Liquid detergent for toilet and toilet liquid detergent product

Abstract

To provide a liquid detergent for toilet that is superior in low-temperature foamability, foam breakability, and urine cleaning capability.SOLUTION: A toilet liquid detergent includes: (A1) an alkyl polyglycoside represented by R-O-[G]n (where R is an alkyl group having 8 to 18 carbon atoms, G is a glycoside residue, and n is an average degree of condensation, being a number of 1 to 5); (A2) a polyoxyalkylene alkyl ether represented by R11-(OR12)m-OH (where R11 is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, R12 is an alkylene group having 2 or 3 carbon atoms, and m is an average repetition number of (OR12), being a number of 16 to 70); and (B) an aminocarboxylic acid-based chelating agent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid toilet cleaner and a liquid toilet cleaner product.

Background Art

[0002] As a cleaner for hard surfaces such as housing facilities, a foam spray type cleaner that discharges foam from a spray container tends to be preferred in terms of convenience and cleaning effect. As a foam spray type liquid toilet cleaner using a chelating agent, for example, a cleaner composition described in Patent Document 1 has been proposed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] It is desirable to have a product that takes into account that liquid toilet cleaners are used in a relatively low-temperature environment. For this reason, there is a demand for a toilet cleaner that has a large amount of foam when sprayed at low temperatures (good low-temperature foaming property), the foam disappears moderately easily (good foam breakability), and has good detergency against urine stains. However, it has been difficult for conventional technologies to fully meet these requirements. An object of the present invention is to provide a liquid toilet cleaner having good low-temperature foaming property, foam breakability, and detergency against urine stains.

Means for Solving the Problems

[0005] The present invention has the following aspects. [1] Component (A1): An alkyl polyglycoside represented by the following formula (1), Component (A2): A polyoxyalkylene alkyl ether represented by the following formula (2), and (B) Component: A liquid toilet cleaner containing an aminocarboxylic acid chelating agent. R-O-[G]n ···(1) [In the formula, R is an alkyl group having 8 to 18 carbon atoms, G is a glycoside residue, and n is the average degree of condensation and is a number from 1 to 5.] R 11 -(OR 12 )m-OH ···(2) (In the formula, R 11 is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, R 12 is an alkylene group having 2 or 3 carbon atoms, and m is the average number of repetitions of (OR 12 ) and is a number from 16 to 70.) [2] The liquid toilet cleaner according to [1], wherein the mass ratio (A1) / (A2) representing the content of the component (A1) to the content of the component (A2) is 0.3 to 10. [3] The liquid toilet cleaner according to [1] or [2], wherein the mass ratio (A1) / (B) representing the content of the component (A1) to the content of the component (B) is 0.1 to 6. [4] Further, the liquid toilet cleaner according to any one of [1] to [3], which contains a component (C): a carboxylic acid chelating agent (excluding the component (B)). [5] The liquid toilet cleaner according to [4], wherein the total content of the component (B) and the component (C) is 1 to 3.2% by mass based on the total mass of the liquid toilet cleaner. [6] A liquid toilet cleaner product having the liquid toilet cleaner according to any one of [1] to [5] and a discharge container containing the liquid toilet cleaner.

Advantages of the Invention

[0006] According to the present invention, a liquid toilet cleaner having good low-temperature foaming property, foam-breaking property, and detergency against urine stains can be obtained.

Embodiments for Carrying Out the Invention

[0007] ≪Liquid Toilet Cleaner≫ The liquid toilet cleaner of the present embodiment (hereinafter also simply referred to as the liquid cleaner) is a composition containing component (A1), component (A2), and component (B). Further, it may contain one or more selected from component (C), component (D), component (E), component (F), and component (G). In this specification, the numerical range represented by "~" means a numerical range with the numerical values before and after "~" as the lower limit value and the upper limit value, respectively.

[0008] <Component (A1)> Component (A1) is an alkyl polyglycoside. Examples of the alkyl polyglycoside include compounds represented by the general formula (1). R-O-[G]n ···(1) [In the formula, R is an alkyl group having 8 to 18 carbon atoms, G is a glycoside residue, and n is the average degree of condensation and is a number from 1 to 5.]

[0009] The alkyl group represented by R is preferably linear. From the viewpoint of detergency, in formula (1), the number of carbon atoms of R is preferably 8 to 16, more preferably 8 to 10. G is a glycoside residue. The reducing sugar that is the raw material of the glycoside may be either an aldose or a ketose. Examples of the reducing sugar include trioses, tetroses, pentoses, and hexoses having 3 to 6 carbon atoms. Specific examples of aldoses include apiose, arabinose, galactose, glucose, lyxose, mannose, gulose, allose, idose, talose, and xylose. Specific examples of ketoses include fructose. Among these, aldopentoses or aldohexoses having 5 or 6 carbon atoms are preferred. Among them, glucose is most preferred. That is, G is most preferably a glucoside residue. In the general formula (1), n represents the average degree of condensation of the sugar, preferably a number from 1 to 2, particularly preferably a number from 1 to 1.5.

[0010] (Component (A1) may be synthesized by a conventionally known manufacturing method or may be a commercially available product. Examples of the product names of commercially available products include GreenAPG 1214, GreenAPG 0810 (Nikko Chemicals Co., Ltd.), Myadol 10 (Kao Corporation), Triton CG-10 (Dow DuPont Co., Ltd.), Glucopon650, Glucopon215up (BASF), EcoSense 919 (Dow Chemical Company), AG6210 (Nouryon), etc.)

[0011] <(Component (A2))> (Component (A2) is a polyoxyalkylene alkyl ether.) Examples of the polyoxyalkylene alkyl ether include compounds represented by the general formula (2).

[0012] R 11 -(OR 12 )m-OH ···(2) In formula (2), R 11 is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, OR 12 is an oxyalkylene group having 2 or 3 carbon atoms, and m represents the average number of repetitions of OR 12 and is a number from 16 to 70.

[0013] R 11 The aliphatic hydrocarbon group which is R 11 may be linear or branched. R 11 may be a saturated hydrocarbon or an unsaturated hydrocarbon. R R 11 Preferably, R 11 is a linear or branched alkyl group or a linear or branched alkenyl group. When the number of carbon atoms of R

[0014] OR 12 is an oxyethylene group or an oxypropylene group, and these may be mixed.) OR 2As for this, an oxyethylene group is preferable. When an oxyethylene group and an oxypropylene group are mixed, they may be mixed randomly or in a block form. m is a number from 16 to 70, preferably from 31 to 70, and more preferably from 45 to 65. If m is at least the above lower limit value, the foaming property is further enhanced and the amount of foam increases. If m is at most the above upper limit value, the foaming property is good and the handling when made into a composition is also good.

[0015] <Component (B)> Component (B) is an aminocarboxylic acid-based chelating agent. Component (B) has a nitrogen atom and a carboxy group. (B) components include, for example, DEG (dihydroxyethylglycine: N-(2-hydroxylethyl)glycine), HEIDA (N-(2-hydroxyethyl)iminodiacetic acid), HEDTA (hydroxyethyl ethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid), DTPA (diethylenetriaminepentaacetic acid), HEDTA (hydroxyethyl ethylenediamine triacetic acid), EDTA (ethylenediaminetetraacetic acid), MGDA (methylglycine diacetic acid), GLDA (L-glutamic acid diacetic acid), ASDA (aspartic acid diacetic acid), EDDS (ethylenediamine disuccinic acid), HIDS (hydroxyiminodisuccinic acid), IDS (iminodisuccinic acid), and salts (e.g., alkali metal salts) and hydrates of the above compounds. Among them, MGDA, GLDA, EDTA, and their alkali metal salts are preferred. (B) component may be used alone or in combination of two or more.

[0016] <(C) component> (C) component is a carboxylic acid chelating agent (excluding (B) component). (C) component has a carboxy group and does not contain a nitrogen atom. The carboxy group may form a salt. (C) component may have only a carboxy group as a functional group, or may have a functional group other than a carboxy group. Examples of the (C) component having a functional group other than a carboxy group include hydroxycarboxylic acid (salt). Examples of the (C) component include 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, gluconic acid, or salts thereof. Among them, citric acid, malic acid, and lactic acid are particularly preferable as the (C) component. (C) component may be used alone or in combination of two or more.

[0017] <(D) component> The liquid detergent of the present embodiment may further contain a compound represented by the following formula (3) as the (D) component. The (D) component is a glycol ether, which is a so-called glycol type solvent.

[0018]

Chemical formula

[0019] In formula (3), R 13 is an alkylene group having 2 or 3 carbon atoms. That is, OR 13 is an oxyalkylene group. R 13 is an ethylene group or a propylene group, preferably an ethylene group. k is the average repetition number of (OR 13 ), that is, the average addition mole number of ethylene oxide or propylene oxide. k is a number from 1 to 6, preferably from 1 to 3, and more preferably 1. Examples of the (D) component include monoethylene glycol monophenyl ether, triethylene glycol monophenyl ether, monopropylene glycol monophenyl ether, tripropylene glycol monophenyl ether, etc. Among them, from the viewpoint of detergency, as the component (D), monoethylene glycol monophenyl ether is particularly preferable. The component (D) may be used alone or in combination of two or more.

[0020] <(E) component> The liquid detergent of the present embodiment may further contain one or more selected from the compounds represented by the following formulas (E-1), (E-2), and (E-3) (hereinafter also referred to as the (E-1) component, the (E-2) component, and the (E-3) component, respectively) as the component (E). The component (E) is a quaternary ammonium salt and is a cationic surfactant. The component (E) contributes to the improvement of the sterilization effect of the toilet.

[0021]

Chemical formula

[0022] In formula (E-1), two or more of R 1 ~R 4 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and the rest are a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms. Z - is a halogen ion or an alkyl sulfate ion.

[0023] In formula (E-2), R 5 is a linear or branched alkyl group having 8 to 16 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms. R 6 is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or an aromatic hydrocarbon group having 5 to 20 carbon atoms. x and y represent the average number of repeating units of the oxyethylene group, and are each independently a number of 0 or more, and x + y is 10 or more. Z - is a halogen ion or an alkyl sulfate ion.

[0024] In formula (E-3), R 7 and R8 is, independently of one another, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R 9 is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, and R 10 is an alkylene group having 1 to 3 carbon atoms. Z - is a counter ion.

[0025] Among the (E-1) component, (E-2) component, and (E-3) component, the (E-1) component is more preferable. In formula (E-1), one or two of R 1 ~R 4 are preferably a linear or branched alkyl group having 8 to 18 carbon atoms, or a linear or branched alkenyl group having 8 to 18 carbon atoms. Further, it is preferable that only one of R 1 ~R 4 is a linear or branched alkyl group having 8 to 18 carbon atoms, or a linear or branched alkenyl group having 8 to 18 carbon atoms. The alkyl group which is any of R 1 ~R 4 is preferably linear. The alkenyl group which is any of R 1 ~R 4 is preferably linear. The carbon number of the alkyl group or alkenyl group which is any of R 1 ~R 4 is more preferably 10 to 16.

[0026] Examples of component (E) include lauryltrimethylammonium salt, cetyltrimethylammonium salt, stearyltrimethylammonium salt, dioctyldimethylammonium salt, dinonyldimethylammonium salt, didecyldimethylammonium salt, diundecyldimethylammonium salt, didodecyldimethylammonium salt, octylnonylammonium salt, octyldecyldimethylammonium salt, octylundecyldimethylammonium salt, octyldodecyldimethylammonium salt, nonyldecyldimethylammonium salt, nonylundecyldimethylammonium salt, nonyldodecyldimethylammonium salt, decylundecyldimethylammonium salt, decyldodecyldimethylammonium salt, undecyldodecyldimethylammonium salt, benzyldodecylammonium salt, and the like. Among these, from the viewpoints of easy availability and improvement of detergency, lauryltrimethylammonium salt, cetyltrimethylammonium salt, stearyltrimethylammonium salt, dioctyldimethylammonium salt, didecyldimethylammonium salt, and didodecyldimethylammonium salt are preferred; lauryltrimethylammonium salt, cetyltrimethylammonium salt, dioctyldimethylammonium salt, and didecyldimethylammonium salt are more preferred; lauryltrimethylammonium salt, cetyltrimethylammonium salt, dioctyldimethylammonium salt, and benzyldodecyldimethylammonium salt are even more preferred.

[0027] In formula (E-1), formula (E-2), and formula (E-3), the counter ion Z - Examples thereof include halide ion, alkyl sulfate ion, sulfate ion, alkylbenzene sulfonate ion, alkyl carbonate ion, and carbonate ion. Among them, halide ion and alkyl sulfate ion are preferred, and halide ion is more preferred. Examples of the halide ion include chloride ion, bromide ion, and iodide ion. Among them, chloride ion is preferred.

[0028] In particular, as the component (E), lauryltrimethylammonium chloride, decyltrimethylammonium chloride, stearyltrimethylammonium chloride, dioctyldimethylammonium chloride, didodecyldimethylammonium chloride, didodecyldimethylammonium chloride, and benzyldodecyldimethylammonium chloride are preferable, lauryltrimethylammonium chloride, decyltrimethylammonium chloride, dioctyldimethylammonium chloride, didodecyldimethylammonium chloride, and benzyldodecyldimethylammonium chloride are more preferable, and lauryltrimethylammonium chloride, decyltrimethylammonium chloride, and dioctyldimethylammonium chloride are even more preferable.

[0029] As the component (E), those synthesized by a conventionally known production method may be used, or commercially available products may be used. Examples of the product names of commercially available products include "Lipcard series" (Lion Specialty Chemicals Co., Ltd.), "Econol", "Revon series", "Cation DSV", "Cation LQ" (Sanyo Chemical Industries, Ltd.), "Bardac LF80" (Lonza Japan Co., Ltd.), "Didodecyldimethylammonium chloride" (Tokyo Ohka Kogyo Co., Ltd.), and the like. As the component (E), one kind may be used alone, or two or more kinds may be used in combination.

[0030] <(F) component> The liquid detergent of the present embodiment may contain a lower alcohol as the component (F). The component (F) contributes to the improvement of foam breakage. In addition, in the method of spraying the foam of the liquid detergent on the toilet seat or the floor and then wiping it with toilet paper or the like, it contributes to the improvement of the wiping property that it is difficult to leave wiping marks or stickiness. As the lower alcohol, a linear or branched monohydric alcohol having 1 to 6 carbon atoms is preferable, and a linear or branched saturated monohydric alcohol having 1 to 6 carbon atoms is more preferable. The number of carbon atoms of the lower alcohol is preferably 1 to 4, more preferably 2 to 3. Examples of the lower alcohol include ethanol, n-propanol, isopropanol, butanol, etc. Among these, ethanol and isopropanol are preferred, and ethanol is more preferred. The lower alcohol may be used alone or in combination of two or more.

[0031] <(G) component> The liquid detergent of the present embodiment may further contain one or more selected from aromatic sulfonic acids, aromatic carboxylic acids, and salts thereof as the (G) component. The (G) component is a hydrotrope (other than ethanol). The (G) component mainly contributes to the foaming power of the composition. As the (G) component, at least one selected from the group consisting of toluenesulfonic acid, toluenesulfonate, cumenesulfonic acid, cumenesulfonate, benzoic acid, and benzoate is preferable in terms of excellent effect of improving storage stability particularly under low temperature conditions. Two or more may be mixed and used. Toluenesulfonic acid, toluenesulfonate, cumenesulfonic acid, and cumenesulfonate as the (G) component may be any of the three isomers of o-form, m-form, and p-form, and among these, the p-form is preferable because it is easily available. Among them, cumenesulfonic acid and cumenesulfonate are preferable from the viewpoint of foamability. Examples of the salt form in toluenesulfonate, cumenesulfonate, and benzoate include salts of alkali metals such as sodium and potassium; salts of alkaline earth metals such as magnesium and calcium; ammonium salts; and alkanolamine salts such as monoethanolamine, diethanolamine, and triethanolamine. Among them, salts of alkali metals are preferable, and sodium salts are more preferable.

[0032] <Other surfactants> The liquid detergent may contain other surfactants that do not fall under any of the above (A1) component, (A2) component, and (E) component. As other surfactants, nonionic surfactants other than the (A1) component and the (A2) component, cationic surfactants other than the (E) component, amphoteric surfactants (hereinafter also referred to as the (A3) component), anionic surfactants (hereinafter also referred to as the (A4) component), and amine oxide type surfactants (hereinafter also referred to as the (A5) component) can be mentioned. Other surfactants can be appropriately selected and used from known surfactants according to the purpose. Other surfactants may be used alone or in combination of two or more.

[0033] [(A3) component] Examples of the amphoteric surfactant as the (A3) component include betaine-based amphoteric surfactants and amino acid-based amphoteric surfactants. Among these, betaine-based amphoteric surfactants are preferred. Examples of the betaine-based amphoteric surfactant include carboxybetaine-based amphoteric surfactants, amidobetaine-based amphoteric surfactants, sulfobetaine-based (hydroxysulfobetaine-based, amidosulfobetaine-based) amphoteric surfactants, imidazolinium betaine-based amphoteric surfactants, phosphobetaine-based amphoteric surfactants, aminopropionic acid-based amphoteric surfactants, (7) amino acid-based amphoteric surfactants, etc. Carboxybetaine-based amphoteric surfactants and amidobetaine-based amphoteric surfactants are preferred, and amidobetaine-based amphoteric surfactants are more preferred.

[0034] Examples of the carboxybetaine-based amphoteric surfactant include lauric acid dimethylaminoacetic acid betaine, myristyl dimethylaminoacetic acid betaine, stearyl dimethylaminoacetic acid betaine, etc.

[0035] Examples of the amidobetaine-based amphoteric surfactant include coconut oil fatty acid amidopropyl betaine (cocamidopropyl betaine), lauric acid amidopropyl betaine, isostearamide propyl betaine, etc.

[0036] Examples of sulfobetaine amphoteric surfactants include coconut oil fatty acid dimethylaminohydroxy sulfobetaine, lauryldimethylaminohydroxy sulfobetaine, lauryl hydroxy sulfobetaine, coconut oil fatty acid dimethylsulfopropyl betaine, lauryl sulfobetaine, stearyl sulfobetaine, myristyl sulfobetaine, etc.

[0037] Examples of imidazolinium betaine amphoteric surfactants include coconut oil alkyl-N-hydroxyethyl imidazolinium betaine, coconut oil alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, etc.

[0038] Examples of sulfobetaine amphoteric surfactants include lauryl hydroxyphosphobetaine, etc.

[0039] Examples of aminopropionic acid amphoteric surfactants include sodium laurylaminodipropionate, triethanolamine laurylaminodipropionate, etc.

[0040] Examples of amino acid amphoteric surfactants include lauryl amino fatty acid salts, stearyl amino fatty acid salts, myristyl amino fatty acid salts, etc.

[0041] Among the above, as the component (A3), 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.

[0042] (A3) component is commercially available. Examples of the product names of (A3) component include "Enajicol L-30B (manufactured by Ichifunka Oil Industry Co., Ltd.)" which is lauramidopropyl betaine, "CAB-30 (manufactured by Lion Specialty Chemicals Co., Ltd.)" which is coconut oil fatty acid amide propyl betaine, "TEGOBETAIN CK-OK (manufactured by EVONIK)" which is coconut oil fatty acid amide propyl betaine, "Ampholex PB-1 (manufactured by Miyoshi Oil & Fat Co., Ltd.)" which is palm kernel oil fatty acid amide propyl betaine, "Revon LD-36 (manufactured by Sanyo Chemical Industries, Ltd.)" and "Obazolin LB-SF (manufactured by Toho Chemical Industry Co., Ltd.)" which are lauryldimethylaminoacetate betaine, and "Anhitol 86B (manufactured by Kao Corporation)" which is stearyldimethylaminoacetate betaine.

[0043] [(A4) component] As the (A4) component, conventionally known anionic surfactants can be used, and examples include the following surfactants (1) to (11). (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 an alkyl (or alkenyl) ether sulfate (AES) having a linear or branched 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 on average by 0.5 to 10 moles. (6) Any of alkylene oxides having 2 to 4 carbon atoms, or an alkyl (or alkenyl) phenyl ether sulfate having a linear or branched 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 on average by 3 to 30 moles. (7) An alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group with 10 to 20 carbon atoms to which any one of alkylene oxides 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) is added on average by 0.5 to 10 moles. (8) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl 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) having 10 to 20 carbon atoms.

[0044] Examples of the above 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 salts (monoethanolammonium), diethanolamine salts (diethanolammonium), and triethanolamine salts (triethanolammonium); ammonium salts, etc. Among them, sodium salts and potassium salts are preferred.

[0045] [Component (A5)] Examples of the amine oxide type surfactant (semi-polar surfactant) as the component (A5) include alkylamine oxides such as dodecyldimethylamine oxide, myristyldimethylamine oxide, and coconut alkyl dimethylamine oxide; amidoamine oxides such as coconut oil fatty acid amidopropylamine oxide and lauric acid amidopropylamine oxide. Among them, dodecyldimethylamine oxide is preferred.

[0046] <Water> From the viewpoints of ease of handling during production and solubility in water during use, etc., the liquid detergent preferably contains water as a solvent. Examples of water include ion-exchanged water and pure water. The water content is preferably 80 to 98% by mass, more preferably 90 to 95% by mass, based on the total mass of the liquid detergent.

[0047] <Other optional components> The liquid detergent can, if necessary, contain, in addition to the above components, components that can usually be used in liquid detergents for toilets. Examples of such optional components include organic solvents, preservatives, chelating agents, bactericides, preservatives, antifungal agents, pigments, antioxidants, thickeners, ultraviolet absorbers, solubilizers, fragrances, pH adjusters, and the like.

[0048] The pH adjuster is not particularly limited, but it is preferably sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and its derivatives, monoethanolamine, diethanolamine, or triethanolamine; more preferably sulfuric acid, sodium hydroxide, potassium hydroxide, monoethanolamine, or triethanolamine; and even more preferably sulfuric acid, sodium hydroxide, or potassium hydroxide. The pH adjuster may be one type or a combination of two or more types.

[0049] <Content ratio> In the liquid detergent, the components (A1) and (A2) are nonionic surfactants and are components that affect foaming properties and foam breakage properties. In the liquid detergent, the component (A1) contributes to the improvement of foaming properties. If there is too much of the component (A1), the foam breakage property tends to become insufficient. The component (A2) contributes to the improvement of detergency. If there is too much of the component (A2), the foaming property tends to become insufficient. The content of the component (A1) is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 3.0% by mass, based on the total mass of the liquid detergent. The content of the component (A2) is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 3.0% by mass, based on the total mass of the liquid detergent. With respect to the total mass of the liquid detergent, (A1+A2), which represents the total content of the (A1) component and the (A2) component, is preferably 0.5 to 10% by mass, more preferably 0.5 to 5% by mass, and still more preferably 1 to 5% by mass.

[0050] In the liquid detergent, (A1) / (A2), which represents the mass ratio of the content of the (A1) component to the content of the (A2) component, is preferably 0.3 to 10, more preferably 0.5 to 6, and still more preferably 0.5 to 3. When (A1) / (A2) is at least the lower limit of the above range, the foaming property is excellent, and when it is at most the upper limit, the detergency is excellent.

[0051] (B) component contributes to the improvement of detergency. If there is too much (B) component, the foaming property tends to be insufficient. With respect to the total mass of the liquid detergent, the content of the (B) component is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 2.0% by mass, and still more preferably 0.8 to 2.0% by mass. (A1) / (B), which represents the mass ratio of the content of the (A1) component to the content of the (B) component, is preferably 0.1 to 6, more preferably 0.2 to 3, and still more preferably 0.4 to 2. When it is at least the lower limit of the above range, the foaming property is excellent, and when it is at most the upper limit, the detergency is excellent.

[0052] (C) component contributes to the improvement of detergency. If there is too much (C) component, the foaming property tends to be insufficient. With respect to the total mass of the liquid detergent, the content of the (C) component is preferably 0.01 to 5.0% by mass, more preferably 0.1 to 1.0% by mass. (B+C), which represents the total of the content of the (B) component and the content of the (C) component, is preferably 1 to 3.2% by mass, more preferably 1.6 to 2.6% by mass. When (B+C) is at least the lower limit of the above range, the detergency is excellent, and when it is at most the upper limit, the foaming property is excellent. (B) / (C), which represents the mass ratio of the content of the (B) component to the content of the (C) component, is preferably 0.2 to 160, more preferably 1 to 20, and still more preferably 1.1 to 6. If (B) / (C) is within the above range, the detergency is enhanced.

[0053] (D) component contributes to the bactericidal effect. The content of (D) component is preferably 0.2 to 5% by mass, more preferably 0.5 to 3% by mass, based on the total mass of the liquid detergent.

[0054] (E) component contributes to the bactericidal effect. The content of (E) component is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, based on the total mass of the liquid detergent.

[0055] By adding (F) component in addition to (A1) component and (A2) component, the foam breakage property and wiping property can be improved. The content of (F) component is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, still more preferably 2.5 to 5% by mass, based on the total mass of the liquid detergent.

[0056] (G) component contributes to the foaming property. The content of (G) component is preferably 0.1 to 3% by mass, more preferably 0.1 to 1% by mass, still more preferably 0.1 to 0.3% by mass, based on the total mass of the liquid detergent. When the content of (G) component is not less than the lower limit value of the above range, the transparent appearance of the liquid detergent can be more stably maintained during storage over time even under low temperature conditions. When it is not more than the upper limit value, the foaming and the persistence of the foam amount are further improved. By using (G) component and (F) component in combination, the low temperature stability can be further improved. In particular, it is preferable to use (G) component and ethanol in combination.

[0057] The ratio of (A1 + A2) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, based on the total mass of the nonionic surfactant contained in the liquid detergent. It may be 100% by mass. The ratio of (E) component is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, based on the total mass of the cationic surfactant contained in the liquid detergent. It may be 100% by mass.

[0058] <Physical properties> The pH of the liquid detergent at 25°C is preferably from 4 to 10, more preferably from 4 to 8. In this specification, the pH of the liquid detergent is a value measured by a method in accordance with JIS Z 8802:2011 "pH Measurement Method".

[0059] <Toilet liquid detergent product> A toilet liquid detergent product (hereinafter sometimes simply referred to as "liquid detergent product") has a discharge container and the toilet liquid detergent of the present invention accommodated in the discharge container.

[0060] Examples of the discharge container for accommodating the liquid detergent include a spray container and a squeeze container. Among them, a spray container is preferred because of its excellent coating property for the object to be cleaned. Examples of the spray container include an aerosol spray container, a trigger spray container (direct pressure type or accumulator type), a dispenser spray container, etc. These containers may be manual or electric. Examples of the aerosol spray container include those described in, for example, JP-A-9-3441 and JP-A-9-58765. When filling an aerosol spray container, LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide gas, nitrogen gas, nitrous oxide gas, etc. can be used as the propellant. These propellants may be used alone or in combination of two or more. Examples of the trigger spray container include those described in, for example, JP-A-9-268473 and JP-A-10-76196. Examples of the dispenser spray container include those described in, for example, JP-A-9-256272. Examples of the accumulator type trigger spray container include those described in, for example, JP-A-2013-154276.

[0061] <Manufacturing method> The liquid detergent is manufactured by a conventionally known manufacturing method. For example, there is a method of adding the components (A1), (A2), (B), and (C) to water and mixing them. The liquid detergent product is manufactured by manufacturing the liquid detergent by the above method and storing it in a discharge container.

[0062] <Usage method> As a usage method of the liquid detergent, for example, there is a usage method of storing the liquid detergent in a discharge container, applying an appropriate amount of the liquid detergent from this discharge container to the toilet bowl, and rinsing it with running water after a certain period of time, that is, "rinsing and washing". Also, as another usage method, there is a usage method of applying an appropriate amount of the liquid detergent to the toilet bowl and scrubbing it with a cleaning brush, that is, "scrubbing and washing". Alternatively, there is a usage method of applying the liquid detergent to the toilet seat, the floor of the toilet, etc. and wiping it off with a cloth or paper, that is, "wiping and washing".

[0063] The liquid detergent for toilet of the present embodiment is excellent in low-temperature foaming property, foam breakability, and detergency against urine stains. Although the reason for obtaining such an effect is not clear, it is considered that the cleaning power by the component (B) is enhanced because (B) dissolves in the foam formed using the components (A1) and (A2), and the contact state between the surface to be cleaned and the component (B) becomes good. In particular, it is considered that the component (A2) contributes to the solubilization of the component (B).

Examples

[0064] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.

[0065] (Raw materials used) (A1) component: alkyl polyglycoside ·A1-1: C8-10APG, product name "Glucopon215up" manufactured by BASF, a compound in which R is a linear alkyl group having 8 to 10 carbon atoms, G is a glucoside residue, and n is 1.5 in the formula (1). ·A1-2: C8-16 APG, the product name "Glucopon 650" manufactured by BASF, a compound in formula (1) where R is a linear alkyl group with 8 to 16 carbon atoms, G is a glucoside residue, and n is in the range of 1 to 1.5. ·A1-3: C8+C10 APG, the product name "AG6210" manufactured by Nouryon, a compound in formula (1) where R is a linear alkyl group with 8 and 10 carbon atoms, G is a glucoside residue, and n is in the range of 1 to 1.5. Note that the above "C8-10" means that the carbon number of R is distributed in the range of 8 to 10, and "C8+C10" means a mixture of a compound with R having 8 carbon atoms and a compound with R having 10 carbon atoms.

[0066] (Component (A2)): Polyoxyalkylene ether ·A2-1: Polyoxyethylene alkyl ether (EO40), (described as "C13EO40" in the table. Product name "Leocol TDA400-75" manufactured by Lion Specialty Chemicals Co., Ltd.), in formula (2) where R 11 is a branched alkyl group with 13 carbon atoms, and OR 12 is an oxyethylene group, and m is 40. ·A2-2: Polyoxyethylene lauryl ether (EO50), (described as "C12EO50" in the table. Product name "Emalex 750" manufactured by Nippon Emulsion Co., Ltd.), in formula (2) where R 11 is a linear alkyl group with 12 carbon atoms, and OR 12 is an oxyethylene group, and m is 50. ·A2-3: Polyoxyethylene alkyl ether (EO60), (described as "C13EO60" in the table. Product name "TA600-75" manufactured by Lion Chemical Co., Ltd.), in formula (2) where R 11 is a branched alkyl group with 13 carbon atoms, and OR 12 is an oxyethylene group, and m is 60. ·A2’-1 (comparative component): POE (polyoxyethylene) lauryl ether, (described as "C12EO7" in the table. Product name "Emalex 707" manufactured by Nippon Emulsion Co., Ltd.), in formula (2) where R 11is a linear alkyl group having 12 carbon atoms, and OR 12 is an oxyethylene group, and a compound where m is 7. ·A2’-2 (comparative component): POE lauryl ether (EO15), (described as “C12EO15” in the table. Product name “Emalex 715” manufactured by Nippon Emulsion Co., Ltd.), in formula (2) R 11 is a linear alkyl group having 12 carbon atoms, and OR 12 is an oxyethylene group, and a compound where m is 15.

[0067] (Component (B)): Aminocarboxylic acid chelating agent ·B-1: Ethylenediaminetetraacetic acid (EDTA), product name “Disolvin Z” manufactured by Nouryon. ·B-2: Trisodium methylglycinediacetate (sodium salt of MGDA), product name “Trilon M” manufactured by BASF. ·B-3: Tetrasodium glutamate diacetate (sodium salt of GLDA), manufactured by Nouryon.

[0068] (Component (C)): Carboxylic acid chelating agent. ·C-1: Citric acid, product name “Purified Citric Acid (Anhydrous)” manufactured by Fuso Chemical Industry Co., Ltd. ·C-2: Lactic acid, manufactured by Wako Pure Chemical Industries, Ltd. (reagent). ·C-3: Malic acid, manufactured by Wako Pure Chemical Industries, Ltd. (reagent).

[0069] Also, as optional components, the following components were appropriately used. (Component (D)) ·D-1: Phenoxyethanol (monoethylene glycol monophenyl ether), manufactured by Nippon Emulsifier Co., Ltd., in formula (3) OR 13 is an oxyethylene group, and a compound where k = 1. (Component (E)) ·E-1: Dodecyltrimethylammonium chloride (lauryltrimethylammonium chloride), product name “Lipgard 12-37w” manufactured by Lion Specialty Chemicals Co., Ltd., described as “C12 monoalkyl” in the table, in formula (E-1), R 1 ~R 4Among them, three are methyl groups, and the remaining one is a linear alkyl group with 12 carbon atoms, and Z - is a compound in which is a chloride ion. (F) component ·F-1: Ethanol, manufactured by Nippon Alcohol Sales Co., Ltd. (G) component ·G-1: Sodium p-cumene sulfonate (product name "Teika Tox N5040" manufactured by Teika Co., Ltd.). ·pH adjuster: Sodium hydroxide (reagent).

[0070] (Evaluation method) (Evaluation of low-temperature foaming property) The liquid detergent of each example was placed in a discharge container (product name "TA-FA" manufactured by Yoshino Kogyosho Co., Ltd., foam trigger spray container accumulator type, 1 stroke (about 0.8 g / stroke)). After adjusting the temperature to 5°C, 5 strokes of the liquid detergent were discharged from this discharge container into a 200 mL tall beaker. After measuring the height of the foam with a ruler, the foam height per unit weight was calculated, and the foaming property was evaluated with N number = 3. A foam height per unit weight average value of 0.6 cm / g or more was considered qualified.

[0071] (Evaluation of foam breakage property) The liquid detergent of each example was placed in the above discharge container (product name "TA-FA"). Immediately after discharging 3 strokes of the liquid detergent from this discharge container into a 200 mL graduated cylinder, 100 ml of tap water was measured with another graduated cylinder and poured in at a rate of 10 ml / s. The height of the foam (X) immediately after pouring the tap water and the height of the foam (Y) 5 minutes after pouring the tap water were measured with a ruler. The defoaming rate A was calculated by the following formula, and the foam breakage property was evaluated with N number = 3. An average value of the defoaming rate A of 0.2 or more was considered qualified. Defoaming rate A = (X - Y) / X

[0072] (Urine detergency: Evaluation of detergency after 5 minutes of standing against dried urine stains) Urine from 5 adult males was placed on a PP plate at 100 μL and left at room temperature for 24 hours to dry. After drying, the liquid detergent for each case was contained in the said discharge container (product name "TA-FA"). The liquid cleaning solution was discharged onto the PP plate with dirt attached from this discharge container. After leaving it for 5 minutes, it was wiped off with toilet paper folded three times. The remaining degree of dirt was visually observed and scored in 0.5-point increments according to the following evaluation criteria. It was evaluated with N = 3, and an average score of 3 or more was considered a pass. ≪Dirt removal evaluation criteria≫ 5 points: The dirt has completely fallen off. 4 points: Almost all the dirt has fallen off. 3 points: About half of the dirt has fallen off. 2 points: Some dirt has fallen off. 1 point: None of the dirt has fallen off.

[0073] <Examples 1 to 56, Comparative Examples 1 to 5> Liquid detergents were manufactured with the formulations shown in the table (unit: mass%). Into a 300 ml beaker, the (F) component was put into 150 g of ion-exchanged water so that the total amount would be a composition of 200 g on the scale, and it was stirred with a stirrer. Next, the (A1) component and the (A2) component were put in and stirred with a stirrer. Next, after adding the (B) to (E) components and the (G) component and stirring, sodium hydroxide as a pH adjuster was added so that the pH would be about 7, and the remaining water was added and stirred to obtain a liquid detergent. Note that the formulation amounts in the table are values in terms of pure components. Also, components not described with formulation amounts in the table are not formulated. The content "appropriate amount" of the pH adjuster is the amount required to adjust the pH of the liquid composition in each case to a predetermined value. Also, the content "balance" of water means the remainder added so that the total formulation amount (mass%) of all the formulation components contained in the liquid composition becomes 100 mass%.

[0074]

Table 1

[0075]

Table 2

[0076]

Table 3

[0077]

Table 4

[0078]

Table 5

[0079]

Table 6

[0080]

Table 7

[0081]

Table 8

[0082]

Table 9

[0083] As shown in Tables 1 to 9, Examples 1 to 56 had good low-temperature foaming properties, foam breakage properties, and detergency against urine stains. Comparative Example 1, which did not contain the (A1) component, was inferior in low-temperature foaming properties. Comparative Example 2, which did not contain the (A2) component, was inferior in urine detergency. Comparative Examples 3 and 4, in which the (A2) component was replaced with a comparative component having a short EO chain length, were inferior in low-temperature foaming properties. Comparative Example 5, which did not contain the (B) component, was inferior in urine detergency.

Claims

1. Component (A1): An alkyl polyglycoside represented by the following formula (1), Component (A2): A polyoxyalkylene alkyl ether represented by the following formula (2), and Component (B): A liquid toilet cleaner containing an aminocarboxylic acid-based chelating agent. R−O−[G]n... (1) [In the formula, R is an alkyl group having 8 to 18 carbon atoms, G is a glycoside residue, and n is the average degree of condensation and is a number from 1 to 5.] R １１ -(OR １２ )m-OH... (2) (In the formula, R １１ is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, R １２ is an alkylene group having 2 or 3 carbon atoms, and m is the average repeating number of (OR １２ ) and is a number from 16 to 70.)

2. The liquid toilet cleaner according to claim 1, wherein (A1) / (A2), which represents the mass ratio of the content of component (A1) to the content of component (A2), is 0.3 to 10.

3. The liquid toilet cleaner according to claim 1, wherein (A1) / (B), which represents the mass ratio of the content of component (A1) to the content of component (B), is 0.1 to 6.

4. Further, the liquid toilet cleaner according to claim 1, comprising component (C): a carboxylic acid-based chelating agent (excluding the component (B)).

5. The liquid toilet cleaner according to claim 4, wherein the total content of the component (B) and the component (C) is 1 to 3.2% by mass based on the total mass of the liquid toilet cleaner.

6. A liquid toilet cleaner product having the liquid toilet cleaner according to any one of claims 1 to 5 and a discharge container containing the liquid toilet cleaner.

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