Liquid detergent for hard surfaces and liquid detergent product for hard surfaces

Abstract

To provide a liquid detergent for hard surfaces that is superior in low-temperature foamability, foam breakability, wipability and low-temperature stability.SOLUTION: A liquid detergent for hard surfaces 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 (F) a lower alcohol. A mass ratio represented by (F / (A1+A2)) is 0.01 to 5.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid detergent for hard surfaces and a liquid detergent product for hard surfaces.

Background Art

[0002] As a detergent for hard surfaces such as residential facilities, a foam spray type detergent that discharges foam from a spray container tends to be preferred in terms of convenience and cleaning effect. As a liquid detergent for hard surfaces of the foam spray type, for example, the detergent compositions described in Patent Documents 1 and 2 have been proposed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] For example, when applied to the hard surface of a toilet, in addition to the method of spraying foam into the toilet bowl and flushing it with water, it is desired that it can be used by the method of spraying foam on the toilet seat or floor and then wiping it with toilet paper or the like. Also, a product that takes into account being used and stored in an environment with a relatively low temperature such as a toilet is desired. Therefore, a liquid detergent for hard surfaces is required that has a large amount of foam when sprayed at a low temperature (good low-temperature foaming property), the foam disappears moderately easily (good foam breakability), is easy to wipe off (good wipe-off property), and its properties do not change even when stored at a low temperature (good low-temperature stability). However, it has been difficult for conventional technologies to fully satisfy these requirements. An object of the present invention is to provide a liquid detergent for hard surfaces having good low-temperature foaming property, foam breakability, wipe-off property, and low-temperature stability.

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 Component (F): containing a lower alcohol, a liquid detergent for hard surfaces, wherein the mass ratio of component (F) to the total content of component (A1) and component (A2) [represented by (F / (A1+A2))] is 0.01 to 5. 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 detergent for hard surfaces according to [1], wherein the mass ratio of component (A1) to component (A2) [represented by (A1 / A2)] is 0.1 to 10. [3] Further, the liquid detergent for hard surfaces according to [1] or [2], comprising component (G): one or more selected from the group consisting of aromatic sulfonic acids, aromatic carboxylic acids, and salts thereof. [4] A liquid detergent product for hard surfaces, having the liquid detergent for hard surfaces according to any one of [1] to [3] and a discharge container containing the liquid detergent for hard surfaces. [Advantages of the Invention]

[0006] According to the present invention, a liquid detergent for hard surfaces with good low-temperature foaming property, foam-breaking property, wiping property, and low-temperature stability can be obtained. [Modes for Carrying Out the Invention]

[0007] ≪Liquid Detergent for Hard Surfaces≫ The liquid detergent for hard surfaces of this embodiment (hereinafter, also simply referred to as liquid detergent) is a composition containing component (A1), component (A2), and component (F). Further, it may contain one or more selected from component (B), component (C), component (D), component (E), and component (G). In this specification, the numerical range represented by "~" means a numerical range having 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 good foaming when sprayed, in the 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 aldose or ketose. Examples of the reducing sugar include triose, tetrose, pentose, and hexose having 3 to 6 carbon atoms. Specific examples of aldose include apiose, arabinose, galactose, glucose, lyxose, mannose, gulose, allose, idose, talose, xylose. Specific examples of ketose include fructose. Among these, aldopentose or aldohexose having 5 or 6 carbon atoms is preferable. Among them, glucose is most preferable. That is, G is most preferably a glucoside residue. In the general formula (1), n indicates the average degree of condensation of the sugar, and preferably a number from 1 to 2, particularly a number from 1 to 1.5 is good.

[0010] As the (A1) component, those synthesized by a conventionally known production method may be used, or commercially available products may be used. Examples of the trade names of commercially available products include GreenAPG 1214, GreenAPG 0810 (Nikko Chemicals Co., Ltd.), Myadol 10 (Kao Corporation), Triton CG-110 (Dow DuPont Co., Ltd.), Glucopon650, Glucopon215up (BASF), EcoSense 919 (Dow Chemical Company), AG6210 (Nouryon), etc.

[0011] <(A2) component> The (A2) component 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 The number of carbon atoms of R 11 is from 8 to 18, preferably from 10 to 16, and more preferably from 10 to 14. 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 not less than the above lower limit value, the foaming property is further enhanced and the amount of foam increases. If m is not more than the above upper limit value, the foaming property is good and the handleability when formulating the composition is also good.

[0015] <(Component F)> (Component F) is a lower alcohol. By containing (Component F), the foaming property and the wiping property become good. 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, and more preferably 2 to 3. Examples of the lower alcohol include ethanol, n-propanol, isopropanol, butanol and the like. Among these, ethanol and isopropanol are preferable, and ethanol is more preferable. The lower alcohol may be used alone or in combination of two or more.

[0016] <(Component G)> (Component G) is one or more selected from aromatic sulfonic acids, aromatic carboxylic acids, and salts thereof. (Component G) mainly contributes to the foaming power and storage stability of the liquid detergent. As (Component G), 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 under low temperature conditions. Two or more kinds may be mixed and used. (G) component, toluenesulfonic acid, toluenesulfonate, cumenesulfonic acid, and cumenesulfonate may each be any of the three isomers of the o-form, m-form, and p-form. Among these, the p-form is preferred because it is easily available. Further, among them, cumenesulfonic acid and cumenesulfonate are preferred from the viewpoint of foaming properties. As the salt form in toluenesulfonate, cumenesulfonate, and benzoate, 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 can be mentioned. Among them, salts of alkali metals are preferred, and sodium salts are more preferred.

[0017] <(B) component> The liquid detergent of the present embodiment may further contain an aminocarboxylic acid-based chelating agent as the (B) component. The (B) component has a nitrogen atom and a carboxy group. (B) components include, for example, DEG (dihydroxyethyl glycine: N-(2-hydroxylethyl)glycine), HEIDA (N-(2-hydroxyethyl)iminodiacetic acid), HEDTA (hydroxyethyl ethylenediamine tetraacetic acid: N-(hydroxyethyl)ethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid: Nitrilo Triacetic Acid), DTPA (diethylenetriamine pentaacetic acid: Diethylene Triamine Pentaacetic Acid), HEDTA (hydroxyethyl ethylenediamine triacetic acid: Hydroxyethyl Ethylene Diamine Triacetic Acid), EDTA (ethylenediamine tetraacetic acid: Ethylene Diamine Tetraacetic Acid), MGDA (methylglycine diacetic acid: MethylGlycine Diacetic Acid), GLDA (L-glutamic acid diacetic acid: Dicarboxymethyle Glutamic Acid), ASDA (aspartic acid diacetic acid: Aspartate Diacetic Acid), EDDS (ethylenediamine disuccinic acid: Ethylenediamine Disuccinic Acid), HIDS (hydroxyiminodisuccinic acid: Hydroxye Iminodisuccinic Acid), IDS (iminodisuccinic acid: Iminodisuccinic Acid), and salts (e.g., alkali metal salts) and hydrates of the above compounds, etc. 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.

[0018] <(C) component> The liquid detergent of this embodiment may further contain a carboxylic acid-based chelating agent (excluding the (B) component) as the (C) component. The (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 preferred as the (C) component. (C) component may be used alone or in combination of two or more.

[0019] <(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.

[0020]

Chemical formula

[0021] 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 number of repetitions of (OR 13 ), that is, the average number of moles of ethylene oxide or propylene oxide added. 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, and the like. 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.

[0022] <(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) has an excellent antibacterial effect.

[0023]

Chemical formula

[0024] 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.

[0025] 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.

[0026] In formula (E-3), R 7 and R8 is independently 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.

[0027] 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.

[0028] Examples of the 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 preferable; lauryltrimethylammonium salt, cetyltrimethylammonium salt, dioctyldimethylammonium salt, and didecyldimethylammonium salt are more preferable; and lauryltrimethylammonium salt, cetyltrimethylammonium salt, dioctyldimethylammonium salt, and benzyldodecyldimethylammonium salt are even more preferable.

[0029] In formula (E-1), formula (E-2), and formula (E-3), the counter ion Z - Examples thereof include halide ions, alkyl sulfate ions, sulfate ions, alkylbenzene sulfonate ions, alkyl carbonate ions, and carbonate ions. Among them, halide ions and alkyl sulfate ions are preferable, and halide ions are more preferable. Examples of the halide ions include chloride ions, bromide ions, and iodide ions. Among them, chloride ions are preferable.

[0030] In particular, as the component (E), lauryl trimethyl ammonium chloride, decyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, and dodecyl benzyl dimethyl ammonium chloride are preferable, lauryl trimethyl ammonium chloride, decyl trimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, and didodecyl dimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride are more preferable, and lauryl trimethyl ammonium chloride, decyl trimethyl ammonium chloride, dioctyl dimethyl ammonium chloride are even more preferable.

[0031] 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 "Lipocard series" (Lion Specialty Chemicals Co., Ltd.), "Econol", "Revon series", "Cation DSV", "Cation LQ" (Sanyo Chemical Industries, Ltd.), "Bardac LF80" (Lonza Japan Co., Ltd.), "Didodecyl dimethyl ammonium chloride" (Tokyo Ohka Kogyo Co., Ltd.), etc. As the component (E), one kind may be used alone, or two or more kinds may be used in combination.

[0032] <Other surfactants> The liquid detergent may contain other surfactants that do not fall under any of the above components (A1), (A2), and (E). Examples of other surfactants include nonionic surfactants other than the components (A1) and (A2), cationic surfactants other than the component (E), amphoteric surfactants (hereinafter also referred to as component (A3)), anionic surfactants (hereinafter also referred to as component (A4)), and amine oxide type surfactants (hereinafter also referred to as component (A5)). 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] [Component (A3)] Examples of the amphoteric surfactant that is the component (A3) include betaine-based amphoteric surfactants, amino acid-based amphoteric surfactants, etc. Among these, betaine-based amphoteric surfactants are preferred. Examples of the betaine-based amphoteric surfactants 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 surfactants include lauric acid dimethylaminoacetic acid betaine, myristyl dimethylaminoacetic acid betaine, stearyl dimethylaminoacetic acid betaine, etc.

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

[0036] Examples of the sulfobetaine-based amphoteric surfactants include, for example, coconut oil fatty acid dimethylamino hydroxysulfobetaine, lauryl dimethylamino hydroxysulfobetaine, lauryl hydroxysulfobetaine, 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-hydroxyethylimidazolinium betaine, coconut oil alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and the like.

[0038] Examples of sulfobetaine amphoteric surfactants include lauryl hydroxyphosphobetaine and the like.

[0039] Examples of aminopropionic acid amphoteric surfactants include sodium laurylaminodipropionate, triethanolamine laurylaminodipropionate, and the like.

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

[0041] Among the above, as the component (A3), lauric acid amidopropyl betaine, lauryl dimethylaminoacetic acid betaine, and stearyl dimethylaminoacetic acid betaine are preferable, and lauric acid amidopropyl betaine and lauryl dimethylaminoacetic acid betaine are particularly preferable from the viewpoint of wiping property.

[0042] (A3) component is commercially available. Examples of the product name of (A3) component include "Enajicol L-30B (manufactured by Lion Specialty Chemicals 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 "Obazoline LB-SF (manufactured by Toho Chemical Industry Co., Ltd.)" which are lauryldimethylaminoacetate betaines, 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 in an average amount of 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 in an average amount of 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 sulfonate 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> If necessary, the liquid detergent may contain, in addition to the above components, components that can usually be used in liquid detergents for hard surfaces. 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] Examples of pH adjusters include sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and ammonia. Among these, sulfuric acid, sodium hydroxide, and potassium hydroxide are preferred, and sulfuric acid and potassium hydroxide are more preferred, from the viewpoint of easy pH adjustment. The pH adjuster may be one kind or a combination of two or more kinds.

[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. By containing the components (A1) and (A2), foam can be discharged from the spray container. In particular, when the component (A2) is contained, the foaming property during spraying at normal temperature and low temperature is further enhanced, and the amount of foam increases. The content of the component (A1) is preferably 0.1 to 5.0% by mass, more preferably 0.1 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 0.1 to 3.0% by mass, based on the total mass of the liquid detergent. (A1 + A2), which represents the total content of the components (A1) and (A2), is preferably 0.5 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1.5 to 5% by mass, based on the total mass of the liquid detergent.

[0050] In liquid detergents, when the ratio of component (A1) to component (A2) increases, while the foaming property and foam collapse increase, the wiping property tends to decrease. The mass ratio (A1 / A2) representing the content of component (A1) to the content of component (A2) is preferably from 0.05 to 15, more preferably from 0.1 to 10, still more preferably from 0.5 to 6, and particularly preferably from 0.5 to 3.

[0051] By adding component (F) in addition to component (A1) and component (A2), the foaming property and the wiping property can be improved. Also, although the foaming property becomes good by adding component (F), if too much is added, the foaming property tends to decrease. The content of component (F) is preferably from 0.1 to 10% by mass, more preferably from 1 to 8% by mass, still more preferably from 2 to 5% by mass with respect to the total mass of the liquid detergent. Within this range, the foaming property and the wiping property when wiping the surface with toilet paper or the like after spray spraying become good. The mass ratio (F / (A1 + A2)) representing the content of component (F) to the total content of component (A1) and component (A2) is from 0.01 to 5, preferably from 0.1 to 5, more preferably from 0.5 to 5, and still more preferably from 1 to 5. When (F / (A1 + A2)) is within the above range, particularly good wiping property is easily obtained.

[0052] When containing component (G), the foaming power becomes good and the appearance stability of the liquid detergent after low-temperature storage becomes good. The content of component (G) is preferably from 0.1 to 3% by mass, more preferably from 0.1 to 1% by mass, still more preferably from 0.1 to 0.3% by mass with respect to the total mass of the liquid detergent. When the content of component (G) is not less than the lower limit value of the above range, even under low-temperature conditions, it becomes easier to maintain the transparent appearance of the liquid detergent more stably during storage over time. When it is not more than the upper limit value, the foaming and the persistence of the foam amount are further improved. By using component (G) and component (F) in combination, the low-temperature stability can be further improved. In particular, it is preferable to use component (G) and ethanol in combination.

[0053] With respect to the total mass of the nonionic surfactant contained in the liquid detergent, 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. It may be 100% by mass. With respect to the total mass of the cationic surfactant contained in the liquid detergent, the ratio of the component (E) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more. It may be 100% by mass.

[0054] <Physical properties> The pH of the liquid detergent at 25°C is preferably 4 to 10, more preferably 4 to 8. In this specification, the pH of the liquid detergent is a value measured by a method conforming to JIS Z 8802:2011 "Method for Measuring pH".

[0055] The viscosity of the liquid detergent is not particularly limited. However, when using a spray container or a squeeze container, from the ease of foaming, 1 to 50 mPa·s is preferable, and 1 to 15 mPa·s is more preferable. In this specification, the viscosity of the liquid detergent is a value measured at a liquid temperature of 25°C, using a B-type viscometer, with a rotor number of No. 1 and a rotor rotation speed of 60 rpm, 60 seconds after the start of the rotor rotation.

[0056] <Liquid detergent product for hard surfaces> A liquid detergent product for hard surfaces (hereinafter sometimes simply referred to as "liquid detergent product") has a discharge container and the liquid detergent for hard surfaces of the present invention housed in the discharge container.

[0057] Examples of the discharge container for housing the liquid detergent include a spray container and a squeeze container. Among them, a spray container is preferable because of its excellent coatability to the object to be cleaned. Examples of spray containers include aerosol spray containers, trigger spray containers (direct pressure type or accumulator type), dispenser spray containers, etc. These containers may be manual or electric. Examples of aerosol spray containers include those described in, for example, Japanese Patent Laid-Open No. 9-3441 and Japanese Patent Laid-Open No. 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 trigger spray containers include those described in, for example, Japanese Patent Laid-Open No. 9-268473 and Japanese Patent Laid-Open No. 10-76196. Examples of dispenser spray containers include those described in, for example, Japanese Patent Laid-Open No. 9-256272. Examples of accumulator type trigger spray containers include those described in, for example, Japanese Patent Laid-Open No. 2013-154276.

[0058] <Manufacturing method> The liquid detergent is manufactured by a conventionally known manufacturing method. For example, a method of adding the (A1) component and the (A2) component, and components used as necessary to water with the (F) component added as a solvent and mixing them is mentioned. The liquid detergent product is manufactured by manufacturing the liquid detergent by the above method and storing it in a discharge container.

[0059] <Usage method> As a usage method of the liquid detergent, for example, 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 an object to be washed (for example, a bathtub or a toilet bowl), and rinsing it with running water after a certain period of time, that is, "rinsing and washing" is mentioned. Also, as another usage method, a usage method of applying an appropriate amount of the liquid detergent to an object to be washed (for example, a bathtub or a toilet bowl) and scrubbing it with a cleaning brush, that is, "scrubbing and washing" is mentioned. Alternatively, there is a usage method of "wipe washing" in which a liquid detergent is applied to an object to be washed (for example, a toilet seat, a floor, a wall, etc.) and then wiped off with a cloth or paper.

[0060] The object to be washed may be a hard surface such as an article, and examples thereof include hard surfaces in a bathroom, bathroom supplies, hard surfaces in a toilet, toilet supplies, hard surfaces in a kitchen, and kitchen supplies (tableware, cooking utensils, etc.). The hard surface means a surface made of a hard material such as plastics, ceramics, glass, stainless steel, etc. Since the liquid detergent of the present embodiment has good low-temperature foaming property, foam-breaking property, wiping property, and low-temperature stability, it is particularly suitable as a liquid detergent for toilets used for cleaning inside the toilet.

Examples

[0061] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by the following description.

[0062] (Raw materials used) (Component (A1)): Alkyl polyglycoside · A1-1: C8-10 APG, 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 formula (1). · A1-2: C8-16 APG, product name "Glucopon650" manufactured by BASF, a compound in which R is a linear alkyl group having 8 to 16 carbon atoms, G is a glucoside residue, and n is in the range of 1 to 1.5 in formula (1). · A1-3: C8 + C10 APG, product name "AG6210" manufactured by Nouryon, a compound in which R is a linear alkyl group having 8 and 10 carbon atoms, G is a glucoside residue, and n is in the range of 1 to 1.5 in formula (1).

[0063] (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) R 11 is a branched alkyl group with 13 carbon atoms, and OR 12 is an oxyethylene group, and a compound where 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) R 11 is a straight-chain alkyl group with 12 carbon atoms, and OR 12 is an oxyethylene group, and a compound where 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) R 11 is a branched alkyl group with 13 carbon atoms, and OR 12 is an oxyethylene group, and a compound where 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) R 11 is a straight-chain alkyl group with 12 carbon atoms, and OR 12 is an oxyethylene group, and a compound where m is 7. ·A2’-2 (Comparative component): POE (Polyoxyethylene) lauryl ether, (described as "C12EO15" in the table. Product name "Emalex 715" manufactured by Nippon Emulsion Co., Ltd.), in formula (2) R 11 is a straight-chain alkyl group with 12 carbon atoms, and OR 12 is an oxyethylene group, and a compound where m is 15.

[0064] (Component (F)): Lower alcohol ·F-1: Ethanol, manufactured by Nippon Alcohol Sales Co., Ltd. ·F-2: Isopropyl alcohol (described as "IPA" in the table), manufactured by Tokuyama Corporation. · F-3: Propylene glycol manufactured by The Dow Chemical Company (described as "PG" in the table).

[0065] (G) component: Aromatic sulfonic acid, aromatic carboxylic acid · G-1: Sodium p-cumene sulfonate (product name "Teikatoz N5040" manufactured by Teika Co., Ltd.). · G-2: p-Toluenesulfonic acid (product name "PTS-70" manufactured by Myu Industries Co., Ltd.). · G-3: m-Xylenesulfonic acid (product name "SXA" manufactured by Itochu Chemical Frontier Co., Ltd.).

[0066] Also, as optional components, the following components were appropriately used. (B) component · B-1: Ethylenediaminetetraacetic acid (EDTA), product name "Disolvin Z" manufactured by Nouryon. (C) component · C-1: Citric acid, product name "Purified Citric Acid (Anhydrous)" manufactured by Fuso Chemical Industry Co., Ltd. (D) component · D-1: Phenoxyethanol (monoethylene glycol monophenyl ether), manufactured by Nippon Emulsifier Co., Ltd., a compound in which OR in formula (3) 13 is an oxyethylene group and k = 1. (E) component · E-1: Dodecyltrimethylammonium chloride (lauryltrimethylammonium chloride), product name "Lipoguard 12-37w" manufactured by Lion Specialty Chemicals Co., Ltd., described as "C12 monoalkyl" in the table, in formula (E-1), R 1 ~R 4 Three of which are methyl groups and the remaining one is a linear alkyl group with 12 carbon atoms, and Z - is a chloride ion. pH adjuster: Sodium hydroxide (reagent), the addition amount was adjusted to achieve pH 7. Fragrance: Fragrance composition A described in JP-A-2003-183697.

[0067] (Evaluation method) (Evaluation of low-temperature foaming property) Each example of the liquid detergent was placed in a discharge container (product name "TA-FA" manufactured by Yoshino Kogyosho Co., Ltd., a foaming trigger spray container of the accumulator type, 1 stroke (about 0.8 g / stroke)). After adjusting the temperature to 5°C, the liquid detergent was discharged from this discharge container into a 200 mL tall beaker in 5 strokes. 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 = 3. A foam height per unit weight with an average value of 0.6 cm / g or more was considered a pass.

[0068] <Evaluation of foam collapse property> Each example of the liquid detergent was placed in the above discharge container (product name "TA-FA"). Immediately after discharging the liquid detergent from this discharge container into a 200 mL graduated cylinder in 3 strokes, 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 immediately after pouring the tap water (X) and the height of the foam 5 minutes after pouring the tap water (Y) were measured with a ruler. The defoaming rate A was calculated by the following formula, and the foam collapse property was evaluated with N = 3. A defoaming rate A with an average value of 0.2 or more was considered a pass. Defoaming rate A = (X - Y) / X

[0069] <Wiping property> 100 μL of each example of the liquid detergent was placed on a slide glass and gently wiped once with a folded toilet paper eight times. After drying, a professional panel (N = 2) scored the remaining state of the wiping marks according to the following evaluation criteria. An average score of 3 or more was considered a pass. ≪Evaluation criteria≫ 5 points: No wiping marks remain at all. 4 points: Thin linear wiping marks remain, and there is no stickiness. 3 points: Thin linear wiping marks remain, and there is a slight stickiness but it is not bothersome. 2 points: Wiping marks remain partially. 1 point: Wiping marks remain over the entire surface.

[0070] <Low-temperature stability> 40 ml of the liquid detergent composition of each example was placed in 6 PS standard bottles. After covering the bottles, they were stored in a thermostat at -5°C for 7 days. Then, after returning to room temperature, a professional panel (N = 2) visually evaluated the state of the liquid appearance according to the following evaluation criteria and gave scores. An average score of 3 or more was considered a pass. ≪Evaluation Criteria≫ 5 points: It was uniformly transparent. 4 points: It was slightly turbid. 3 points: The liquid was separated into two layers. When the bottle was shaken, it became uniformly transparent. 2 points: The liquid was separated into two layers. Even when the bottle was shaken, it did not become transparent. 1 point: Precipitates occurred in the liquid or it was in a solidified state.

[0071] <Examples 1 to 43, Comparative Examples 1 to 6> Liquid detergents were manufactured with the formulations shown in the table (unit: mass%). The (F) component was added to 150 g of ion-exchanged water in a 300 ml beaker so that the total amount became a composition of 200 g on a scale, and it was stirred with a stirrer. Next, the (A1) component and the (A2) component were added and stirred with a stirrer. Then, the (B) to (E) components, the (G) component, and the fragrance were added and stirred. After that, sodium hydroxide as a pH adjuster was added so that the pH became 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 listed with formulation amounts in the table are not formulated. The content of the pH adjuster "appropriate amount" is the amount required to adjust the pH of the liquid composition of each example to a predetermined value. Also, the content of water "balance" means the remainder added so that the total formulation amount (mass%) of all the formulated components contained in the liquid composition becomes 100 mass%.

[0072]

Table 1

[0073]

Table 2

[0074] [Table 3]

[0075] [Table 4]

[0076] [Table 5]

[0077] [Table 6]

[0078] [Table 7]

[0079] As shown in Tables 1 to 7, Examples 1 to 43 had good low-temperature foaming properties, foam breakage properties, wiping properties, and low-temperature stability. Comparative Example 1, which did not contain the (A1) component, had poor low-temperature foaming properties. Comparative Example 2, which did not contain the (A2) component, had poor wiping properties. Comparative Examples 3 and 4, in which the (A2) component was replaced with a comparative component having a short EO chain length, had poor low-temperature foaming properties. Comparative Example 5, which did not contain the (F) component, had poor wiping properties. Comparative Example 6, in which (F / (A1+A2)) was less than 0.01, had poor wiping properties and low-temperature stability.

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 (F): containing a lower alcohol, A liquid detergent for hard surfaces, wherein the mass ratio (F / (A1 + A2)) representing the content of component (F) relative to the total content of component (A1) and component (A2) is 0.01 to 5. 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 detergent for hard surfaces according to claim 1, wherein the mass ratio (A1 / A2) representing the content of component (A1) relative to the content of component (A2) is 0.1 to 10.

3. Further, a liquid detergent for hard surfaces according to claim 1, comprising (G) component: one or more selected from the group consisting of aromatic sulfonic acids, aromatic carboxylic acids, and salts thereof.

4. A liquid detergent product for hard surfaces, comprising the liquid detergent for hard surfaces according to any one of claims 1 to 3, and a discharge container containing the liquid detergent for hard surfaces.

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