Liquid detergent for hard surface, liquid detergent product for hard surface, and washing method of hard surface

Abstract

To provide a liquid detergent for a hard surface which is good in washing power and rinsing properties.SOLUTION: A liquid detergent for a hard surface includes: a component (A) which is selected from a non-soap-based anion surfactant and an ampholytic surfactant; a component (B) which is represented by R1-O-(C2H4O)x-(C3H6O)y-R2(R1 and R2 are, for example, a 1-6C alkyl group); a component (C) which is an aminocarboxylic acid chelating agent; and a component (D) which is a nonionic aromatic compound selected from a compound represented by a formula (d1) or a formula (d2). The liquid detergent for the hard surface has a pH at 25°C of 8.5 or more. A mass ratio A / D is 0.1 to 1,000. In the formula (d1), X is an oxygen atom or a 1-4C alkylene group, Y is a chlorine atom or a bromine atom, a, b, and c are each 0 or an integer of 1 to 3, m is 0 or 1, and n is 0 or 1. In the formula (d2), V and W are a hydrogen atom and a 1-4C alkyl group and R3 is a hydrogen atom or a 1-4C alkyl group.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In recent years, in the cleaning of hard surfaces such as bathrooms, a liquid detergent has been developed that can remove dirt without rubbing, simply by spraying a detergent solution onto the object to be cleaned and then rinsing it with water, without using a cleaning tool such as a sponge. For example, Patent Document 1 proposes a liquid detergent for bathrooms containing a non-soap anionic surfactant, a glycol-based solvent, and an aminocarboxylic acid type chelating agent.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In a method of removing dirt without rubbing, it is necessary to attach the detergent to the entire surface of the object to be cleaned, which increases the amount of detergent used and tends to deteriorate the rinsability. When the rinsability deteriorates, the time required to rinse off the detergent by pouring water increases, and the amount of rinsing water also increases. Conventional liquid detergents tend to have inferior detergency when the rinsability is improved, and it has been difficult to achieve both good rinsability and detergency. An object of the present invention is to provide a liquid detergent for hard surfaces having good detergency and rinsability.

Means for Solving the Problems

[0005] The present invention has the following aspects. [1](A) Component: One or more selected from the group consisting of non-soap anionic surfactants (a1) and amphoteric surfactants (a2), (B) Component: One or more compounds represented by the following general formula (I), (C) Component: One or more aminocarboxylic acid type chelating agents, and (D) Component: Contains one or more nonionic aromatic compounds selected from the group consisting of the compound represented by the following formula (d1) and the compound represented by the following formula (d2), The pH at 25 °C is 8.5 or higher, A hard surface liquid detergent in which A / D, which represents the mass ratio of the content of the (A) component to the content of the (D) component, is 0.1 to 1000. R 1 -O-(C 2 H 4 O) x -(C 3 H 6 O) y -R 2 (I) (R 1 、R 2 Each independently represents a hydrogen atom, an alkyl group or an alkenyl group having 1 to 6 carbon atoms, x is 0 to 5, y is 0 to 5, and x and y do not become 0 at the same time.)

[0006]

Chemical formula

[0007] [In formula (d1), X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms, Y is each independently a chlorine atom or a bromine atom, a, b, and c are each independently 0 or an integer of 1 to 3, m is 0 or 1, and n is 0 or 1.]

[0008]

Chemical formula

[0009] [In formula (d2), V and W are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, R3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. [2] The hard surface liquid detergent according to [1], wherein (B + C) / D, which represents the mass ratio of the total content of the (B) component and the (C) component to the content of the (D) component, is 2 to 3000. [3] The hard surface liquid detergent according to [1], further comprising (E) a nonionic surfactant. [4] The hard surface liquid detergent according to [1], which is for use in a bathroom. [5] A hard surface liquid detergent product, comprising the hard surface liquid detergent according to any one of [1] to [4] and a discharge container containing the hard surface liquid detergent. [6] A method for cleaning a hard surface, comprising bringing a liquid obtained by diluting the hard surface liquid detergent according to any one of [1] to [4] with water into contact with an object to be cleaned. [Advantages of the Invention]

[0010] According to the present invention, a hard surface liquid detergent having good detergency and rinsability can be obtained. [Embodiments for Carrying Out the Invention]

[0011] [[Hard Surface Liquid Detergent]] The hard surface liquid detergent of the present invention (hereinafter sometimes simply referred to as "liquid detergent") is a composition containing components (A) to (D). It is preferably further contains component (E). In the present specification, a 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.

[0012] [Component (A)] Component (A) is at least one selected from the group consisting of a non-soap anionic surfactant (a1) and an amphoteric surfactant (a2). The non-soap anionic surfactant is an anionic surfactant excluding soap. In the present specification, "soap" means a salt of a higher fatty acid (fatty acid having 8 to 24 carbon atoms). In the present invention, component (A) functions as a component for enhancing detergency.

[0013] [Non-soap anionic surfactant (a1)] (a1) component can be exemplified as follows. (1) Linear alkylbenzene sulfonic acid or its salt. The number of carbon atoms in the alkyl group is preferably 8 to 16, more preferably 10 to 14. (2) Alkyl sulfuric acid or its salt. The number of carbon atoms in the alkyl group is preferably 10 to 20, more preferably 10 to 16. (3) Alkyl ether sulfuric acid or its salt or alkenyl ether sulfuric acid or its salt. A polyoxyethylene alkyl ether sulfuric acid or its salt or polyoxyethylene alkenyl ether sulfuric acid or its salt having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average of 1 to 10 moles of ethylene oxide added thereto is preferred. (4) α-olefin sulfonic acid or its salt. α-olefin sulfonic acid is an olefin sulfonic acid in which the carbon-carbon double bond is at the 1-position (α-position). The number of carbon atoms is preferably 10 to 20, more preferably 10 to 16. (5) Internal olefin sulfonic acid or its salt. Internal olefin sulfonic acid is an olefin sulfonic acid in which the carbon-carbon double bond is at the 2-position or higher (internal). The number of carbon atoms is preferably 16 to 24, more preferably 16 to 18. (6) Alkane sulfonic acid or its salt. A secondary alkane sulfonic acid or its salt having an alkyl group having 10 to 20 (preferably 14 to 17) carbon atoms is preferred. (7) α-sulfo fatty acid ester or its salt. An α-sulfo fatty acid ester or its salt having 10 to 20 (preferably 10 to 18) carbon atoms is preferred. (8) Polyoxyalkylene ether carboxylic acid or its salt. A polyoxyethylene alkyl ether carboxylic acid or its salt or polyoxyethylene alkenyl ether carboxylic acid or its salt having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average of 1 to 10 moles of ethylene oxide added thereto is preferred.

[0014] Examples of the salt of the component (a1) include alkali metal salts, alkaline earth metal salts, alkanolamine salts, ammonium salts and the like. Examples of the alkali metal salt include sodium salts, potassium salts and the like. Examples of the alkaline earth metal salt include magnesium salts, calcium salts and the like. Examples of the alkanolamine salt include monoethanolamine salts (monoethanolamine), diethanolamine salts (diethanolamine), triethanolamine salts (triethanolamine) and the like. Among these, as the salt of the component (A), an alkali metal salt is preferable, and a sodium salt and a potassium salt are more preferable.

[0015] In terms of detergency and rinsability, it is preferable that the component (A) contains a component (Aa) selected from the group consisting of α-olefin sulfonic acid or its salt (AOS), internal olefin sulfonic acid or its salt (IOS), linear alkylbenzene sulfonic acid or its salt (LAS), alkyl sulfate or its salt (AS), and alkyl ether sulfate or its salt (AES). Of the total mass of the component (A) contained in the liquid detergent, the total of the component (Aa) is preferably more than 10% by mass, more preferably more than 30% by mass, and even more preferably more than 50% by mass. It may be 100% by mass.

[0016] Particularly, it is preferable that the component (A) contains α-olefin sulfonic acid or its salt (AOS). For example, of the total mass of the component (A) contained in the liquid detergent, the proportion of AOS is preferably more than 30% by mass, more preferably more than 50% by mass. It may be 100% by mass.

[0017] [Amphoteric surfactant (a2)] Examples of the component (a2) include amino acid type amphoteric surfactants, betaine type amphoteric surfactants, and amine oxide type amphoteric surfactants. The amphoteric surfactant may be used alone or in appropriate combination of two or more. Among these, betaine type amphoteric surfactants and amine oxide type amphoteric surfactants are more preferable in terms of detergency.

[0018] The number of carbon atoms of the amine oxide type amphoteric surfactant is preferably 8 to 20, more preferably 8 to 18. Specific examples include lauryldimethylamine oxide, coconut alkyl dimethylamine oxide, lauryldiethylamine oxide, lauric acid amidopropyldimethylamine oxide, myristyldimethylamine oxide and the like.

[0019] <Component (B)> Component (B) is one or more compounds represented by the following general formula (I). Component (B) is a glycol ether solvent and functions as a component for enhancing detergency in the present invention. R 1 -O-(C 2 H 4 O) x -(C 3 H 6 O) y -R 2 (I) (R 1 、R 2 each independently represents a hydrogen atom, an alkyl group or an alkenyl group having 1 to 6 carbon atoms, x is 0 to 5, y is 0 to 5, provided that x and y do not simultaneously become 0.)

[0020] In formula (I), x is a number representing the average number of repeating units of oxyethylene groups, preferably 2 to 6, more preferably 2 to 4. In formula (I), y is a number representing the average number of repeating units of oxypropylene groups, preferably 0 to 5, more preferably 0 to 2.

[0021] Specific examples of component (B) include diethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene glycol monohexyl ether and the like. From the viewpoint of detergency, diethylene glycol monobutyl ether is particularly preferred.

[0022] In terms of detergency, it is preferable that the component (B) contains a component (Bb) which is at least one selected from the group consisting of diethylene glycol monobutyl ether and diethylene glycol monohexyl ether. Of the total mass of the component (B) contained in the liquid detergent, the total of the component (Bb) is preferably more than 30% by mass, more preferably more than 50% by mass, still more preferably more than 70% by mass. It may be 100% by mass.

[0023] <Component (C)> The component (C) is an aminocarboxylic acid type chelating agent. The component (C) contained in the liquid detergent may be one kind or two or more kinds. In the present invention, the component (C) functions as a component for enhancing detergency.

[0024] Examples of the component (C) include the following compounds and their salts (for example, alkali metal salts). The component (B) may be a hydrate. MethylGlycineDiacetic Acid (abbreviation "MGDA"), Ethylene Diamine Tetraacetic Acid (abbreviation "EDTA"), N-(hydroxyethyl)ethylenediamine tetraacetic acid (abbreviation "HEDTA"), N-(2-hydroxylethyl)glycine (abbreviation "DHEG"), Diethylene Triamine Pentaacetic Acid (abbreviation "DTPA").

[0025] As the component (C), MGDA or its salt, EDTA or its salt, HEDTA or its salt, DHEG or its salt, DTPA or its salt is preferable. In terms of detergency, it is preferable that the component (C) contains a component (Cc) which is at least one selected from the group consisting of MGDA or its salt, EDTA or its alkali metal salt. The salt is preferably an alkali metal salt, more preferably a sodium salt. Of the total mass of the component (C) contained in the liquid detergent, the total of the component (Cc) is preferably more than 30% by mass, more preferably more than 50% by mass, still more preferably more than 70% by mass. It may be 100% by mass.

[0026] <(D) component> (D) component is at least one nonionic aromatic compound selected from the group consisting of the compound (d1) represented by the following formula (d1) and the compound (d2) represented by the following formula (d2). In the present invention, the component (D) contributes to the improvement of rinsability. In addition, although the liquid detergent is more likely to cause separation during storage as the concentration is higher (as the water content is lower), the component (D) suppresses such separation and contributes to storage stability.

[0027]

Chemical formula

[0028] In formula (d1), -(Y)b means that b of the hydrogen atoms bonded to the carbon atoms constituting the benzene ring are substituted by Y. The same applies to -(Y)c, -(OH)m and -(OH)n. In formula (d1), X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms. An oxygen atom is preferred. Each Y is independently a chlorine atom or a bromine atom. A chlorine atom is preferred. a, b, c are each independently 0 or an integer of 1 to 3. a is preferably 0 or 1. a = 0 represents a single bond. It is preferable that at least one of b and c is 1 or more, and more preferably both are 1 or more. The total of b and c is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 to 3. m is 0 or 1. n is 0 or 1. The sum of m and n is from 0 to 2, preferably from 0 to 1, and particularly preferably 0.

[0029] Examples of the component (d1) include monochlorohydroxydiphenyl ether, dichlorohydroxydiphenyl ether, trichlorohydroxydiphenyl ether, and benzyl chlorophenol. The following compounds are preferred in terms of rinsability. Dichlorosan (4,4'-dichloro-2-hydroxydiphenyl ether, a compound in which X = oxygen atom, Y = chlorine atom, a = 1, b = 1, c = 1, n = 0, m = 0 in the formula (d1)), Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether, a compound in which X = oxygen atom, Y = chlorine atom, a = 1, b = 2, c = 1, n = 0, m = 0 in the formula (d1)).

[0030] [Chemical formula]

[0031] In the formula (d2), V and W are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is preferred that both V and W are alkyl groups having 1 to 4 carbon atoms. R 3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom is preferred. As the component (d2), isopropylmethylphenol is preferred.

[0032] It is preferred that the component (D) contains one or more selected from the group consisting of dichlorosan, triclosan, and isopropylmethylphenol. For example, in the total mass of the component (D) contained in the liquid detergent, the total of dichlorosan, triclosan, and isopropylmethylphenol is preferably more than 90% by mass, more preferably more than 93% by mass, still more preferably more than 95% by mass, and particularly preferably more than 98% by mass. It may also be 100% by mass. Particularly, it is preferable that the component (D) contains dichlorosan. For example, among the total mass of the component (D) contained in the liquid detergent, the proportion of dichlorosan is preferably more than 90% by mass, more preferably more than 93% by mass, still more preferably more than 95% by mass, and particularly preferably more than 98% by mass. It may be 100% by mass.

[0033] <Component (E)> The component (E) is a nonionic surfactant. In the present invention, the component (E) contributes to the storage stability of the liquid detergent. Examples of the component (E) include polyoxyalkylene type nonionic surfactants, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, fatty acid polyglycerol esters, sugar fatty acid esters, alkylene oxide adducts of hydrogenated castor oil, alkyl glycosides, alkyl polyglycosides, and alkyl glyceryl ethers. The component (E) may be used alone or in combination of two or more.

[0034] As the component (E), from the viewpoints of storage stability and rinsability, polyoxyalkylene type nonionic surfactants, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, and fatty acid polyglycerol esters are preferable. Particularly, it is preferable that the component (E) contains a polyoxyalkylene type nonionic surfactant (e1). As the component (e1), it is preferable to contain a polyoxyalkylene type nonionic surfactant having a linear or branched alkyl group with 8 to 18 carbon atoms and an average addition mole number of ethylene oxide of 3 to 20. The number of carbon atoms of the alkyl group is preferably 8 to 16, more preferably 10 to 14. The average addition mole number of ethylene oxide is preferably 5 to 18. For example, among the total mass of component (E) contained in the liquid detergent, the total of the polyoxyalkylene type nonionic surfactant (e1) is preferably more than 30% by mass, more preferably more than 50% by mass, still more preferably more than 70% by mass. It may be 100% by mass.

[0035] <Water> From the viewpoints of ease of handling during production and solubility in water when in use, etc., the liquid detergent preferably contains water as a solvent. Examples of the water include ion-exchanged water and pure water. The content of water is preferably 30 to 99.5% by mass, more preferably 70 to 95% by mass, based on the total mass of the liquid detergent.

[0036] <Optional component> The liquid detergent may contain optional components other than components (A) to (E). Examples of the optional components include surfactants other than component (A) and (E) (hereinafter sometimes referred to as "optional surfactants"), pH adjusters, fragrances, dyes, water-soluble polymers, viscosity minerals, etc. Note that the total of components (A) to (E) and the optional components does not exceed 100% by mass.

[0037] Examples of the optional surfactant include amine oxide type surfactants, cationic surfactants, higher fatty acids and their salts (i.e., soaps). The optional surfactant may be one kind or two or more kinds may be used in combination. Examples of the pH adjuster include sodium hydroxide, potassium hydroxide, citric acid, hydrochloric acid, etc.

[0038] <Content · Ratio> The content of component (A) based on the total mass of the liquid detergent is preferably 0.1 to 5% by mass, more preferably 0.3 to 2% by mass. When the content of component (A) is at least the above lower limit value, the detergency is excellent, and when it is at most the above upper limit value, the rinsability is excellent.

[0039] The content of component (B) is preferably 0.1 to 10% by mass, more preferably 0.3 to 6% by mass, based on the total mass of the liquid detergent. When the content of component (B) is at least the above lower limit value, the detergency is excellent, and when it is at most the above upper limit value, the storage stability is excellent.

[0040] The content of component (C) is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on the total mass of the liquid detergent. When the content of component (C) is at least the above lower limit value, the detergency is excellent. When it is at most the above upper limit value, the storage stability is excellent. In addition, the rinsability is excellent.

[0041] The total content of component (B) and component (C) is preferably 0.2 to 25% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass, based on the total mass of the liquid detergent.

[0042] The content of component (D) is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 1.0% by mass, and particularly preferably 0.03 to 0.3% by mass, based on the total mass of the liquid detergent. When the content of component (D) is at least the above lower limit value, the rinsability is excellent, and when it is at most the above upper limit value, the detergency is excellent.

[0043] When the liquid detergent contains component (E), the content of component (E) is preferably 0.01 to 5.0% by mass, more preferably 0.1 to 3.0% by mass, based on the total mass of the liquid detergent. When the content of component (E) is at least the above lower limit value, the effect of improving the storage stability is excellent, and when it is at most the above upper limit value, the rinsability is excellent.

[0044] A / D, which represents the mass ratio of the total content of component (A) to the content of component (D), is 0.1 to 1000, preferably 0.5 to 500, more preferably 1 to 150, and particularly preferably 5 to 30. When the value of A / D is at least the above lower limit value, the detergency is excellent, and when it is at most the above upper limit value, the rinsability is excellent.

[0045] (B + C) / D, which represents the mass ratio of (B + C) to the content of (D), is preferably from 2 to 3000, more preferably from 5 to 500, and particularly preferably from 10 to 100. When the value of (B + C) / D is at least the above lower limit, the total content of the (B) component and the (C) component is excellent in detergency, and when it is at most the above upper limit, it is excellent in rinsability.

[0046] With respect to the total mass of the liquid detergent, the total mass of the detergent base ((A) component + (B) component + (C) component + (D) component + (E) component) is preferably from 0.2 to 10% by mass, more preferably from 0.4 to 8% by mass, and particularly preferably from 0.5 to 5% by mass. Among the total mass of the detergent base, the proportion of the total content of the (A) component and the (E) component is preferably more than 20% by mass, more preferably more than 30% by mass, and even more preferably more than 50% by mass. It may be 100% by mass.

[0047] With respect to the total mass of the detergent base, the content of the (A) component is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, and particularly preferably from 10 to 20% by mass. With respect to the total mass of the detergent base, the content of the (B) component is preferably from 1 to 60% by mass, more preferably from 5 to 50% by mass, and particularly preferably from 10 to 40% by mass. With respect to the total mass of the detergent base, the content of the (C) component is preferably from 1 to 80% by mass, more preferably from 10 to 70% by mass, and particularly preferably from 30 to 60% by mass. With respect to the total mass of the detergent base, the total content of the (B) component and the (C) component is preferably from 10 to 90% by mass, more preferably from 50 to 80% by mass. With respect to the total mass of the detergent base, the content of the (D) component is preferably from 0.001 to 30% by mass, more preferably from 0.01 to 10% by mass, and particularly preferably from 0.02 to 5% by mass. When the liquid detergent contains the (E) component, the content of the (E) component with respect to the total mass of the detergent base is preferably from 1 to 60% by mass, more preferably from 2 to 50% by mass, and particularly preferably from 5 to 40% by mass.

[0048] <ph> The pH of the liquid detergent at 25°C is 8.5 or higher, preferably 9 or higher, more preferably 10 or higher, and particularly preferably 10.5 or higher. When the pH is at or above the lower limit value, the detergency is excellent. The upper limit of the pH is not particularly limited, but from the viewpoint of ease of handling during use, it is preferably 13 or lower, more preferably 12 or lower. 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".

[0049] <Composition of 1-fold dilution product · Composition when diluted and used> The liquid detergent of this embodiment may be used without dilution (also referred to as 1-fold dilution) or may be used after dilution with water. A product that uses a concentrated type stock solution after dilution has the advantage of being able to make the product container compact. The following composition is a preferable composition of a 1-fold dilution product used without dilution. The dilution ratio of the concentrated product used after diluting more than 1-fold is preferably more than 1-fold and 10-fold or less, more preferably 2 to 6-fold. The preferable composition of the diluted solution of the concentrated product, that is, the preferable composition during use, is the same as the preferable composition of the 1-fold dilution product.

[0050] In the case of a 1-fold dilution product used without dilution, the content of component (A) is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and particularly preferably 0.5 to 1.5% by mass with respect to the total mass of the liquid detergent. The content of component (B) is preferably 0.1 to 10% by mass, more preferably 0.3 to 6% by mass, and particularly preferably 0.5 to 3% by mass with respect to the total mass of the liquid detergent. The content of component (C) is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 5% by mass with respect to the total mass of the liquid detergent. With respect to the total mass of the liquid detergent, the total content of component (B) and component (C) is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and particularly preferably 2 to 10% by mass. The content of component (D) relative to the total mass of the liquid detergent is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 1.0% by mass, and particularly preferably 0.03 to 0.3% by mass. When the liquid detergent contains component (E), the content of component (E) relative to the total mass of the liquid detergent is preferably 0.01 to 5.0% by mass, more preferably 0.1 to 3.0% by mass, and particularly preferably 0.2 to 2.0% by mass. Relative to the total mass of the liquid detergent, the total mass of the cleaning base is preferably 2 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 4 to 10% by mass.

[0051] <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 accommodated in the discharge container.

[0052] Examples of the discharge container for accommodating the liquid detergent include spray containers and squeeze containers, etc. However, a spray container is preferred because of its excellent applicability to the object to be cleaned. Examples of the spray container include aerosol spray containers, trigger spray containers, dispenser spray containers, etc. These containers may be manual or electric. The spray container may be any one that can discharge the liquid detergent in a mist form. Also, those that can discharge in either a mist form or a foam form and can switch between these are acceptable. Also, those that can switch between a wide pattern for discharging the liquid detergent over a wide range and a narrow pattern for discharging over a narrow range are acceptable. A trigger-type spray container with a known mechanism can be used, and it may be a direct pressure type or an accumulator type. Examples of the trigger-type spray container include those described in, for example, JP-A-10-146546 and JP-A-2000-24561.

[0053] <Manufacturing method> The liquid detergent of the present invention can be manufactured according to the manufacturing methods of conventionally known liquid detergents. For example, a method of adding the components (A) to (D) to water as a solvent, adding component (E) and optional components as necessary, and mixing them can be mentioned. The liquid detergent product of the present invention is produced by producing a liquid detergent by the above method and storing it in a discharge container.

[0054] <Method for cleaning hard surfaces> A method for cleaning a hard surface using a liquid detergent is a method of diluting the liquid detergent with water or bringing it into contact with the object to be washed without diluting it with water. For example, a liquid detergent (which may be a diluted solution) is stored in a discharge container, and an appropriate amount of the liquid detergent is discharged from this discharge container and brought into contact with the object to be washed. Then, it is left for an arbitrary time, rinsed with water, and the object to be washed is washed. The leaving time is preferably, for example, 10 seconds or more, more preferably 30 seconds or more. The upper limit is preferably 10 minutes or less from the viewpoint of the influence on the object to be washed (such as coloring and deterioration).

[0055] Since the liquid detergent of the present invention has excellent detergency, the object to be washed can be washed without applying mechanical force such as scrubbing the object to be washed with a cleaning tool such as a hand or a sponge. Here, "without applying mechanical force" means that no intentional cleaning operation is performed other than the contact of the liquid detergent. Note that the natural flow-down of the liquid detergent brought into contact with the object to be washed, the transmission of vibrations not intended for cleaning to the object to be washed, and the rinsing of the liquid detergent brought into contact with the object to be washed with water, etc., correspond to the case of washing the object to be washed without applying mechanical force. Alternatively, a method of applying mechanical force to wash the object to be washed may be used. For example, the object to be cleaned may be scrubbed and cleaned with a sponge or the like containing a liquid detergent. After bringing the liquid detergent into contact with the object to be washed, it may be scrubbed and cleaned with a sponge or the like. The object to be washed may be immersed in a diluted solution of the liquid detergent and scrubbed and cleaned with a sponge or the like.

[0056] The object to be washed may be any hard surface such as an article, and examples thereof include hard surfaces in the bathroom, bathroom supplies, hard surfaces in the toilet, toilet supplies, hard surfaces in the 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.

[0057] As described above, according to the liquid detergent of the present invention, since it contains components (A) to (D), has a pH of 8.5 or higher, and the mass ratio of A / D is within a specific range, good detergency and good rinsability can be achieved simultaneously. In addition, since good storage stability can be obtained even when the concentration of the liquid detergent is increased, it can be a concentrated type liquid detergent that is diluted and used. Since the liquid detergent of the present invention does not require mechanical force, it is suitable for cleaning objects with large cleaning target surfaces such as bathtubs, where the labor required for scrubbing is large. Therefore, the liquid detergent of the present invention is suitable as a so-called liquid detergent for bathrooms.

Examples

[0058] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by the following description.

[0059] (Raw materials used) <Component (A)> · A-1: AOS, sodium α-olefin sulfonate with 14 carbon atoms (product name "Lipolan LJ441" manufactured by Lion Specialty Chemicals). · A-2: LAS, sodium linear (C12~14) alkylbenzene sulfonate, (product name "Lipon PS-230" manufactured by Lion Specialty Chemicals). · A-3: AS, alkyl sulfate ester salt (C12) (product name "Sunol EH-1130" manufactured by Lion Specialty Chemicals). · A-4: AES, alkyl ether sulfate ester salt (C12 average ethylene oxide 3 mol adduct) (product name "Sunol LMT-1430" manufactured by Lion Specialty Chemicals). · A-5: IOS: sodium internal olefin sulfonate (sodium internal olefin sulfonate synthesized by the method described in Production Example 1 of JP-A-2018-115329). · A-6: AX (product name of Lion Specialty Chemicals Co., Ltd. "CadenaX DM14D-N"), myristyl dimethylamine oxide, amine oxide type amphoteric surfactant.

[0060] <(Component (B))> · B-1: Demb (diethylene glycol monobutyl ether, product name of Nippon Emulsion Co., Ltd. "butyl diglycol", alias butyl carbitol). · B-2: hexyl diglycol (diethylene glycol monohexyl ether, product name of Nippon Emulsion Co., Ltd. "hexyl diglycol").

[0061] <(Component (C))> · C-1: EDTA-4H (ethylenediaminetetraacetic acid, product name of Kiresto Co., Ltd. "Kiresto A"). · C-2: MGDA (methylglycine diacetic acid, product name of BASF Japan Ltd. "Trilon M").

[0062] <(Component (D))> · D-1: dichlorosan (4,4'-dichloro-2-hydroxydiphenyl ether) (product name of BASF "Tinosan HP200"). · D-2: triclosan (product name of Tokyo Chemical Industry Co., Ltd. "triclosan"). · D-3: IPMP (isopropylmethylphenol, product name of Wako Pure Chemical Industries, Ltd. "4-isopropyl-3-methylphenol").

[0063] <(Component (E))> · E-1: polyoxyethylene tridecyl ether (average ethylene oxide 7 mol adduct of branched C13 alcohol) (product name of BASF Japan Ltd. "Lutensol TO-7"). · E-2: polyoxyethylene alkyl ether (average ethylene oxide 7 mol adduct of linear C15 alcohol) (product name of Nippon Emulsion Co., Ltd. "EMALEX715").

[0064] <Optional component> ·pH adjuster: Sodium hydroxide (manufactured by Kanto Chemical Co., Inc., special grade). <Water> ·Water: Ion-exchanged water.

[0065] ≪Evaluation method≫ <Rinsability evaluation> The liquid detergent prepared in each example was put into a trigger spray container with the product name "Look Plus Bathtub Cleaning" manufactured by Lion Corporation, and sprayed 15 times so that the liquid detergent covered the entire inner wall surface of a general household bathtub. After waiting for 60 seconds after spraying, rinsing was started by spraying tap water (temperature 40 °C, flow rate 0.2 L / second) onto the wall surface with a shower, and the time until the bubbles completely disappeared from the drain and rinsing was completed (rinsing time) was measured. Evaluation was carried out according to the following rinsability evaluation criteria. In the following evaluation criteria, ◎, ○, and △ were considered passing. [Rinsability evaluation criteria] ◎: Less than 25 seconds. ○: 25 seconds or more and less than 30 seconds. △: 30 seconds or more and less than 35 seconds. ×: 35 seconds or more.

[0066] <Cleaning power> In advance, after fixing a test piece (2 cm × 10 cm) made of glass fiber reinforced plastic (FRP) to the inner wall surface of a general household bathtub, three adult men took a bath three times each (taking a bath once a day for three consecutive days, during which only the bath water was changed and the bathtub was used without being washed), and dirt was adhered to the test piece. After the test piece with adhered dirt was sufficiently dried, the liquid detergent prepared in each example was dropped onto the test piece (5 pieces) so that the entire surface was wetted, left for 30 seconds (short-time cleaning), and then rinsed with tap water (15 °C). Then, the test piece was sufficiently dried, and the removal state of the dirt on the surfaces of the 5 test pieces was evaluated visually and by touch according to the following cleaning power evaluation criteria. In the following evaluation criteria, ◎, ○, and △ were considered passing. [Evaluation criteria] ◎: The dirt removal is very good. [Among the 5 test pieces, no dirt was observed visually for all 5 pieces, and a smooth touch was obtained for the entire surface of all 5 test pieces] 〇: The dirt removal is quite good. [Among 5 test pieces, no dirt was visually observed on 4 pieces, and a smooth fingertip feel was obtained over the entire surface of the test piece] △: The dirt removal is good. [Among 5 test pieces, no dirt was visually observed on 3 pieces, and a smooth fingertip feel was obtained over the entire surface of the test piece] ×: The dirt removal is poor or no dirt is removed at all. [Among 5 test pieces, dirt was visually observed on 3 or more pieces, a rough fingertip feel was felt, or the visually observed dirt and the rough fingertip feel are the same as before washing]

[0067] <Storage stability> The liquid detergents prepared in each example were allowed to stand at 50 °C, 40 °C, and 25 °C, respectively, and visually confirmed 2 weeks after the start of storage. The storage stability was evaluated according to the following criteria. Those stored at 50 °C for 2 weeks are designated as sample (50), those stored at 40 °C for 2 weeks as sample (40), and those stored at 25 °C for 2 weeks as sample (25). In the following evaluation criteria, ◎, ○, and △ were considered as passing. [Evaluation criteria for low-temperature stability] ◎: Neither phase separation nor precipitation occurred in sample (50). 〇: At least one of phase separation or precipitation occurred in sample (50), but neither phase separation nor precipitation occurred in sample (40). △: At least one of phase separation or precipitation occurred in sample (40), but neither phase separation nor precipitation occurred in sample (25). ×: At least one of phase separation or precipitation occurred in sample (25).

[0068] <Examples 1 to 25, Comparative Examples 1 to 8> According to the compositions shown in Tables 1 to 5, components (A) to (E) and optional components were added to water and mixed to prepare the liquid detergents of each example. In Examples 24 and 25, a total of 3 types of liquid detergents were prepared: a liquid detergent prepared with the composition diluted 1-fold as shown in Table 4, and liquid detergents obtained by diluting it 3-fold and 5-fold with ion-exchanged water. Note that the compounding amounts in the table are values converted to pure components. The "appropriate amount" of the compounding amount is the amount necessary to adjust the liquid detergent to the pH shown in the table, and the "balance" is the remainder necessary to make the liquid detergent 100% by mass. Also, for Tables 1 to 5, those without compounding amounts shown in the table indicate that the component is not compounded. The results of evaluating the liquid detergents prepared in each example by the above evaluation method are shown in the table. Tables 6 to 10 show the values obtained by converting the compositions of each example shown in Tables 1 to 5 into compositions based on the total mass of the cleaning base.

[0069]

Table 1

[0070]

Table 2

[0071]

Table 3

[0072]

Table 4

[0073]

Table 5

[0074]

Table 6

[0075]

Table 7

[0076]

Table 8

[0077]

Table 9

[0078]

Table 10

[0079] As shown in the results of Tables 1 to 5, the examples containing components (A) to (D), having a pH of 8.5 or higher, and having a mass ratio of A / D of 0.1 to 1000 had good detergency and rinsability. In addition, the storage stability was also good. Comparative Example 1 in which A / D was greater than 1000 had poor rinsability. Comparative Example 2 in which A / D was less than 0.1 had poor detergency. In addition, the storage stability was also poor. Comparative Example 3 not containing component (A) had poor detergency. In addition, the storage stability was also poor. Comparative Example 4 not containing component (B) had poor detergency. In addition, the storage stability was also poor. Comparative Example 5 not containing component (C) had poor detergency. In addition, the storage stability was also poor. Comparative Example 6 not containing component (D) had poor rinsability. In addition, the storage stability was also poor. Both Comparative Example 7 and the 1-fold dilution of Example 24 had compositions with a high total content of components B and D. Comparative Example 7 not containing component D had poor storage stability and rinsability. Comparative Example 8 in which the pH of the liquid detergent was less than 8.5 had poor detergency compared to Example 21.< / ph>

Claims

Claim 1 Component (A): one or more selected from the group consisting of a non-soap anionic surfactant (a1) and an amphoteric surfactant (a2), Component (B): one or more of the compounds represented by the following general formula (I), Component (C): one or more of aminocarboxylic acid type chelating agents, and Component (D): containing one or more nonionic aromatic compounds selected from the group consisting of the compound represented by the following formula (d1) and the compound represented by the following formula (d2), having a pH of 8.5 or more at 25°C, A liquid detergent for hard surfaces, wherein A / D, which represents the mass ratio of the content of component (A) to the content of component (D), is 0.1 to 1000. R １ -O-(C ２ H ４ O) ｘ -(C ３ H ６ O) ｙ -R ２ (I) (R １ , R ２ each independently represents a hydrogen atom, an alkyl group or an alkenyl group having 1 to 6 carbon atoms, x is 0 to 5, y is 0 to 5, and x and y do not become 0 at the same time.) 【Chemical 1】 [In formula (d1), X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms, Y is each independently a chlorine atom or a bromine atom, a, b, and c are each independently 0 or an integer of 1 to 3, m is 0 or 1, and n is 0 or 1.] 【Chemical 2】 In formula (d2), V and W are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, R ３ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.] Claim 2 The liquid detergent for hard surfaces according to claim 1, wherein (B + C) / D, which represents the mass ratio of the total content of component (B) and component (C) to the content of component (D), is 2 to 3000. Claim 3 The liquid detergent for hard surfaces according to claim 1, further comprising (E) a nonionic surfactant. Claim 4 The liquid detergent for hard surfaces according to claim 1, which is for use in a bathroom. Claim 5 A liquid detergent product for hard surfaces, comprising the liquid detergent for hard surfaces according to any one of claims 1 to 4 and a discharge container containing the liquid detergent for hard surfaces. Claim 6 A method for cleaning a hard surface, comprising bringing a liquid obtained by diluting the liquid detergent for hard surfaces according to any one of claims 1 to 4 with water into contact with an object to be cleaned.

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