and even more preferably 5,000 to 1,300,000. If the weight-average molecular weight of component (C) is above the lower limit, the spreadability of the water flow can be improved even when the water is used repeatedly. If the weight-average molecular weight of component (C) is within the above range, the spreadability of the water flow can be improved even when the water is used repeatedly. The weight-average molecular weight of component (C) is a value measured, for example, using the SEC-MALLS-RI system (measurement conditions: column = TSKgel α series α-M column 30 cm manufactured by Tosoh Corporation, solvent = 0.3 M aqueous solution of sodium nitrate).

[0050] The content of component (C) is preferably 0.2 to 4% by mass, more preferably 0.5 to 4% by mass, and even more preferably 0.8 to 4% by mass, based on the total mass of the liquid detergent composition. If the content of component (C) is above the lower limit, the spread of the water flow can be further enhanced. If the content of component (C) is below the upper limit, the spread of the water flow can be further enhanced.

[0051] The mass ratio of component (A) to component (C), expressed as (A) / (C) (A / C ratio), is preferably 0.2 to 12, more preferably 0.3 to 11, and even more preferably 0.3 to 9. If the A / C ratio is above the lower limit, the spreadability of the flowing water can be further enhanced. If the content of component (C) is below the upper limit, the spreadability of the flowing water can be enhanced even when the flowing water is used repeatedly.

[0052] <Optional ingredients> The liquid cleaning agent composition of the present invention may optionally contain, in addition to the above-mentioned components, components that are commonly used in toilet cleaning agent compositions. Examples of such optional components include water, organic solvents other than component (B), preservatives, chelating agents, disinfectants, antifungal agents, dyes, antioxidants, thickeners, ultraviolet absorbers, solubilizers, fragrances, pH adjusters, and the like.

[0053] The water content is preferably 80 to 95% by mass, and more preferably 88 to 94% by mass, relative to the total mass of the liquid detergent composition.

[0054] Examples of organic solvents include monohydric alcohols and glycol ethers. Examples of monohydric alcohols include ethanol and isopropanol. Examples of glycol ethers include ethylene glycol ethers such as ethylene glycol monomethyl ether, propylene glycol ethers such as propylene glycol monoethyl ether, dialkyl glycol ether solvents, monoethylene glycol monophenyl ether, and others.

[0055] Examples of preservatives include isothiazolinone-based preservatives such as benzisothiazolinone, methylisothiazolinone, butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, and dichlorooctylisothiazolinone. Among these, 1,2-benzisothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferred as preservatives.

[0056] As chelating agents, aminocarboxylic acid-based chelating agents include DEG (dihydroxyethylglycine), HEIDA (N-(2-hydroxyethyl)iminodiacetic acid), HEDTA (hydroxyethylethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid), DTPA (diethylenetriaminepentaacetic acid), HEDTA (hydroxyethylethylenediaminetriacetic acid), EDTA (ethylenediaminetetraacetic acid), MGDA (methylglycinediacetic acid), GLDA (L-glutamic acid diacetic acid), ASDA (aspartic acid diacetic acid), and EDDS. Examples of polycarboxylic acid chelating agents (non-nitrogen-containing) include ethylenediamine succinic acid, HIDS (hydroxyiminodisuccinic acid), IDS (iminodisuccinic acid), and salts (e.g., alkali metal salts) or hydrates of the above compounds, as well as acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, carboxymethyloxysuccinic acid, glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, or gluconic acid, or salts thereof.

[0057] While not particularly limited, it is preferable to use an alkaline agent selected from sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and its derivatives, monoethanolamine, diethanolamine, triethanolamine, etc., and more preferably an alkaline agent selected from sodium hydroxide, potassium hydroxide, monoethanolamine, and triethanolamine, with sodium hydroxide and potassium hydroxide being even more preferable. pH adjusters may be used individually or in combination of two or more types.

[0058] <Physical properties> The pH (25°C) of the liquid detergent composition is preferably 5 to 9, and more preferably 6 to 8. The pH (25°C) is the value measured at 25°C using a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.).

[0059] The viscosity (at 25°C) of the liquid detergent composition is preferably 0.8 to 50 mPa·s, more preferably 0.8 to 30 mPa·s, and even more preferably 0.8 to 10 mPa·s. When the viscosity is below the above upper limit, it is easier to aim when dispensing from the dispensing container in the usage method described later. The viscosity (at 25°C) is the value measured at 25°C using a B-type viscometer, with rotor number No. 1, rotor rotation speed of 60 rpm, 60 seconds after the start of rotor rotation.

[0060] (Manufacturing method) Liquid detergent compositions are manufactured by conventionally known manufacturing methods. For example, one method involves adding components (A) to (C) to water, which is the solvent, adding any optional components as needed, and mixing them together.

[0061] (How to use) One method of using the liquid cleaning agent composition is to place the liquid cleaning agent composition in a dispensing container, apply an appropriate amount of the liquid cleaning agent composition to the toilet bowl from the dispensing container, and then rinse it off with a flush or the like after a certain period of time. Another method of using the liquid cleaning agent composition involves applying an appropriate amount of the liquid cleaning agent composition to the toilet bowl and then scrubbing it with a cleaning brush. Alternatively, one method of use involves applying the liquid cleaning agent composition to the toilet seat or bathroom floor and then wiping it off with a cloth or paper towel.

[0062] Examples of dispensing containers for liquid detergent compositions include spray containers and squeeze containers. Among these, spray containers are preferred as dispensing containers for liquid detergent compositions because they offer excellent coating properties for the object to be cleaned. The dispensing container used in the present invention can be any container capable of dispensing the internal solution (liquid detergent), and examples include aerosol-type dispensing containers that dispense with high-pressure gas, and non-aerosol-type dispensing containers. Among these, non-aerosol-type dispensing containers are preferred in terms of usability and environmental impact. Examples of non-aerosol-type dispensing containers include spray type, squeeze type, and pump type. Among these, spray type is preferred in terms of usability. Examples of spray type include trigger spray type and pump spray type, and among these, trigger spray type is preferred in terms of ease of aiming.

[0063] Trigger-type sprayers come in two main types: direct pressure and stored pressure. Stored pressure is preferable due to its ease of aiming and longer spray retention. A pressurized sprayer is designed so that even when the trigger is operated, no liquid is sprayed from the nozzle until the liquid pressure inside the cylinder reaches a predetermined level. The liquid is then sprayed only when the liquid pressure inside the cylinder exceeds that level.

[0064] The discharge form can be either foam or mist, but foam is preferred for ease of targeting. One method of dispensing a foamy substance involves a container that mixes the contents with air to create a foamy substance before dispensing it; this is also known as a foamer container. A foam dispensing container typically comprises a container body that holds the detergent composition and a spray nozzle attached to the opening of the container body that dispenses the detergent composition contained within the container body as a foam to the outside. Common mechanisms for the spray nozzle to create a foam from the detergent composition inside the container body include introducing liquid from the container body into a foam-forming cylinder incorporated at the tip of the spray nozzle, causing the liquid to collide with the wall of the foam-forming cylinder to generate turbulence and promote mixing with air, or placing a barrier or mesh in front of the spray nozzle to create a foam. Air for generating the foam is introduced from outside the container. The detailed structure of these mechanisms is not particularly limited and can be based on conventionally known methods. An example of a trigger spray container is the one described in Japanese Patent Publication No. 2005-187601.

[0065] As described above, the liquid detergent composition of the present invention contains components (A) and (B), and therefore has excellent cleaning power and wiping properties. In addition, the liquid detergent composition of the present invention contains component (C), and therefore has excellent water spreadability. [Examples]

[0066] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. The ingredient amounts in the table are calculated on a pure content basis. In the table, the "appropriate amount" of pH adjuster refers to the amount required to bring the liquid detergent composition to pH 7. The "balance" of water refers to the amount required to bring the total volume of the liquid detergent composition to 100% by mass.

[0067] (Raw materials used) <(A) component> A-1: Lauric acid amidopropyl betaine, manufactured by Lion Specialty Chemicals Co., Ltd., "Energicol L-30B". A-2: Lauryldimethylaminoacetic acid betaine, manufactured by Sanyo Chemical Industries, Ltd., "Rebon LD-36". A-3: Stearyldimethylaminoacetic acid betaine, manufactured by Kao Corporation, "Anhitol 86B". A-4: 12-16 alkyl polyglucoside (APG), manufactured by Cognis, "PLANTACARE 1200up". A-5:AX, n-dodecyldimethylamine oxide, manufactured by Lion Specialty Chemicals Co., Ltd., "KadenaX DM12D-W".

[0068] <(B) component> B-1: Ethylene glycol monophenyl ether (phenoxyethanol), manufactured by Nippon Emulsifier Co., Ltd., "Phenyl glycol". B-2: Diethylene glycol monophenyl ether, manufactured by Nippon Emulsifier Co., Ltd., "Phenyl glycol (2 moles)". B-3: Hexaethylene glycol monophenyl ether, manufactured by Nippon Emulsifier Co., Ltd., "Phenyl glycol (5.5 mol)".

[0069] <(B') component> (B) component comparison product B'-1: Diethylene glycol monobutyl ether, manufactured by Nippon Emulsifier Co., Ltd., "butyl diglycol". • B'-2: Propylene glycol, manufactured by Dow Chemical Company, "Propylene Glycol".

[0070] <(C) component> C-1: Acrylic acid, DADMAC copolymer, manufactured by Lubrizol, trade name "Merquat295 Polymer", 5 mol% acrylic acid monomer, 95 mol% diallyldimethylammonium monomer (c2 / c1 ratio = 0.05). • C-2: DADMAC Polymer, manufactured by Lubrizol, trade name "Merquat100 Polymer", 100 mol% diallyldimethylammonium monomer. C-3: DADMAC acrylamide copolymer, manufactured by Lubrizol, trade name "Merquat740", 76 mol% acrylamide monomer, 24 mol% diallyldimethylammonium monomer (c2 / c1 ratio = 3.2). C-4: DADMAC-sulfur dioxide copolymer, manufactured by Nitto Boseki Medical Co., Ltd., product name "PAS-a-1". C-5: Maleic acid, DADMAC, sulfur dioxide copolymer, manufactured by Nitto Boseki Medical Co., Ltd., product name "PAS-84". C-6: Acrylic acid, MAPTAC, acrylamide copolymer, manufactured by Lubrizol, trade name "Merquat2003", 10 mol% acrylic acid, 40 mol% MAPTAC, 50 mol% acrylamide (c2 / c1 ratio = 1.5).

[0071] <(C') component> (C) component comparison product C'-1: Polyethyleneimine, manufactured by Nippon Shokubai Co., Ltd., product name "SP-003", mass-average molecular weight (Mw) 300. C'-2: Cationized cellulose, manufactured by Dow Chemical Company, trade name "RBC-227", 2.625% by mass aqueous solution of cationized cellulose. C'-3: Dimethylamine-ammonia-epichlorohydrin copolymer, manufactured by Senka Co., Ltd., product name "Unisense KHE1000L", molecular weight 20,000-100,000.

[0072] <Optional ingredients> pH adjusters: Sulfuric acid (Kanto Chemical Co., Ltd.), potassium hydroxide (liquid potassium hydroxide, manufactured by Asahi Glass Co., Ltd.). • Polyvinyl alcohol: Manufactured by Kuraray Co., Ltd., product name "PVA-217". • Ethanol: Manufactured by Nippon Alcohol Sales Co., Ltd., "Synthetic 95%". • Fragrance: Fragrance composition A as specified in Japanese Patent Publication No. 2003-183697. • Water: Ion-exchanged water.

[0073] (Evaluation method) <Wipeability> Teng of each example liquid cleaning agent composition was placed on a ceramic plate, and it was rubbed once with toilet paper (5cm x 5cm). After the ceramic plate dried, the surface was checked for wiping marks and evaluated according to the evaluation criteria below.

[0074] ≪Evaluation Criteria≫ 5 points: Absolutely no stickiness. 4 points: It's not sticky at all. 3 points: A small amount of the liquid cleaning agent composition remains, and there is a slight stickiness, but it is not bothersome. Two points: There is some residue of the liquid detergent composition. 1 point: There is residue of the liquid cleaning agent composition throughout.

[0075] <Cleaning power> 100 μL of urine, collected and mixed from five adult males, was placed on a 25 mm x 100 mm ceramic plate and left at 28°C for 18 hours to dry. After drying, 1 mL of each liquid detergent composition was dropped onto the ceramic plate and left for 60 seconds. After washing the ceramic plate with tap water (flow rate 10 mL / s) for 20 seconds, five expert panelists visually evaluated the degree of remaining staining based on the evaluation criteria below. The average of the expert panelists' evaluation scores was calculated.

[0076] ≪Cleaning Power≫ 5 points: The dirt has been removed extremely well. 4 points: Very clean. 3 points: The dirt has been removed quite well. 2 points: Some of the dirt has been removed. 1 point: The stains haven't come off.

[0077] <Spreadability of flowing water> 500 μL of each example's liquid cleaning agent composition was applied to a 50 mm x 100 mm ceramic plate. The surface coated with the liquid cleaning agent composition was rinsed with tap water at a flow rate of 10 mL / s for 20 seconds. The rinsed ceramic plate was dried at 25°C for 8 hours. After drying, the ceramic plate was tilted at 45°C, and tap water was flowed onto one end of the ceramic plate at a flow rate of 5 mL / s for 20 seconds (flowing water operation). In the flowing water operation, tap water was flowed onto the surface of the ceramic plate from a φ5 mm tube. The flowing water operation was performed five times, and the spread of the water was visually checked immediately after the first and fifth operations, and evaluated according to the evaluation criteria below.

[0078] ≪Evaluation Criteria≫ 5 points: The water flow spreads excessively across the ceramic plate compared to the width of the tube's outlet. 4 points: Compared to the width of the tube's outlet, the flowing water spreads out very widely on the ceramic plate. 3. The water flow spreads considerably over the ceramic plate compared to the width of the tube's outlet. Two points: The flowing water spreads out somewhat on the ceramic plate compared to the width of the tube's outlet. 1. The water flow does not spread evenly across the ceramic plate compared to the width of the tube's outlet.

[0079] (Examples 1-31, Comparative Examples 1-8) According to the compositions shown in Tables 1-4, components (A) to (C) and any optional components were added to water and mixed to prepare the liquid detergent compositions for each example. The amounts listed in the table are calculated on a net basis. Additionally, ingredients whose amounts are not listed in the table are not included. For each example of a liquid detergent composition, its wiping ability, cleaning power, and water spreadability were evaluated, and the results are shown in the table. However, Examples 1-23, 26, and 28-31 are for reference only.

[0080] [Table 1]

[0081] [Table 2]

[0082] [Table 3]

[0083] [Table 4]

[0084] As shown in Tables 1-4, Examples 1-31 to which the present invention was applied all received a rating of 3 or higher for wiping performance, cleaning power, and water spreadability (1 time and 5 times). Comparative Example 1, which did not contain component (A), received a score of 1 for its wipeability. Comparative Example 2, which did not contain component (B), and Comparative Examples 3-4, which contained component (B') instead of component (B), received a cleaning power evaluation of 1-2 points. Comparative Example 5, which did not contain component (C), and Comparative Examples 6-8, which contained component (C') instead of component (C), had a water spread rate (1 time and 5 times) of 2 points. From the above results, it was confirmed that applying the present invention results in excellent wiping and cleaning power, as well as excellent water spreadability.

Claims

[Claim 1] (A) Ingredients: Surfactant and (B) Component: A compound represented by the following formula (b1), (C) Component: A polymer having a repeating unit (c1) derived from a monomer having a quaternary ammonium group, and a repeating unit (c2) which is at least one selected from a repeating unit (c2-1) derived from acrylic acid and a repeating unit (c2-2) derived from acrylamide, A liquid toilet cleaner composition containing, The aforementioned component (A) is one or more selected from betaine-based surfactants, alkyl polyglucosides, and amine oxide-type surfactants. The aforementioned component (C) is, diallyldimethylammonium chloride / acrylamide copolymer (where the molar ratio expressed as [repeating unit (c2)] / [repeating unit (c1)] is greater than 0 and less than or equal to 4), Acrylic acid / methacryloylamidopropyltrimethylammonium chloride / acrylamide copolymer (where the molar ratio expressed as [repeating unit (c2)] / [repeating unit (c1)] is greater than 0 and less than or equal to 4), And, Diallyldimethylammonium chloride / sulfur dioxide copolymer, One or more types selected from, The content of component (A) is 0.5 to 5% by mass relative to the total mass of the liquid toilet cleaning agent composition. The content of component (B) is 0.2 to 4.5% by mass relative to the total mass of the liquid toilet cleaning agent composition. The content of component (C) is 0.2 to 4% by mass relative to the total mass of the liquid toilet cleaning agent composition. A liquid toilet cleaning agent composition having a mass ratio of 0.2 to 12 between component (A) and component (C). 【Chemistry 1】 [In formula (b1), R1 is an alkylene group having 2 or 3 carbon atoms, and m is a number from 1 to 6.]

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