Water scale cleaner

Abstract

To provide a water scale cleaner that exhibits a low pungent odor, high solubility for calcium carbonate, and the capability to suppress the re-deposition of calcium salts after cleaning.SOLUTION: The present invention provides a water scale cleaner that contains lactic acid and fumaric acid with a mass ratio of 10:1 to 1:2, and a sprayer product or an aerosol product made using the same.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a cleaning agent for removing limescale from washstands and the like. [Background technology]

[0002] Generally, most of the sink cleaners used on washbasins are weakly alkaline detergents, and because calcium carbonate, the main component of limescale, is an alkaline stain, there is a limit to how much it can dissolve and remove it, making it difficult to remove limescale that has built up during daily cleaning of the sink.

[0003] It is possible to clean the limescale with a cleanser or a special detergent containing abrasives, but this is difficult to do on a daily basis as it may cause scratches.

[0004] To date, detergents for limescale containing citric acid as a main component (Non-Patent Document 1) and detergents for limescale combining acetic acid and fumaric acid (Non-Patent Document 2) are known.

[0005] However, although these combinations of citric acid or acetic acid and fumaric acid are supposedly used to remove limescale, they have problems such as an irritating odor, low solubility of calcium carbonate resulting in weak cleaning power, and low solubility of calcium salts formed by the reaction of calcium carbonate with the above acids after removing the limescale, which can lead to redeposition of limescale that is even more difficult to remove. [Prior art documents] [Non-patent literature]

[0006] [Non-Patent Document 2] Easy with TK pack! Azuma Kaitekihyakka (https: / / azuma-kaitekihyakka.com / view / item / 000000000489) [Non-Patent Document 1] Tinkle Deodorizer Plus for Wet Areas (https: / / www.kincho.co.jp / seihin / housewares / tincle / mizumawari / index.html) Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, the object of the present invention is to provide a limescale cleaner that has a less irritating odor, has high solubility of calcium carbonate, and can inhibit calcium salts from re-adhering after cleaning. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors conducted intensive research to solve the above problems and discovered that by incorporating lactic acid and fumaric acid in a specific mass ratio, it is possible to reduce an irritating odor, increase the solubility of calcium carbonate, and inhibit redeposition of calcium salts after cleaning, thereby completing the present invention.

[0009] That is, the present invention is a detergent for limescale that contains lactic acid and fumaric acid in a mass ratio of 10:1 to 1:2.

[0010] The present invention also relates to a spray product characterized by being filled in a container equipped with a spray valve with the above-mentioned limescale cleaner, or an aerosol product characterized by being filled in a container equipped with an aerosol valve with the above-mentioned limescale cleaner together with liquefied gas. Effect of the Invention

[0011] The detergent for limescale of the present invention has a low irritating odor, has high solubility of calcium carbonate, and can inhibit calcium salts from re-adhering after cleaning.

[0012] Furthermore, when the limescale cleaner of the present invention is combined with a surfactant, the foaming properties are improved, and dripping is prevented.

[0013] Therefore, the limescale cleaner of the present invention is suitable for cleaning limescale that occurs around water such as a wash basin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The detergent for limescale of the present invention (hereinafter simply referred to as "the detergent of the present invention") is a detergent containing lactic acid and fumaric acid, and the mass ratio thereof is 10:1 to 1:2.

[0015] The lactic acid used in the detergent of the present invention is not particularly limited and may be, for example, any of L-, D-, or DL-forms. The content of lactic acid in the detergent of the present invention is not particularly limited and is, for example, 0.1 to 8.0 mass% (hereinafter simply referred to as "%"), preferably 0.5 to 6.0%, and more preferably 0.8 to 2.0%.

[0016] The fumaric acid used in the cleaning agent of the present invention is not particularly limited. The content of fumaric acid in the cleaning agent of the present invention is not particularly limited, but is, for example, 0.1 to 2.0%, preferably 0.6 to 1.0%, and more preferably 0.7 to 0.8%.

[0017] The mass ratio of lactic acid to fumaric acid in the detergent of the present invention is 10:1 to 1:2, preferably 10:1 to 1:1 from the viewpoint of calcium carbonate solubility, and particularly preferably 10:5 to 5:4.

[0018] It is preferable that the detergent of the present invention further contains a surfactant. By containing a surfactant in the detergent of the present invention, the foaming property is improved, so that even a foam-forming product is less likely to drip.

[0019] The surfactant is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, amphoteric surfactants, silicone surfactants, natural surfactants, and amino acid surfactants.

[0020] Examples of nonionic surfactants include C12 / 14 alkyl glucamide, polyoxyethylene (hereinafter referred to as "POE") alkyl ethers such as POE cetyl ether, POE stearyl ether, POE oleyl ether, POE lauryl ether, POE behenyl ether, POE octyldodecyl ether, POE isocetyl ether, and POE isostearyl ether; polyoxyethylene sorbitan fatty acid esters such as POE sorbitan monococonut oil fatty acid, POE sorbitan monostearate, and POE sorbitan monooleate; polyoxyethylene polyoxypropylene alkyl ethers such as POE·POP cetyl ether and POE·POP decyltetradecyl ether; polyoxyethylene glycerin fatty acid esters such as POE glyceryl monostearate; polyoxyethylene lanolin alcohols such as POE lanolin alcohol; polyoxyethylene hydrogenated castor oils such as POE hydrogenated castor oil; and polyethylene glycol monostearate. Examples of the polyglycerin fatty acid esters include polyglycerin fatty acid esters such as glyceryl glycol fatty acid esters, hexaglyceryl monolaurate, hexaglyceryl monomyristate, pentaglyceryl monolaurate, pentaglyceryl monomyristate, pentaglyceryl monooleate, pentaglyceryl monostearate, decaglyceryl monolaurate, decaglyceryl monomyristate, decaglyceryl monostearate, decaglyceryl monoisostearate, decaglyceryl monooleate, and decaglyceryl monolinoleate; polyoxyethylene glycerin fatty acid esters such as POE glyceryl monooleate; polyoxyethylene sorbitan fatty acid esters such as POE sorbitan monopalmitate, POE sorbitan monostearate, POE sorbitan monoisostearate, and POE sorbitan monooleate; polyoxyethylene sorbitan fatty acid esters such as POE sorbitan monolaurate, POE sorbitan tetrastearate, and POE sorbitan tetraoleate; and the like.

[0021] Examples of anionic surfactants include fatty acid salts such as sodium laurate, sodium palmitate, and coconut potassium soap; alkyl ether carboxylates such as POE lauryl ether carboxylate and POP·POE ether myristate; higher alkyl sulfates such as sodium lauryl sulfate, potassium lauryl sulfate, and triethanolamine lauryl sulfate; alkyl ether sulfates such as triethanolamine POE lauryl sulfate and sodium POE lauryl sulfate; N-acylamine salts such as sodium lauroyl sarcosine, sodium lauroyl-N-methyl-β-alanine, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, monosodium N-myristoyl-L-glutamate, and diethanolamine N-palmitoyl aspartate; higher fatty acid amide sulfonates such as sodium N-myristoyl-N-methyl taurine, sodium coconut fatty acid methyl taurine, sodium lauroyl methyl taurine, and sodium POE lauryl amide ether sulfonate; sodium POE oleyl ether phosphate, P Phosphate salts such as OE stearyl ether phosphate and sodium POE lauryl amide ether phosphate; sulfosuccinate salts such as sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, and sodium lauryl polypropylene glycol sulfosuccinate; alkylbenzene sulfonates such as sodium linear dodecylbenzene sulfonate, triethanolamine linear dodecylbenzene sulfonate, and linear dodecylbenzene sulfonic acid; higher fatty acid ester sulfate salts such as hydrogenated coconut oil fatty acid glycerin sulfate sodium, turpentine oil, and other sulfated oils, α-olefin sulfonates, higher fatty acid ester sulfonates, and secondary alcohol sulfate salts; higher fatty acid alkylolamide sulfate salts such as sodium lauroyl monoethanolamide succinate and sodium caseinate; sulfate salts or sulfonate salts of alkyl sulfate salts, polyoxyethylene alkyl sulfate salts, fatty acid amide ether sulfate salts, acyl isethionates, and sulfosuccinate salts;Examples of the surfactant include carboxylic acid type surfactants such as ether carboxylates, fatty acid amide ether carboxylates, N-acyliminodiacetic acid, and N-acylamino acid salts.

[0022] Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; and alkanolamine salts such as monoethanolamine salts and diethanolamine salts.

[0023] Examples of amphoteric surfactants include amine oxides such as cocamidopropyl betaine and alkyldimethylamine oxide, sulfobetaines such as alkyldimesylsulfobetaine, and carbobetaines.

[0024] Other examples of surfactants include silicone surfactants such as polyoxyethylene-methylpolysiloxane copolymer, polyoxypropylene-methylpolysiloxane copolymer, and poly(oxyethylene-oxypropylene)-methylpolysiloxane copolymer; natural surfactants such as sodium surfactin, cyclodextrin, hydrogenated enzyme soy lecithin; N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid potassium, N-coconut oil fatty acid acyl-L-glutamic acid sodium, N-lauroyl-L-glutamic acid triethanolamine, and N-lauroyl-L-glutamic acid potassium. and amino acid surfactants such as N-acyl glutamates, such as sodium N-lauroyl-L-glutamate, potassium N-myristoyl-L-glutamate, sodium N-myristoyl-L-glutamate, and sodium N-stearoyl-L-glutamate; N-acyl glutamic acids, such as N-coconut oil fatty acid acyl-L-glutamic acid, N-lauroyl-L-glutamic acid, and N-stearoyl-L-glutamic acid; N-acyl glycine salts, such as potassium N-coconut oil fatty acid acyl glycine and sodium N-coconut oil fatty acid acyl glycine; and N-acylalanine salts, such as N-coconut oil fatty acid acyl-DL-alanine triethanolamine.

[0025] These surfactants can be used alone or in combination of two or more. Among these surfactants, nonionic surfactants are preferred from the viewpoints of environmental friendliness and low irritation to the human body, C12 / 14 alkyl glucamides are more preferred, and a combination of C12 / 14 alkyl glucamides and POE alkyl ethers is even more preferred.

[0026] The content of the surfactant in the cleaning agent of the present invention is not particularly limited, but is, for example, 0.1 to 5.0%, and preferably 0.5 to 2.0%.

[0027] The cleaning agent of the present invention may contain water such as ion-exchanged water, etc. The content of water in the cleaning agent of the present invention is not particularly limited, but is, for example, 70 to 99%, and preferably 80 to 99%.

[0028] The cleaning agent of the present invention may further contain a buffering agent, a chelating agent, a pH adjusting agent, a fragrance, a solvent, etc. These may be used alone or in combination of two or more kinds.

[0029] The cleaning agent of the present invention is acidic because it contains lactic acid and fumaric acid, and its pH is not particularly limited, but is, for example, 1.5 to 5.0, and preferably 2.0 to 3.0.

[0030] The cleaning agent of the present invention as described above can be sprayed or applied as is to clean limescale, but for spraying it is preferable to prepare a product in a container equipped with a spray valve, a product filled together with liquefied gas in a container equipped with an aerosol valve, or a product filled in a container equipped with a pump former.

[0031] When the detergent of the present invention is filled in a container equipped with a spray valve to produce a product, the detergent of the present invention may be filled in a container made of aluminum, steel, or the like, equipped with a spray valve.

[0032] When the cleaning agent of the present invention is filled together with liquefied gas in a container equipped with an aerosol valve to prepare a product, the cleaning agent of the present invention may be filled together with liquefied gas into a container made of aluminum, steel, or the like, equipped with an aerosol valve such as an upright aerosol valve, an inverted aerosol valve, or a forward and inverted aerosol valve.

[0033] Examples of the liquefied gas include liquefied petroleum gas, which is propane, normal butane, isobutane, and mixtures thereof, hydrofluoroolefins such as trans-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze) and trans-2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf), dimethyl ether, and mixtures thereof, normal pentane, isopentane, and mixtures thereof, etc. These liquefied gases can be used alone or in combination of two or more kinds.

[0034] The pressure when the cleaning agent of the present invention is filled together with a liquefied gas at 35°C is, for example, preferably 0.1 to 0.8 MPa, and more preferably 0.1 to 0.5 MPa.

[0035] When the detergent of the present invention is to be made into a product filled in a container equipped with a pump former, the detergent of the present invention may be filled in a container equipped with a plastic pump former.

[0036] Among these products, a product filled in a container equipped with a spray valve, or a product filled together with liquefied gas in a container equipped with an aerosol valve is preferred, and a product filled together with liquefied gas in a container equipped with an aerosol valve is more preferred.

[0037] The detergent of the present invention and a product filled with the detergent of the present invention can be used to clean limescale that occurs around water such as washbasins, kitchens, and bathrooms, but it is preferable to use it to clean limescale that occurs on washbasins. When cleaning limescale, a suitable amount of the detergent is sprayed or applied to the limescale, and then scrubbed with a cleaning tool such as a sponge, scrubbing brush, or brush, and then rinsed with water. EXAMPLES

[0038] The present invention will be described in detail below by way of examples of the present invention, but the present invention is not limited to these examples in any way.

[0039] Examples 1 to 6 and Comparative Examples 1 to 5 Preparation of limescale cleaner: Limescale cleaners were prepared by stirring and mixing the formulations shown in Table 1. These limescale cleaners were evaluated based on the following criteria for calcium carbonate aqueous solution solubility, foaming ability, low odor, the type of salt assumed to form when limescale reacts with the cleaner, and the water solubility (non-stickiness) of salts generated when left alone (salt assumed to form when limescale reacts with the cleaner), and pH was also measured according to standard methods. The results are shown in Table 1.

[0040] [Table 1]

[0041] <Solubility of calcium carbonate in aqueous solution> The same amount of 2.8% calcium carbonate aqueous solution was dropped into each limescale cleaner and stirred, and the transmittance %T (550 nm wavelength) of the resulting solution was measured using a spectrophotometer. (Evaluation) (Transmittance) × (undissolved and cloudy): 0~0.5%T △ (slightly cloudy and slightly dissolved): 0.5-1.0%T ◎(dissolved): 1.0~%T

[0042] <Foaming property> The same amount of each limescale cleaner was dispensed onto paper using a foamer pump (WP foamer pump (W-5721): manufactured by Yoshino Kogyosho Co., Ltd.), and the foam height (at the highest point) after 5 minutes at room temperature was measured with a ruler. (Rating) (Height) × (bubbles are not retained): 5mm or less △ (slightly retained bubbles): 5mm~10mm ○ (bubbles are retained): 10mm or more

[0043] <Low odor> A sensory evaluation was conducted on the foam state of the limescale cleaner dispensed onto paper using a foamer pump similar to that used for the foaming test, and it was confirmed whether or not it had a pungent odor (acidic odor). (Evaluation) (Content) ×: A strong irritating odor is felt 〇: No irritating odor ◎: Odorless

[0044] <Water solubility of salt generated by leaving it (anti-sticking properties)> Each limescale cleaner was rated as "good" when the water solubility of salts expected to form after cleaning limescale was 20 g / L or more, as the limescale would not re-adhere after cleaning.

[0045] [Table 2]

[0046] From the above results, it was found that a combination of lactic acid and fumaric acid results in a limescale cleaner that is excellent in foaming property, low odor, and solubility of calcium carbonate aqueous solution, and that by setting the mass ratio of lactic acid and fumaric acid at 10:1 to 1:2, preferably 10:1 to 1:1, and particularly preferably 10:5 to 5:4, the solubility of calcium carbonate aqueous solution is increased, and the water solubility of salt generated by standing is also high, resulting in an excellent limescale cleaner that prevents adhesion. On the other hand, the conventional combination of citric acid alone and acetic acid and fumaric acid did not have any that were favorable in all of foaming property, low odor, solubility of calcium carbonate aqueous solution, and water solubility of salt generated by standing.

[0047] Examples 7 to 10 Preparation of limescale cleaner: The formulations shown in Table 3 were stirred and mixed to prepare detergents for limescale. These detergents for limescale were evaluated in the same manner as above for solubility in aqueous calcium carbonate solution, foaming ability, low odor, the type of salt assumed to be formed by the reaction of limescale with detergent, and water solubility (non-stickiness) of salts generated by leaving the detergent (salt assumed to be formed by the reaction of limescale with detergent) based on the following evaluation criteria. The results are also shown in Table 3.

[0048] [Table 3]

[0049] From the above results, when no surfactant is blended in the limescale cleaner of the present invention, although foaming is poor, this is not a particular problem when used in places where dripping is not a major concern. It was also found that, although foaming is improved by blending a surfactant, the type of surfactant is not particularly limited.

[0050] Example 9 Aerosol product preparation: An aerosol product was prepared by filling a total of 220 g of the formulation liquid described in Example 6 of Table 1 (200 g) and 20 g of liquefied LPG (0.4 MPa at 20° C.) into a 300 mL aluminum can equipped with an aerosol valve. [Industrial Applicability]

[0051] The limescale cleaner of the present invention can be used to clean limescale that occurs around water such as on a wash basin.

Claims

1. A detergent for limescale containing lactic acid and fumaric acid in a mass ratio of 10:1 to 1:

2.

2. The limescale cleaner according to claim 1, further comprising a surfactant.

3. 3. A spray product comprising the limescale cleaner according to claim 1 or 2 filled in a container equipped with a spray valve.

4. 3. An aerosol product comprising the limescale cleaner according to claim 1 or 2 filled together with liquefied gas in a container equipped with an aerosol valve.

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