Liquid cleaning agent composition for hard surfaces

Abstract

To provide a liquid cleaning agent composition for hard surfaces that contains a surfactant and a pH indicator, achieving both cleaning power and visibility, which are in a trade-off relationship, and allowing for visual confirmation that the cleaning power has been fully exerted by a color change immediately after dispensing and after a predetermined time has elapsed. [Solution] A liquid cleaning agent composition for hard surfaces comprising (A) component: surfactant, (B) component: pH indicator with a color change range of pH 7.8 to 14, and (C) component: aminocarboxylic acid chelating agent, wherein the mass ratio expressed as [mass of (A) component] / [mass of (B) component] is 600 to 5000, and the pH at 25°C is 10 or higher.

Description

[Technical Field]

[0001] This invention relates to a liquid cleaning agent composition for hard surfaces. [Background technology]

[0002] Liquid cleaning agent compositions for hard surfaces are required to have cleaning power against acidic stains such as sebum and uric acid. In order to fully exert cleaning power against these stains, it is desirable to allow the cleaning agent composition to penetrate the acidic stains thoroughly and stand until the cleaning power is exerted. However, with conventional detergent compositions, it was difficult to determine whether or not they had exhibited cleaning power.

[0003] Patent Document 1 proposes a technology for a liquid composition in which the coloring agent does not easily stain the target object, while ensuring sufficient visibility by setting the ratio and total amount of Direct Blue 86 and Food Green No. 3 to an optimal level. Patent Document 2 proposes a cleaning agent that contains a surfactant, at least one alkaline compound selected from the group consisting of ammonia and an amino group-containing alkaline compound, and at least one color indicator selected from color indicators that change color when the pH changes from alkaline to neutral, wherein the amount of the alkaline compound is such that it is necessary for the alkaline compound to disappear by reacting with carbon dioxide at the same time interval as the time required to remove most of the dirt from the surface of the object to be cleaned. Non-patent document 1 reports that when measuring the pH of a solution containing a nonionic surfactant using pH test paper containing a pH indicator, a negative error occurs, and the effect of the measurement error depends on the pH being measured, the surfactant concentration, the parallel constant of the pH indicator / surfactant complex formation reaction, and the molecular absorbance ratio of acidic and basic color molecules. Non-patent document 1 also states that nonionic surfactants bind to non-dissociative pH indicators to form a pH indicator / surfactant complex. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2018-65952 [Patent Document 2] International Publication No. 1999 / 19446 [Non-patent literature]

[0005] [Non-Patent Document 1] Biological Sample Analysis, Yuji Suzuki, Vol.37, No.5 (2014), 354-363. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, the technology described in Patent Document 1 does not allow the user to be notified whether the cleaning is complete. Applying the technology described in Patent Document 2 to a liquid cleaning agent composition for hard surfaces can achieve both visibility and stain prevention. However, when surfactants are added to ensure cleaning power, the color of the pH indicator changes, leading to a deterioration in visibility. Furthermore, changing the amount of alkaline compounds alters the pH, posing challenges in controlling cleaning power and ensuring safety. In short, in conventional technology, visibility and cleaning power are in a trade-off relationship, making it difficult to achieve both simultaneously. Non-Patent Document 1 describes a technology in which the addition of a nonionic surfactant causes a color change without a change in pH (hereinafter also referred to as "discoloration"), and that the color development of the pH indicator itself decreases at high pH (hereinafter also referred to as "fading"). However, no solutions to these problems have been proposed. Furthermore, the effects of other surfactants besides nonionic surfactants on the pH indicator have not been investigated. Moreover, the method of allowing the detergent composition to fully penetrate acidic stains, letting it stand until it exerts its cleaning power, and determining whether the cleaning power has been exerted by observing the color change has not been investigated.

[0007] The present invention aims to provide a liquid cleaning agent composition for hard surfaces that contains a surfactant and a pH indicator, which balances cleaning power and visibility, which are in a trade-off relationship, and allows for visual confirmation that the cleaning power has been fully exerted by a color change immediately after dispensing and after a predetermined time has elapsed. [Means for solving the problem]

[0008] The present invention has the following aspects. <1> (A) Ingredients: Surfactants and (B) Component: A pH indicator with a color change range of pH 7.8 to 14, (C) Ingredients: Contains an aminocarboxylic acid chelating agent, The mass ratio expressed as [(A) mass] / [(B) mass] is between 600 and 5000. A liquid cleaning agent composition for hard surfaces having a pH of 10 or higher at 25°C. <2> The aforementioned component (A) includes one or more selected from the group consisting of anionic surfactants (a1), nonionic surfactants (a2), and amphoteric surfactants (a3). <1> A liquid cleaning agent composition for hard surfaces as described above. <3> The aforementioned component (B) includes one or more selected from the group consisting of phenolphthalein, thymolphthalein, and thymol blue. <1> or <2> A liquid cleaning agent composition for hard surfaces as described above. <4> Furthermore, it contains component (D), The aforementioned component (D) is a solvent containing a glycol ether-based solvent. <1> ~ <3> A liquid cleaning agent composition for hard surfaces according to any one of the items. <5> It is for use in the bathroom. <1> ~ <4> A liquid cleaning agent composition for hard surfaces according to any one of the items. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a liquid cleaning agent composition for hard surfaces that contains a surfactant and a pH indicator, which is in a trade-off relationship between cleaning power and visibility, and which allows for visual confirmation that the cleaning power has been fully exerted by a color change immediately after dispensing and after a predetermined time has elapsed. [Brief explanation of the drawing]

[0010] [Figure 1] This is a partial cross-sectional view showing an example of a discharge container. [Modes for carrying out the invention]

[0011] The present invention will be described in detail below. ≪Liquid cleaning agent composition for hard surfaces≫ The liquid cleaning agent composition for hard surfaces of the present invention (hereinafter also simply referred to as "liquid cleaning agent composition") is a composition containing the following components (A), (B), and (C). The liquid cleaning agent composition may contain water. Furthermore, the liquid cleaning agent composition may further contain components other than (A), (B), (C), and water (optional components) as needed.

[0012] <(A) component> (A) Component is a surfactant. The cleaning power of the liquid detergent composition can be enhanced by including component (A). Examples of component (A) include anionic surfactants (hereinafter also referred to as "component (a1)"), nonionic surfactants (hereinafter also referred to as "component (a2)"), amphoteric surfactants (hereinafter also referred to as "component (a3)"), semipolar surfactants, and cationic surfactants. Among these, anionic surfactants and amphoteric surfactants are preferred, and anionic surfactants are more preferred, because they easily provide high cleaning power from the time of discharge to the desired time. (A) From the viewpoint of cleaning power, component (A) is preferably one that does not have an aromatic ring.

[0013] (Anionic surfactant) (A1) Examples of components include carboxylic acid-type anionic surfactants such as linear alkylbenzene sulfonic acid or its salt (LAS), α-olefin sulfonic acid or its salt (AOS), linear or branched alkyl sulfate ester or its salt (AS), polyoxyalkylene alkyl (or alkenyl) ether sulfate ester or its salt (AES), alkane sulfonic acid or its salt, α-sulfo fatty acid ester or its salt, internal olefin sulfonic acid or its salt (IOS), hydroxyalkane sulfonic acid or its salt (HAS), alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkylamide ether carboxylic acid or its salt, alkenylamide ether carboxylic acid or its salt, acylaminocarboxylic acid or its salt; and phosphate ester-type anionic surfactants such as alkyl phosphate ester or its salt, polyoxyalkylene alkyl phosphate ester or its salt, polyoxyalkylene alkylphenyl phosphate ester or its salt, glycerin fatty acid ester monophosphate ester or its salt. Examples of salt forms of these anionic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (alkanolammonium salts such as monoethanolamine salt (monoethanolammonium salt) and diethanolamine salt (diethanolammonium salt)). (A1) From the viewpoint of high-temperature stability, it is preferable that the component has only one anionic group in one molecule.

[0014] The component (A1) is preferably an anionic surfactant represented by the following formula (a1), more preferably an anionic surfactant represented by the following formula (a1-1) or the following formula (a1-2), and even more preferably an anionic surfactant represented by the following formula (a1-1-1) or the following formula (a1-2-1).

[0015] R a1 -X-(R a2 ) c -[(EO) m (PO) n-Y ···(a1) In formula (a1), R a1 is a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkenyl group having 2 to 20 carbon atoms, X is a single bond, a phenylene group, -O- or a hydroxyalkylene group, R a2 is a linear or branched alkylene group having 1 to 20 carbon atoms or a linear or branched alkenylene group having 2 to 20 carbon atoms, c is a number of 0 or 1, EO is an oxyethylene group, m is a number of 0 or more representing the average number of repetitions of EO, PO is an oxypropylene group, n is a number of 0 to 6 representing the average number of repetitions of PO, and Y is -SO3M a1 , -CO2M a2 , or -PO3M a3 where M a1 , M a2 , and M a3 are each independently a hydrogen atom, or a monovalent or divalent counter ion.]

[0016] In formula (a1), when c is 0, the number of carbon atoms of the alkyl group or alkenyl group of R a1 is 8 to 20, preferably 8 to 18, more preferably 10 to 16, and even more preferably 12 to 14. As R a1 , a linear alkyl group having 8 to 18 carbon atoms is preferred, a linear alkyl group having 10 to 16 carbon atoms is more preferred, and a linear alkyl group having 12 to 14 carbon atoms is even more preferred. Specifically, it may be a mixture such as a dodecyl group, a tridecyl group, a tetradecyl group, etc. When c is 1 or more, the number of carbon atoms of R a1 +R a2 is preferably 8 to 20, more preferably 10 to 16, and even more preferably 10 to 14.

[0017] m is preferably 0 to 5, more preferably 0 to 3, even more preferably 0 to 2, particularly preferably 0 to 1.5, and most preferably 0 to 1.0. n is 0 to 6, preferably 0 to 3, and more preferably 0. m+n is greater than or equal to 0, preferably between 0 and 10, and more preferably between 0 and 5.

[0018] If m and n are not 0, that is, if AES has EO and PO, then [(EO) m (PO) n There are no particular restrictions on the distribution (order of arrangement) of EO and PO in ]. They may be arranged in blocks or randomly. Also, if EO is "R a1 -X-(R a2 ) c - can be added to "R a1 -X-(R a2 ) c It may be joined with "-". Methods for arranging EO and PO in a block-like manner include, for example, introducing ethylene oxide followed by propylene oxide, introducing propylene oxide followed by ethylene oxide, introducing ethylene oxide followed by propylene oxide, and then introducing ethylene oxide again.

[0019] M a11 M a12 and M a13 Examples of suitable cations include hydrogen ions and cations that can form water-soluble salts. Among these, those that can form water-soluble salts are preferred. Examples of cations that can form water-soluble salts include alkali metal ions such as sodium ions and potassium ions; alkaline earth metal ions such as magnesium ions and calcium ions; ammonium ions; and alkanol ammonium ions such as monoethanolammonium ions (monoethanolammonium salt), diethanolammonium ions (diethanolammonium salt), and triethanolammonium ions (triethanolammonium salt). Among these, alkali metal ions are preferred from the viewpoint of solubility, sodium ions and potassium ions are more preferred, and sodium ions are particularly preferred. Note M a11 M a12 and M a13 If the counterion is divalent or greater, Ma11 M a12 and M a13 It is assumed that it is bonded to a monovalent anion by a number obtained by multiplying by 1 / valence. For example, M a11 If it is a magnesium ion, a11 The number is 1 / 2.

[0020] R a1 -O-(EO) m -SO3 M a1 ...(a1-1) In formula (a1-1), R a1 ,EO,m and M a1 This is the same as above. R a1 -XR a2 -SO3 M a1 ...(a1-2) In formula (a1-2), R a1 X, R a2 and M a1 This is the same as above.

[0021] As for AES, in equation (a1-1), R a1 Preferably, m is a linear or branched alkyl group having 10 to 20 carbon atoms, or a linear or branched alkenyl group having 10 to 20 carbon atoms, where m is 1 to 5. In AES, from the viewpoint of the stability of the liquid detergent composition, it is preferable that the proportion of the compound with m=0 and n=0 in formula (a1) is 35 to 55% by mass of the total mass of the compound represented by formula (a1-1).

[0022] As for AOS, in equation (a1-2), R a1 Preferably, m is a linear or branched alkyl group having 10 to 20 carbon atoms, or a linear or branched alkenyl group having 10 to 20 carbon atoms, where m is 1 to 5. In AOS, from the viewpoint of the stability of the liquid detergent composition, it is preferable that the proportion of the compound with m=0 and n=0 in formula (a1) is 35 to 55% by mass of the total mass of the compound represented by formula (a1-2).

[0023] Ra1 -O-C2H4O-SO3M a1 ...(a1-1-1) In formula (a1-1-1), R a1 and M a1 This is the same as above. R a1 -R a2 -SO3 M a1 ...(a1-2-1) In formula (a1-2-1), R a1 , R a2 and M a1 This is the same as above. (A1) Component (A1) may be used alone or in combination of two or more components.

[0024] (Nonionic surfactant) As component (A2), a nonionic surfactant (a2) represented by the following formula (a2) is preferred, a nonionic surfactant (a2-1) represented by the following formula (a2-1) is more preferred, and a Garbet alcohol-type nonionic surfactant (a2-1-1) represented by the following formula (a2-1-1) is even more preferred.

[0025] R a21 -X-[(EO) x / ( A C21 O) y ]-(EO) z -R a22 ...(a2) [In formula (a2), R a21 is a linear or branched alkyl group having 7 to 21 carbon atoms, or a linear or branched alkenyl group having 7 to 21 carbon atoms, -X- is -O-, -COO-, or -CONH-, and R a22 A is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, EO is an oxyethylene group, x is a number from 2 to 70 indicating the average number of repeats of EO, and A C21 O is an oxypropylene group or an oxybutylene group, and y is A C21 z is a number between 0 and 6 representing the average number of repetitions of O, and z is a number between 0 and 20 representing the average number of repetitions of EO.

[0026] In formula (a2), R a21 The number of carbon atoms in the alkyl or alkenyl group is 8 to 22, preferably 8 to 18, and more preferably 8 to 16. -X-bond R a21 The carbon atoms can be either primary or secondary carbon atoms.

[0027] R a22 If it is an alkyl group, the number of carbon atoms is 1 to 6, and preferably 1 to 3. R a22 If the group is an alkenyl group, the number of carbon atoms is 2 to 6, with 2 or 3 being preferred. R a22 A hydrogen atom is particularly preferred.

[0028] x is between 2 and 70, preferably between 2 and 65, more preferably between 2 and 20, and even more preferably between 4 and 15. If x is above the lower limit, the number of oxygen atoms that can form hydrogen bonds increases, thereby increasing hydrophilicity and thus improving cleaning power. If x is below the upper limit, a moderate level of hydrophobicity is obtained, increasing affinity with oil stains and thus improving cleaning power. y is between 0 and 6, and preferably between 0 and 3. z is between 0 and 20, preferably between 0 and 15, and more preferably between 0 and 10. x+z is between 2 and 70, preferably between 2 and 65, more preferably between 2 and 20, and even more preferably between 2 and 15. If x+z is above the lower limit, the number of oxygen atoms that can form hydrogen bonds increases, thereby increasing hydrophilicity and thus improving cleaning power. If x+z is below the upper limit, moderate hydrophobicity is obtained while maintaining liquid stability, thereby increasing affinity with oil stains and thus improving cleaning power.

[0029] If y is not 0, that is, if the nonionic surfactant (A2) has EO and PO, EO and BO, or EO, ​​PO and BO, then [(EO) x / ( A C21 O) yIn this case, there are no particular limitations on the distribution (arrangement order) of EO and PO, EO and BO, or EO, PO, and BO. They may be arranged in a block pattern or in a random pattern. Also, EO may be bonded to “R a21 -X-”, or PO or BO may be bonded to “R a21 -X-”. When y is not 0, the nonionic surfactant (A2) preferably has EO and PO or EO and BO.

[0030] R a21 -O-(EO) x -H ···(a2-1) In formula (a2-1), R a21 , EO, and x are the same as those described above.

[0031] In formula (a2-1), R a21 is preferably a primary alkyl group having a branched chain and 7 to 21 carbon atoms. The carbon number of R a21 is preferably 8 to 22, more preferably 8 to 18, and even more preferably 8 to 16. The carbon number of the alkyl group constituting the branched chain is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. In formula (a2-1), R a21 is preferably a group represented by the following formula (a2-1-2). [[ID=三十二]]R[[ID=三十三]] a23 [[ID=三十四]]-(X[[ID=三十五]] a21 [[ID=三十六]])[[ID=三十七]] a1 [[ID=三十八]]-(L[[ID=三十九]] a21 [[ID=四十]])[[ID=四十一]] a2 [[ID=四十二]]-(X[[ID=四十三]] a22 [[ID=四十四]])[[ID=四十五]] a3 [[ID=四十六]]-(L[[ID=四十七]] a22 [[ID=四十八]])[[ID=四十九]] a4 [[ID=五十]]-O-(EO)[[ID=五十一]] x [[ID=五十二]]-H ···(a2-1-2)[[ID=五十三]] [[ID=五十四]]In formula (a2-1-2), R[[ID=五十五]] a23 [[ID=五十六]]is a linear or branched alkyl group having 1 to 10 carbon atoms, X[[ID=五十七]] a21 [[ID=五十八]]and X[[ID=五十九]] a22 [[ID=六十]]are each independently a group represented by -CHR[[ID=六十一]] a24 [[ID=六十二]]-, R[[ID=六十三]] a24 [[ID=六十四]]is a linear alkyl group having 1 to 5 carbon atoms, and L[[ID=六十五]] a21 [[ID=六十六]]and L[[ID=六十七]] a22Each of these is independently a linear alkylene group having 1 to 10 carbon atoms, a1 to a4 are each independently 0 or 1, and EO and x are the same as above. In formula (a2-1-2), R a23 The C1-C10 group is a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear or branched primary alkyl group having 1 to 10 carbon atoms is preferred. Examples of linear or branched primary alkyl groups having 1 to 10 carbon atoms include linear primary alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and branched primary alkyl groups such as isopropyl, 3-methylbutyl, 4-methylpentyl, 5-methylhexyl, 6-methylheptyl, 7-methyloctyl, 8-methylnonyl, 9-methyldecyl, neopentyl, 3,3-dimethylbutyl, 4,4-dimethylpentyl, 5,5-dimethylhexyl, and 6,6-dimethylheptyl groups. a23 If the primary alkyl group is a branched chain, the number of carbon atoms is preferably 3 to 6, and more preferably 3 to 5. L a21 and L a22 These are linear alkylene groups having 1 to 10 carbon atoms, including methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and desilene groups. R a24 The group is a linear alkyl group having 1 to 5 carbon atoms, preferably a linear alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.

[0032] R a25 -CHR a26 -CH2-O-(EO) x -H ···(a2-1-1) In formula (a2-1-1), R a25 and R a26 Each of these is independently a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a linear or branched alkenyl group having 2 to 18 carbon atoms, and R a25 and R a26The total number of carbon atoms is between 5 and 19, and EO and x are the same as described above.

[0033] In formula (a2-1-1), R a25 and R a26 The total number of carbon atoms is 5 to 19, preferably 5 to 17, more preferably 5 to 15, and even more preferably 5 to 10. R a25 The number of carbon atoms is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 7. R a26 The number of carbon atoms is preferably 1 to 8, more preferably 1 to 7, and even more preferably 1 to 5.

[0034] R in equation (a2-1-1) a25 -CHR a26 -CH2- is Garbet alcohol (R a25 -CHR a26 It is a residue obtained by removing one hydroxyl group from (-CH2-OH). (A2) Component (A2) may be used alone or in combination of two or more components.

[0035] (Amphoteric surfactant) As the amphoteric surfactant (component (a3)), a compound represented by the following formula (a3) ​​is preferred. R a31 -(A) p -N + (-R a32 )(-R a33 )-R a34 -R a35 ...(a3)

[0036] In formula (a3), R a31 R represents a linear or branched alkyl group having 8 to 18 carbon atoms. a32 and R a33 Each of these independently represents an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, A represents -C=O(-NH-X)-, X represents an alkylene group having 1 to 4 carbon atoms, p is the number 0 or 1, and R a34 R represents an alkylene group with 1 to 2 carbon atoms. a35 -CO2 - or -SO3- It represents.

[0037] R in equation (a3) a31 The number of carbon atoms is preferably 10 to 14, and more preferably 11 to 14. a31 Preferably, it is an alkyl group derived from oil and fat raw materials. R a32 , R a33 Each of these is preferably an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group, R a32 and R a33 It is particularly preferable that all of them are methyl groups. R a34 The group is preferably a methylene group or an ethylene group, with the methylene group being more preferred.

[0038] (a3) Examples of components include carboxylate-type amphoteric surfactants, sulfate-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphate-type amphoteric surfactants. Among these, carboxylate-type betaine-type amphoteric surfactants and sulfonate-type betaine-type amphoteric surfactants are preferred. Examples of carboxylate salt-type amphoteric surfactants include octanoamide propyl dimethylaminoacetic acid betaine, decanoamide propyl dimethylaminoacetic acid betaine, laurate propyl dimethylaminoacetic acid betaine, myristate propyl dimethylaminoacetic acid betaine, stearate propyl dimethylaminoacetic acid betaine, oleamide propyl dimethylaminoacetic acid betaine, coconut oil fatty acid amide propyl dimethylaminoacetic acid betaine, palm oil fatty acid amide propyl dimethylaminoacetic acid betaine, and palm kernel oil fatty acid amide propyl dimethylaminoacetic acid betaine. Examples of sulfonate-type amphoteric surfactants include sulfobetaines such as N-lauryl-N,N-dimethylammonium-N-propyl sulfobetaine, N-lauryl-N,N-dimethylammonium-N-(2-hydroxypropyl) sulfobetaine, and N-lauryl-N,N-dimethyl-N-(2-hydroxy-1-sulfopropyl)ammonium sulfobetaine.

[0039] (Semi-polar surfactant) Examples of semipolar surfactants (component (a4)) include alkylamine oxide type semipolar surfactants and alkylamidoamine oxide type semipolar surfactants. (a4) The compound represented by the following formula (a4) is preferred as component (a4).

[0040] R a41 -(A) p -N(-R a42 )(-R a43 )→O ···(a4) In formula (a4), R a41 R is a linear or branched alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms. a42 and R a43 Each of these is independently an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and A is -C=O(-NH-R a44 )- represents R a44 is an alkylene group having 1 to 4 carbon atoms, and p is an integer of 0 or 1.

[0041] R in equation (a4) a41 The number of carbon atoms is preferably 10 to 14, and more preferably 11 to 14. a41 Preferably, it is an alkyl group derived from oil and fat raw materials. R a42 and R a43 Each of these is independently preferably a C1-C3 alkyl group or a C1-C3 hydroxyalkyl group, more preferably a C1-C3 alkyl group, and even more preferably a methyl group. a41 and R a43 It is particularly preferable that all of them are methyl groups. p is preferably 0. Among these, examples include alkyldimethylamine oxides such as lauryldimethylamine oxide, coconut alkyldimethylamine oxide, and lauryl diethylamine oxide; and alkanoylamide alkyldimethylamine oxides such as lauric acid amidopropyl dimethylamine oxide. Of these, alkyldimethylamine oxides are preferred from the viewpoint of cleaning power, and lauryldimethylamine oxide is even more preferred from the viewpoint of foaming power. (a4) The component may be used alone or in combination of two or more types. (A) Component may be used alone or in combination of two or more types.

[0042] The content of component (A) is preferably 0.5 to 30.0% by mass, more preferably 1.8 to 10.0% by mass, and even more preferably 2.5 to 5.0% by mass, relative to the total mass of the liquid detergent composition. If the content of component (A) is above the lower limit, the cleaning power of component (A) can be enhanced. If the content of component (A) is below the upper limit, discoloration and fading of component (B) by component (A) can be easily suppressed.

[0043] <(B) component> Component (B) is a pH indicator with a color change range of pH 7.8 to 14. The liquid detergent composition containing component (B) allows for visual confirmation that the detergent has achieved sufficient cleaning power, as the color changes immediately after dispensing and again after a predetermined period of time. (B) Component is preferably a pH indicator with a color change range of pH 7.8 to 12.0, from the viewpoint of controlling the color change time and safety.

[0044] (B) For component (B), the absorption wavelengths of the liquid detergent composition before spraying and the liquid detergent composition 10 minutes after spraying are measured in accordance with JIS K 0115, and it is preferable that the difference in wavelength at which the respective absorption peaks appear changes by 10 nm or more, and more preferably by 50 nm or more.

[0045] (B) Examples of components include thymolphthalein, phenolphthalein, thymol blue, p-xylenol blue, o-cresolphthalein, p-naphtholbenzeyne, 1,3,5-trinitrobenzene, alizarin yellow GG, alizarin yellow R, tetril, tropeoline O, and indigo carmine. The color change range and color of these compounds are shown in Table 1.

[0046] [Table 1]

[0047] (B) As component (B), a compound represented by the following formula (b1) is preferred.

[0048] [ka]

[0049] In equation (b1), X is -C (=O)- or -SO2-, and multiple R b1 Each is independently a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and multiple R b2 Each of these is independently a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

[0050] R b1 Examples of linear or branched alkyl groups having 1 to 3 carbon atoms include methyl groups, ethyl groups, and isopropyl groups. R b2 Examples of linear or branched alkyl groups having 1 to 3 carbon atoms include methyl groups, ethyl groups, and isopropyl groups. Examples of substances represented by formula (b1) include thymolphthalein, phenolphthalein, thymol blue, p-xylenol blue, and o-cresolphthalein. Among these, thymolphthalein, phenolphthalein, and thymol blue are preferred. (B) Component may be used alone or in combination of two or more types.

[0051] (B) The content of component (B) is preferably 0.0001 to 1% by mass, more preferably 0.0015 to 0.1% by mass, and even more preferably 0.002 to 0.01% by mass, relative to the total mass of the liquid detergent composition. If the content of component (B) is above the lower limit, the visibility of component (B) is enhanced at pH 10.0 or higher, making it easier to prevent fading and to prevent discoloration when the pH changes. If the content of component (B) is below the upper limit, manufacturing costs can be reduced by not using more component (B) than necessary, and it is easier to produce a color that gives users a sense of cleanliness at pH 10.0 or higher.

[0052] The mass ratio of component (A) to component (B) (hereinafter also referred to as the "A / B ratio") is preferably 600 to 5000, more preferably 1000 to 3000, and even more preferably 1300 to 1800. If the A / B ratio is above the lower limit, the proportion of component (A) increases, making it easier to increase cleaning power. If the A / B ratio is below the upper limit, the proportion of component (B) increases, making it easier to improve visibility and prevent discoloration and fading.

[0053] <(C) component> Component (C) is an aminocarboxylic acid-based chelating agent. The liquid cleaning agent composition contains component (C), which chelates metal ions (such as calcium ions) in tap water, thereby increasing the solubility of component (A) and enhancing cleaning power, while also suppressing the adhesion and accumulation of limescale on hard surfaces.

[0054] (C) Examples of component (C) include aminocarboxylic acids or salts thereof such as methylglycine diacetic acid or its salt, glutamate diacetic acid or its salt, nitrilotriacetic acid or its salt, ethylenediaminetetraacetic acid or its salt, diethylenetriaminepentaacetic acid or its salt, β-alanine diacetic acid or its salt, L-aspartate diacetic acid or its salt, iminodisuccinic acid or its salt, ethylenediaminedisuccinic acid or its salt (however, those having a hydroxyl group, an amino group, and a carboxyl group are classified as hydroxyaminocarboxylic acids); serine diacetic acid or its salt, hydroxyiminodisuccinic acid or its salt, hydroxyethylethylenediaminetriacetic acid or its salt, dihydroxyethylglycine or its salt, and other hydroxyaminocarboxylic acids or salts thereof. (C) Component is preferably methylglycindiacetic acid or a salt thereof, or ethylenediaminetetraacetic acid or a salt thereof.

[0055] Examples of salts that make up chelating agents include alkali metal salts, alkaline earth metal salts, alkanolammonium salts, and ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of alkaline earth metal salts include magnesium salts and calcium salts. Examples of alkanol ammonium salts include monoethanolammonium salt, diethanolammonium salt, and triethanolammonium salt. (C) Component may be used alone or in combination of two or more types.

[0056] The content of component (C) is preferably 0.5 to 15.0% by mass, more preferably 1.0 to 10.0% by mass, and even more preferably 2.0 to 5.0% by mass, relative to the total mass of the liquid detergent composition. If the content of component (C) is above the lower limit, it slows down the discoloration and fading of component (B) and enhances the cleaning power against aliphatic metal salts, urine stains, sebum, proteins, etc. If the content of component (C) is below the upper limit, it is possible to reduce manufacturing costs by not using more component (C) than necessary and to prevent a decrease in liquid stability due to the precipitation of component (C).

[0057] The mass ratio of component (A) to component (C) (hereinafter also referred to as "A / C") is preferably 0.1 to 3.0, more preferably 0.3 to 2.0, and even more preferably 0.6 to 1.0, relative to the total mass of the liquid detergent composition. If the A / C ratio is above the lower limit, the proportion of component (A) increases, thereby enhancing the cleaning power of component (A) by chelating metal ions in tap water. If the A / C ratio is below the upper limit, the proportion of component (C) increases, making it easier to prevent discoloration and fading of component (B) by component (A).

[0058] <Water> Liquid detergent compositions preferably contain water as a solvent, from the viewpoint of ease of handling and improved rinsability. For the water source, you can use deionized water, distilled water, or tap water.

[0059] The water content is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 95% by mass, relative to the total mass of the liquid detergent composition. When the water content is within the above range, the liquid detergent composition is easy to prepare. In addition, the solubility in water is good when using the liquid detergent composition.

[0060] <Optional ingredients> Optional components include, for example, organic solvents (hereinafter also referred to as "component (D)"), chelating agents other than component (C), metal sequestering agents, pH adjusters, disinfectants, preservatives, antifungal agents, dyes other than component (B), antioxidants, thickeners, UV absorbers, solubilizers, emulsifiers, and fragrances.

[0061] (organic solvent) As the organic solvent (component (D)), a water-soluble organic solvent is preferred. A water-soluble organic solvent is an organic solvent that dissolves in 50g or more of water at 25°C. The inclusion of an organic solvent enhances the solubility of component (B) and makes it easier to prevent the formation of a complex with component (A). Furthermore, it is easier to adjust the time from immediately after dispensing until the pH changes and the color changes, so that the time from immediately after dispensing until the dirt is removed is similar.

[0062] Examples of component (D) include polar group-containing solvents represented by the following formula (d).

[0063] [ka]

[0064] In formula (d), R d1 is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms, and X is -(AO) n -, where AO is an alkylene oxy group having 2 to 4 carbon atoms, n is the average number of repeats of AO, a number from 1 to 120, Y is a linear or branched alkylene group having 2 to 6 carbon atoms, or -SO2-, and s, t, u and v are each independently a number of 0 or 1.

[0065] In formula (d), R d1 Examples of linear or branched alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, and isopropyl groups, with methyl and isopropyl groups being preferred. Examples of alkylene oxy groups in X include ethylene oxy groups and propylene oxy groups, with ethylene oxy groups being preferred. n is a number between 1 and 120, preferably between 1 and 80, and more preferably between 1 and 46. Examples of linear or branched alkylene groups having 2 to 6 carbon atoms in Y include ethylene, propylene, and butylene groups, with ethylene and propylene groups being preferred.

[0066] (d) Component is preferably, for example, a polar group-containing aromatic solvent represented by the following formula (d1) and a glycol-based solvent represented by the following formula (d2).

[0067] [ka]

[0068] In formula (d1), R d1 Y, t, and v are the same as above.

[0069] [ka]

[0070] In formula (d2), R d1 X, t, and u are the same as described above, Z is a linear or branched alkylene group having 2 to 6 carbon atoms, and m is the average number of repeats of Z, which is either 0 or 1.

[0071] Z is a linear or branched alkylene group having 2 to 6 carbon atoms, preferably an ethylene group or a propylene group.

[0072] (d1) Examples of components include aromatic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, and cumenesulfonic acid, and aromatic alcohols such as phenoxyethanol and phenylethyl alcohol. Among these, aromatic alcohols are preferred, and phenoxyethanol is more preferred. (d2) Examples of the component include glycol-based solvents, such as dialcohols like ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monohexyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, and other ethylene glycol monoalkyl ethers; propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and other propylene glycol monoalkyl ethers; pentylene glycol monoalkyl ethers such as 3-methoxy-3-methylbutanol; and polyethers such as polyethylene glycol and polypropylene glycol. Among these, diethylene glycol monobutyl ether (butyl carbitol) is preferred. The weight-average molecular weight of polyethylene glycol is preferably 50 to 5,000, more preferably 100 to 3,500, and even more preferably 150 to 2,000. (D) Component may be used alone or in combination of two or more types.

[0073] The content of component (D) is preferably 0.1 to 5.0% by mass, more preferably 1.0 to 4.0% by mass, and even more preferably 1.5 to 3.0% by mass, relative to the total mass of the liquid detergent composition. If the content of component (D) is above the lower limit, it is easier to increase the solubility of component (B) and prevent the formation of a complex with component (A). If the content of component (D) is below the upper limit, it is easier to adjust the time from immediately after dispensing until the pH changes and the color changes, and the time from immediately after dispensing until the dirt is removed, to be close.

[0074] (Chelating agents other than component (C)) (C) The chelating agent other than component (C) is not particularly limited, and any general chelating agent that has been used in liquid detergent compositions can be used. The chelating agent may be either a low molecular weight chelating agent with a molecular weight of 800 or less, or a high molecular weight chelating agent with a weight-average molecular weight of 800 or more. In this specification, the molecular weight of low molecular weight chelating agents can be measured by mass spectrometry, and the weight-average molecular weight of high molecular weight chelating agents can be calculated by a standard polystyrene equivalent method using gel permeation chromatography (GPC).

[0075] Examples of low-molecular-weight chelating agents include hydroxycarboxylic acid-based chelating agents. Examples of hydroxycarboxylic acid chelating agents (excluding those that fall under the category of aminocarboxylic acid chelating agents) include lactic acid or its salts, malic acid or its salts, citric acid or its salts, tartaric acid or its salts, glycolic acid or its salts, gluconic acid or its salts, etc. Among these, citric acid or salts thereof are more preferred from the viewpoint of cleaning power against aliphatic metal salts, proteins, sebum, urine stains, etc. on hard surfaces.

[0076] Examples of polymer chelating agents include those having a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or a phosphate group or a salt thereof as an anionic group. Among these, polycarboxylic acid polymers or salts thereof having a carboxyl group or a salt thereof are preferred. Examples of polycarboxylic acid polymers or salts thereof include polyacrylic acid or salts thereof, copolymers of acrylic acid and sulfonic acid monomers or salts thereof, and copolymers of maleic acid and acrylic acid or salts thereof. Graft polymers of these polymers with polyalkylene glycol or salts thereof can also be suitably used.

[0077] Examples of salts that make up chelating agents include alkali metal salts, alkaline earth metal salts, alkanolammonium salts, and ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of alkaline earth metal salts include magnesium salts and calcium salts. Examples of alkanol ammonium salts include monoethanolammonium salt, diethanolammonium salt, and triethanolammonium salt. These chelating agents may be used individually or in combination of two or more.

[0078] (Other chelating agents) Other chelating agents include, for example, organic carboxylic acids, phosphonic acids, phosphonocarboxylic acids, and phosphoric acids. Examples of organic carboxylic acids 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, and gluconic acid. Examples of phosphonic acids include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and its derivatives, 1-hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, and aminotrimethylenephosphonic acid. Examples of phosphonocarboxylic acids include 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, and α-methylphosphonosuccinic acid. Examples of phosphates include orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, and condensed phosphates such as phytic acid. Other chelating agents may be used individually or in combination of two or more.

[0079] The content of other chelating agents is preferably 1.0 to 5.0% by mass, and more preferably 1.5 to 3.5% by mass, relative to the total mass of the liquid detergent composition.

[0080] (pH adjuster) Examples of pH adjusting agents include inorganic acids such as hydrochloric acid and sulfuric acid; and alkaline agents selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, and their derivatives. Among these, hydrochloric acid, sulfuric acid, sodium hydroxide, and potassium hydroxide are preferred. pH adjusters may be used individually or in combination of two or more types.

[0081] The total amount of the components constituting the liquid detergent composition is 100% by mass.

[0082] <Physical properties> (viscosity) The viscosity of the liquid detergent composition at 25°C is 30 mPa·s or less, preferably 1 mPa·s or more and 30 mPa·s or less, more preferably 1 to 20 mPa·s, and even more preferably 3 to 15 mPa·s. If the viscosity at 25°C is above the lower limit, it exhibits excellent retention on hard surfaces. If the viscosity at 25°C is below the upper limit, it becomes easier to spray from dispensing containers such as spray bottles, and also exhibits excellent liquid stability.

[0083] The viscosity of the liquid detergent composition can be adjusted by controlling the water content, adding thickeners, etc. The viscosity of the liquid detergent composition is measured at 25°C using a B-type viscometer, with rotor number No. 1 and rotor speed of 60 rpm, 60 seconds after the start of rotor rotation.

[0084] (pH) The pH of the liquid detergent composition at 25°C is 10.0 or higher, preferably 10.0 to 14.0, and more preferably 10.5 to 12.0. If the pH at 25°C is above the lower limit, the cleaning power of component (A) can be enhanced. Also, a decrease in pH is more likely to occur due to reaction with carbon dioxide and acidic stains, resulting in a greater likelihood of color change. If the pH at 25°C is below the upper limit, it is easier to adjust the time from immediately after dispensing until the pH changes and the color changes, and the time from immediately after dispensing until the stains are removed, to be close. In addition, the solubility and stability of each component can be maintained, and the liquid stability can be enhanced.

[0085] The pH of the liquid detergent composition can be adjusted by adding an appropriate amount of pH adjusting agent. The pH of the liquid detergent composition is the value measured at 25°C using a method compliant with JIS Z 8802:2011 "Method for Measuring pH".

[0086] ≪Manufacturing method≫ Liquid detergent compositions are manufactured by conventionally known manufacturing methods. For example, they can be obtained by adding components (A), (B), and (C), along with optional components other than pH adjusters as needed, to water, and adjusting the pH to the desired level with a pH adjuster as needed.

[0087] ≪Container-packaged cleaning products≫ The containerized cleaning agent product (hereinafter sometimes simply referred to as "contained product") comprises the hard surface liquid cleaning agent composition of the present invention and a dispensing container containing it. Examples of dispensing containers 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 due to their ease of use and environmental impact.

[0088] Examples of non-aerosol dispensing containers include spray type, squeeze type, and pump type. Among these, the spray type is preferred due to its ease of use. Examples of spray-type dispensing containers include aerosol spray containers, trigger spray containers (direct pressure type or pressurized type), and dispenser spray containers. These containers may be manually operated or electrically operated. Examples of aerosol spray containers include those described in Japanese Patent Publication No. 9-3441 and Japanese Patent Publication No. 9-58765. When filling an aerosol spray container, LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide, nitrogen gas, nitrous oxide gas, etc., can be used as propellants. These propellants may be used individually or in mixtures of two or more.

[0089] Examples of trigger spray containers include those described in Japanese Patent Publication No. 9-268473 and Japanese Patent Publication No. 10-76196, among others. Examples of dispenser spray containers include those described in Japanese Patent Publication No. 9-256272, for example. Examples of pressurized trigger spray containers include those described in Japanese Patent Publication No. 2013-154276, etc. Among these, a trigger spray container is preferred as the dispensing container because it makes it easy to spray the liquid cleaning agent composition onto the target. Trigger spray containers can be of the direct-pressure type or the stored-pressure type, but the stored-pressure type is preferred because it makes it easier to spray the liquid detergent composition onto the target and further enhances the retention of the liquid detergent composition. A pressurized trigger spray container is designed so that even when the trigger is operated, the contents are not discharged from the nozzle until the liquid pressure inside the cylinder reaches a predetermined level. The liquid is then sprayed when the liquid pressure inside the cylinder exceeds that level. The discharge form can be either foam or mist, but foam is preferred because it makes it easier to spray the liquid detergent composition onto the target and further enhances the retention of the liquid detergent composition.

[0090] Containers that dispense contents in a foamy form include dispensing containers that dispense the contents in a foamy form by mixing them with air. Such dispensing containers are also called foaming containers. A foaming container typically comprises a container body that holds a liquid detergent composition, and a spray nozzle attached to the opening of the container body that dispenses the liquid detergent composition contained within the container body in a foamy form. The mechanism by which the spray nozzle turns the liquid detergent composition inside the container into foam includes a mechanism in which liquid is introduced from the container into a foam-forming cylinder incorporated at the tip of the spray nozzle, and this liquid is made to collide with the wall of the foam-forming cylinder to generate turbulence and promote mixing with air. Another example is a mechanism in which a barrier or mesh is placed in front of the spray nozzle to discharge the liquid in a foamy state. The 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 structures.

[0091] Figure 1 shows an example of a dispensing container. The discharge container 1 in Figure 1 is a direct-pressure trigger-type sprayer. It comprises a container body 2 and a spray nozzle 6 provided at the opening of the container body 2. The spray nozzle 6 is connected to a suction pipe 7 that extends vertically inside the container body 2. A nozzle hole 10 is formed at the tip of the spray nozzle 6. The spray nozzle 6 is provided with a trigger 3 that extends downward from near the tip. Inside the spray nozzle 6 are a piston 4 and a spring 5. The spring 5 is connected to the trigger 3 via the piston 4. To dispense the contents (liquid detergent composition) from the discharge container 1, pull the trigger 3 towards the piston 4. When the trigger 3 is pulled towards the piston 4, the piston 4 and spring 5 are activated, and the contents are drawn up into the spray nozzle 6 by the suction pipe 7. The drawn-up contents are discharged from the nozzle hole 10 in the form of a mist or foam.

[0092] ≪How to use≫ The liquid cleaning agent composition can be used in the following ways: "rinse-and-clean (no scrubbing)" by spraying an appropriate amount onto a hard surface and rinsing with a shower or flush after a certain period of time; "scrub-and-clean" by spraying an appropriate amount onto a hard surface and scrubbing it with a cleaning brush; and "wipe-and-clean" by wiping it with a cloth or paper. The liquid cleaning agent composition for hard surfaces of the present invention is preferably for use in bathrooms and toilets, and more preferably for use in bathrooms. Let's take a bathroom-use container product as an example. One method of use is to spray an appropriate amount of liquid cleaning agent composition from the dispensing container into the bathroom, such as a bathtub, and after a certain period of time, check for a color change, then rinse with a shower or similar device ("rinse without scrubbing"). In this case, because the liquid cleaning agent composition has good dispensing properties, it is easy to spray the liquid cleaning agent composition to the desired location. In addition, because the liquid cleaning agent composition has excellent cleaning power and excellent retention properties, dirt inside the bathroom can be cleaned by rinsing without scrubbing.

[0093] <Effects> The mechanism by which the effects of the present invention are obtained is not clear, but it is presumed to be as follows. (A) By including this ingredient, the cleaning power can be improved. (B) By containing component (B), visibility is achieved, and the color develops in a way that gives the user a sense of cleanliness. In addition, the color changes in response to changes in pH, allowing users to visually confirm that the dirt has been sufficiently removed. By including component (C), the cleaning power is enhanced, and by preventing discoloration and fading of component (B) by component (A), the time required for color change due to pH change and the time sufficient for cleaning to be achieved can be adjusted to be close together. Most of the components of (B) have weakly acidic groups such as phenolic hydroxyl groups, so they ionize in alkaline conditions and become protonated as the pH changes towards neutral, changing the resonance structure and causing a color change. Fig. 1 of Non-Patent Literature 1 shows that a complex is formed between a nonionic surfactant and a non-dissociating pH indicator, and that at low to neutral pH levels around pH 4.0, the addition of a nonionic surfactant causes a color change (discoloration) without any pH fluctuation. Fig. 1 also shows that when a complex is formed between a surfactant and a pH indicator, the color development of the pH indicator itself decreases (fading) at high pH levels of pH 5.6 or higher. Furthermore, Figs. 2 and 3 show that using a nonionic surfactant that is easily soluble in water makes it easier to cause discoloration of a pH indicator that is not easily soluble in water. Based on these descriptions in Non-Patent Literature 1, it can be inferred that using other surfactants that are more soluble in water (especially anionic surfactants and amphoteric surfactants) would be more likely to cause discoloration and fading than using nonionic surfactants. However, contrary to this expectation, the present invention suppresses discoloration and fading by adding component (C), even when using a wide range of surfactants. The mechanism by which the effects of this invention are obtained is not clear, but it is presumed to be as follows. It is believed that when component (C) chelates metal ions in tap water, the surfactant becomes more soluble in water, thereby preventing electrostatic interactions between the hydrophilic or hydrophobic regions of components (A) and (B), inhibiting the formation of a complex, and thus suppressing discoloration and fading of (B). Therefore, contrary to the results of Non-Patent Document 1, for example, it is presumed that in the present invention, a larger difference in ClogP value and octanol / water partition coefficient between components (A) and (B) is preferable. Furthermore, since component (B) contains many aromatic ring-containing compounds, it is presumed that if component (A) has linear or branched hydrocarbon groups and does not have an aromatic ring, the interaction (π-π stacking) with component (B) which has an aromatic ring can be reduced, making it easier to suppress the formation of a complex, and thus making it easier to suppress discoloration and fading of (B). [Examples]

[0094] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following description.

[0095] "Raw materials used" <(A) component> • a-1: C14-α-olefin sulfonate sodium (AOS) (Lion Specialty Chemicals Co., Ltd., product name "Liporan LJ441"), in formula (a1-2-1), R a1 is an n-octyl group, R a2 This is a 5-hexenylene group, M a1 It is a compound that contains sodium ions. a-2: Linear alkylbenzene sulfonic acid (LAS) (C10-16) (Lion Specialty Chemicals Co., Ltd., product name "Lypon PS-230"). • a-3: Polyoxyethylene isotridecyl ether (average ethylene oxide 7-mol adduct of branched C13 alcohol) (BASF Japan Ltd., trade name "Lutensol TO-7", in formula (a2-1), R a21 A compound in which x is a branched-chain primary alkyl group with 13 carbon atoms, and x is 7. • a-4: Lauric acid amidopropyl betaine (LPB) (manufactured by Lion Specialty Chemicals Co., Ltd., product name "Energicol (registered trademark) L-30B"), in formula (a3), R a31 A is a linear alkyl group with 11 carbon atoms, A represents -C=O(-NH-X)-, X is a propylene group, p is 1, and R a32 is a methyl group, R a33 R is a methyl group, a34 is a methylene group, R a35 -CO2 - A compound that is • a-5: Lauryldimethylaminoacetic acid betaine (LDB) (Sanyo Chemical Industries, Ltd., product name "Rebon LD-36"), in formula (a3), R a31 is a linear alkyl group with 12 carbon atoms, p is 0, and R a32 is a methyl group, R a33 R is a methyl group, a34 is a methylene group, R a35 -CO2 - A compound that is

[0096] <(B) component> b-1: Thymolphthalein (Kishida Chemical Co., Ltd., product name "Special Grade Thymolphthalein (Reagent)"), in formula (b1), two R b1 Both are isopropyl groups, two R b2 These are all compounds in which a methyl group is present and X is -C(=O)-. b-2: Phenolphthalein (Fujifilm Wako Pure Chemical Industries, Ltd., trade name "Phenolphthalein"), in formula (b1), two R b1Both are hydrogen atoms, two R b2 These are all compounds in which the hydrogen atom is X and X is -C(=O)-. b-3: Thymol blue (Fujifilm Wako Pure Chemical Corporation, product name "Thymol Blue"), in formula (b1), two R b1 Both are isopropyl groups, two R b2 These are all compounds in which a methyl group is present and X is -SO2-. ·b'-1: Bromothymol blue (Fujifilm Wako Pure Chemical Industries, Ltd., product name "Bromothymol Blue"), a comparative product of component (B). pH color change range: 6.0~7.6. A compound having bromo groups at the ortho positions of the two hydroxyl groups of thymol blue.

[0097] <(C) component> • c-1: Trisodium methylglycine diacetate (BASF, trade name "Trilon M"). • c-2: Tetrasodium ethylenediaminetetraacetate (Nurion Co., Ltd., trade name "DISSOLVINE E-39").

[0098] <Optional ingredients> (D) Component ·d-1: Diethylene glycol monobutyl ether (Nippon Emulsifier Co., Ltd., trade name "Butyl Diglycol"), in formula (d2), R d1 A compound in which is an n-butyl group, t is 1, X is an ethyleneoxy group, u is 1, Z is an ethylene group, and m is 1. (pH adjuster) • Sodium hydroxide (Kanto Chemical Co., Ltd., special grade) • Citric acid (manufactured by Fuso Chemical Industry Co., Ltd., product name "Anhydrous Citric Acid") (water) • Water: Ion-exchanged water. The amount is such that the total mass is 100% by mass.

[0099] Examples 1-22, Comparative Examples 1-7 <Preparation of liquid cleaning agent composition for hard surfaces> ≪Composition preparation method≫ In a 300 ml beaker, components (A) and (C) were added sequentially to 150 g of deionized water to create a composition with a total volume of approximately 200 g. Sodium hydroxide was added to adjust the pH to 12.0, then component (B) was added sequentially and stirred with a stirrer. After adding the remaining optional components and stirring, sodium hydroxide or citric acid, which are pH adjusters, were added to adjust the pH to the extent shown in Tables 2 to 5. The remaining balance water was added and stirred to prepare the hard surface liquid cleaning agent compositions of Examples 1 to 22 and Comparative Examples 1 to 7. The composition (ingredients and their content (mass%)) of the hard surface liquid cleaning agent compositions obtained for each example is shown in the table. Unless otherwise specified, mass% indicates the pure content. If there are blank spaces for an ingredient in the table, that ingredient is not included. In the table, the "appropriate amount" for the pH adjuster content is the amount required to bring the pH of each hard surface liquid cleaning agent composition to the value shown in the table. In the table, the "balance" for the water content refers to the remainder added so that the total amount (mass%) of all ingredients in the hard surface liquid cleaning agent composition becomes 100 mass%.

[0100] ≪Evaluation Method≫ 1. Cleaning power A test piece made of fiberglass-reinforced plastic (FRP) (2cm x 10cm) was fixed to the inner wall of a bathtub in a typical household. Three adult men then each took a bath three times (one bath per day for three days, during which only the bathwater was changed, and the bathtub was not cleaned), allowing dirt to adhere to the test piece. After thoroughly drying the test pieces with the contaminated surface, the hard surface liquid cleaning agents for each example were dropped onto the test pieces, diluted 3-fold and 5-fold respectively with deionized water, so that the entire surface was wet. After letting it stand for 30 seconds, it was rinsed with tap water (15°C). After thoroughly drying the test pieces, the degree of dirt removal on the surfaces of the five test pieces was evaluated visually and by touch according to the following evaluation criteria for cleaning power. In the evaluation criteria below, a score of △ or higher was considered a pass. The results are shown in Tables 2 to 5. (Evaluation Criteria) ◎: Excellent stain removal. ○: Removes stains very well. △: Good at removing stains. ×: Does not clean well.

[0101] 2. Evaluation of Visibility For the interior walls of typical household bathtubs, each hard-surface liquid cleaning agent was placed in a container of Lion Corporation's Bathtub Cleanser and sprayed once onto the inside of the bathtub so that the cleaning solution covered the inside of the bathtub. The appearance was then visually inspected for 2 seconds immediately after spraying and evaluated according to the following evaluation criteria. In the evaluation criteria below, a score of △ or higher was considered a pass. The results are shown in Tables 2-5. (Evaluation Criteria) ◎: The area where the liquid has been applied can be easily identified from a distance of 2m. ○: The area where the liquid has been applied can be easily identified from a distance of 1 meter. △: The area where the liquid has been applied can be easily identified from a distance of 0.3m. ×: It is not easy to identify the area where the liquid has been applied from a distance of 0.3m.

[0102] 3. Evaluation of color change In a typical household bathtub, each hard-surface liquid cleaner was placed in a container of Lion Corporation's Bathtub Cleanser and sprayed once onto the inside of the bathtub. The time from spraying until the color changed was measured. A test was considered successful if the measured time fell within the following range. A score of △ or higher was considered successful according to the evaluation criteria below. The results are shown in Tables 2-5. (Evaluation Criteria) ○: 25 seconds or more but less than 55 seconds. △: 55 seconds or more but less than 85 seconds. ×: Less than 25 seconds, 85 seconds or more, or no change.

[0103] [Table 2]

[0104] [Table 3]

[0105] [Table 4]

[0106] [Table 5]

[0107] As is clear from Tables 2-5, the hard surface liquid cleaning agent compositions of each example had a cleaning power of "△~◎", visibility of "△~◎", and color change of "△~◎". Comparative Example 1, with an A / B ratio of 150, showed a "×" in cleaning power. Comparative Example 2, with an A / B ratio of 10000, showed "X" for both visibility and color change. Comparative Example 3, which used a comparative sample of component (B) with a color change range of pH 6.0 to 7.6, showed no color change ("×"). Comparative Example 4, with a pH of 9.0, showed "X" for both visibility and color change. Comparative Example 5, which did not contain ingredient (A), had a cleaning power of "×". Comparative Example 6, which did not contain component (B), showed "X" for both visibility and color change. Comparative Example 7, which did not contain component (C), showed no color change ("×").

Claims

1. (A) Ingredients: Surfactant and (B) Component: A pH indicator with a color change range of pH 7.8 to 14, (C) Components: Contains an aminocarboxylic acid-based chelating agent, The mass ratio expressed as [mass of component (A)] / [mass of component (B)] is between 600 and 5000. A liquid cleaning agent composition for hard surfaces having a pH of 10 or higher at 25°C.

2. The liquid cleaning agent composition for hard surfaces according to claim 1, wherein the component (A) comprises one or more selected from the group consisting of anionic surfactants (a1), nonionic surfactants (a2), and amphoteric surfactants (a3).

3. The liquid cleaning agent composition for hard surfaces according to claim 1 or 2, wherein the (C) component comprises one or more selected from the group consisting of phenolphthalein, thymolphthalein, and thymol blue.

4. Furthermore, it contains component (D), The liquid cleaning agent composition for hard surfaces according to claim 1 or 2, wherein the (D) component is a solvent containing a glycol ether-based solvent.

5. A liquid cleaning agent composition for hard surfaces according to claim 1 or 2, for use in bathrooms.

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