JP2008214621A - Detergent and method for using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent excellent in cleansing effect to effectively remove pollution at a place to be applied, in odor-eliminating effect for eliminating existing odor, and in deodorizing effect for preventing odor from developing. <P>SOLUTION: The detergent comprises a salt of copper (II) ion and/or zinc ion, at least one acid component selected from the group consisting of a 1-6C alkyl sulfonic acid, a 5-14C aryl sulfonic acid, amido-sulfuric acid, and their derivatives, each optionally substituted by at least one group selected from the groups consisting of amine group, imine group, and hydroxyl group, a surfactant, and water as a solvent. The concentration of the salt contained in the detergent is higher than 0.001 mM and lower than 10 mM. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a cleaning agent suitable for washing around water and deodorizing and a method of using the same, and is particularly suitable for washing and deodorizing toilets, bathrooms and bathrooms.

  In recent years, consumers' interest in the living environment has increased, and it has become more desirable to remove unpleasant odors around us. In particular, nitrogen-based odors such as amines and ammonia, and sulfur-based odors such as methyl mercaptan are bad odors that give unpleasant feelings to everyone because they have a raw odor or a strong irritation to the nasal cavity. As one of the technologies for preventing the generation of these unpleasant odors, there is known a method for preventing the generation of ammonia-based odor components by inhibiting the urea decomposition action by enzyme urease by flowing water containing free chlorine. (For example, see Patent Document 1).

  The following are known as deodorization techniques using metal salts. That is, it is known to adsorb and remove nitrogen-based and sulfur-based malodorous substances using a liquid antibacterial / deodorizing agent containing copper gluconate (see, for example, Patent Document 2). In addition, it is known to deodorize N-type and S-type malodors of industrial waste by using a deodorant containing a zinc compound such as zinc gluconate and a nonionic surfactant (for example, Patent Document 3). reference).

  The following are known as deodorization techniques using an acid. That is, it is known to deodorize and deodorize by neutralizing amines and sulfides that are odorous compounds with acids such as phosphoric acid, hydrochloric acid, citric acid, and the like (see, for example, Patent Document 4). In addition, it is known that formaldehyde and the like are deodorized by a deodorizing agent in which an aliphatic primary amine having a sulfonic acid group such as aminoethanesulfonic acid (taurine) is supported on a porous carrier such as magnesium silicate clay mineral. (For example, see Patent Document 5). Furthermore, it is also known to remove odors of tap water and the like with nitrogen-containing organic compounds such as taurine (see, for example, Patent Document 6).

  Inorganic antibacterial agents containing antibacterial metals, anionic surfactants, alkaline builders such as carbonates, and detergents containing aluminosilicates can effectively wash and wash clothes stains, and antibacterial clothing after washing It is known that the property can be imparted (see, for example, Patent Document 7).

WO96 / 6237 Japanese Unexamined Patent Publication No. 8-198709 JP 2001-321427 A JP 2001-37861 A JP 2000-107274 A JP 7-138552 A JP 2006-169379

  The present inventors now have a group consisting of a salt of copper (II) ion and / or zinc ion, a specific alkylsulfonic acid, a specific arylsulfonic acid, amidosulfuric acid, and derivatives thereof in water as a solvent. By containing at least one acid component selected from the above and a specific anionic surfactant and / or nonionic surfactant, the cleaning effect for removing dirt at the application site and the odor that already exists are eliminated. It was found that a cleaning agent excellent in deodorizing effect and deodorizing effect preventing odor generation can be obtained.

  Accordingly, an object of the present invention is to provide a cleaning agent that is excellent in a cleaning effect for removing dirt on a target part, an effect of erasing and deodorizing an already existing odor, and an anti-odor effect that prevents the generation of odor.

  That is, the cleaning agent according to the present invention is a carbon that may be substituted with a salt of copper (II) ion and / or zinc ion and at least one selected from the group consisting of an amine group, an imine group, and a hydroxyl group. At least one acid component selected from the group consisting of alkyl sulfonic acids having 1 to 6 carbon atoms, aryl sulfonic acids having 5 to 14 carbon atoms, amidosulfuric acid, and derivatives thereof; and a non-carboxylate type anionic interface It comprises an active agent and / or a nonionic surfactant and water as a solvent, and the salt is contained in an amount exceeding 0.001 mM and less than 10 mM.

Cleaning Agent The cleaning agent according to the present invention comprises a salt of copper (II) ions and / or zinc ions, a specific acid component, a specific surfactant component, and water as a solvent. The specific acid component is at least one selected from the group consisting of alkyl sulfonic acid and aryl sulfonic acid, amidosulfuric acid, and derivatives thereof. The alkyl sulfonic acid has 1 to 6 carbon atoms, The acid has 5 to 14 carbon atoms and may be substituted with at least one selected from the group consisting of an amine group, an imine group, and a hydroxyl group. The surfactant component is an anionic and / or nonionic surfactant having no carboxylic acid group in the chemical structure. The salt of copper (II) ions and / or zinc ions effectively suppresses the generation of odors, particularly the generation of nitrogenous odors (for example, trimethylamine and ammonia). This is presumed that the activity of enzymes that promote the production of odorous substances such as urease, which is a urea hydrolase, is inhibited by these metal ions. It is not limited at all. On the other hand, the acid component neutralizes and eliminates the odor of nitrogen-based odors (for example, trimethylamine and ammonia). In general, it is known that various acids and their derivatives eliminate nitrogen-based odors by neutralization, and copper (II) ions and / or zinc ions eliminate sulfur-based odors (for example, methyl mercaptan). When the acid of the above is used in combination with a salt of copper (II) ion and / or zinc ion, these metal ions are combined with an acid (for example, carboxyl group) by chelation or the like, which contributes to deodorization or deodorization. There was a tendency for the amount of metal ions to be significantly reduced. On the other hand, even if a large amount of metal salt is added in order to compensate for the loss, the liquid agent is strongly colored by high-concentration metal ions, resulting in leaving a color mark at the application site during use, resulting in a loss of aesthetics. End up. In the cleaning agent according to the present invention, as the acid component, at least one selected from the group consisting of the above-mentioned specific alkylsulfonic acid and arylsulfonic acid, amidosulfuric acid, and derivatives thereof is used. By avoiding the addition of a salt of copper (II) ions and / or zinc ions to a very low concentration of more than 0.001 mM and less than 10 mM, the deodorizing effect of eliminating the odor already present and Both the deodorizing effect which prevents generation | occurrence | production of an odor can fully be exhibited. And since a metal salt component is a low density | concentration as above-mentioned, it does not leave a coloring trace in a to-be-applied location.

  In addition, the surfactant component effectively cleans and removes dirt and restores the aesthetics of the application area, improves the penetration and wettability of the cleaning agent to the application area, and provides the deodorizing effect. It is effective for exerting deodorizing effect and ensuring aesthetics. The cleaning effect of surfactants and the effect of improving penetrability and wettability are generally known. However, when any surfactant is used in combination with a copper (II) ion and / or zinc ion salt, Metal ions are combined with surfactants (for example, surfactants containing carboxylic acid groups) due to chelation or insoluble salt formation, and the net amount of metal ions contributing to deodorization or deodorization is greatly reduced. There was a tendency to end up. On the other hand, even if a large amount of metal salt is added to compensate for the loss, the liquid agent is strongly colored by high-concentration metal ions, leaving colored marks at the application site during use, resulting in a loss of aesthetics. End up. This is because the color mark is not washed away with water in a place where water does not come into contact in a normal use mode, which may greatly impair the value as a consumer product. In the cleaning agent according to the present invention, by using a surfactant having no carboxylic acid group as a surfactant, these problems can be avoided and copper (II) ions and / or specific components can be avoided. By simply adding a zinc ion salt so as to have an extremely low concentration of more than 0.001 mM and less than 10 mM, both the deodorizing effect for eliminating the existing odor and the deodorizing effect for preventing the generation of the odor are sufficiently obtained. It can be demonstrated. And since a metal salt component is a low density | concentration as above-mentioned, it does not leave a coloring trace in a to-be-applied location.

  The salt component used in the cleaning agent of the present invention is a salt of copper (II) ions and / or zinc ions. The concentration of the salt component in the cleaning agent is more than 0.001 mM and less than 10 mM, preferably 0.005 mM to 5 mM, more preferably 0.01 mM to 2 mM, and most preferably 0.1 mM to 1 mM. is there. Since these concentration ranges are extremely low, there is little or no coloration trace caused by copper (II) ions and / or zinc ions. In addition, while having such a low concentration, the activity of the enzyme that promotes the generation of odorous substances can be inhibited, and an excellent deodorizing effect can be exhibited.

According to a preferred embodiment of the present invention, preferred examples of the salt of copper (II) ion and / or zinc ion include gluconate, sulfate, malate, and lactate. From the viewpoint of ensuring safety to the human body, the LD ₅₀ (half lethal dose) of the salt is 300 mg / kg or more, preferably 300 mg / kg or more and 2000 mg / kg or less. Here, the LD ₅₀ value indicates a half-lethal dose after oral ingestion, and generally indicates a value measured by animal experiments according to OECD guidelines: OECD 420 (effective in 2001). According to OECD 420, the identification of a numerical value with an LD ₅₀ value exceeding 2000 mg / kg is not required in principle from the viewpoint of animal welfare. Therefore, the value of LD ₅₀ given by the test according to OECD 420 is 2000 mg / kg at the maximum. That is, the value of LD ₅₀ according to this test method for a substance having an LD ₅₀ substantially exceeding 2000 mg / kg is 2000 mg / kg. Therefore, in the present invention, a substance having an LD ₅₀ value of 2000 mg / kg includes a substance having a substantial LD ₅₀ exceeding 2000 mg / kg. The preferred salts described above satisfy this preferred LD ₅₀ range. In particular, both copper gluconate and zinc gluconate have been designated as food additives, and in recent years, nutrient fortifiers using the same salt have been marketed, which is preferable because of its high safety to the human body.

The acid component used in the cleaning agent of the present invention may be substituted with at least one selected from the group consisting of an amine group, an imine group, and a hydroxyl group. -14, preferably 6-10, of at least one selected from the group consisting of arylsulfonic acid, amidosulfuric acid, and derivatives thereof. According to a preferred aspect of the present invention, the derivative preferably does not have a chain hydrocarbon group having 7 or more carbon atoms in the molecular structure. According to a preferred embodiment of the present invention, the alkylsulfonic acid and / or arylsulfonic acid is a compound group represented by the following chemical structural formula:
R ¹ —SO ₃ H (1)
(Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 5 to 14 carbon atoms, preferably 6 to 10 carbon atoms),
R ²
> N—R ⁴ —SO ₃ H (2)
R ³
(R ² and R ³ are each independently a hydrogen atom, an amine group, a hydroxyl group, a sulfonic acid group, or a hydrocarbon group having 1 to 6 carbon atoms (preferably an alkyl group) or 5 to 14 carbon atoms, preferably Is an aryl group of 6 to 10, provided that at least one hydrogen atom of the alkyl group and aryl group may be substituted with a hydroxyl group, an amine group, or a sulfonic acid group, and R ² and R ³ are They may be bonded to each other. R ⁴ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 5 to 14 carbon atoms, preferably 6 to 10 carbon atoms, and at least one hydrogen atom of the alkyl group and aryl group is a hydroxyl group, an amine group, Alternatively, it may be substituted with a sulfonic acid group. ) Are preferably selected, and more preferably those containing no carbonyl group or carboxyl group. According to such a compound, the deodorization performance by a metal ion and the deodorization performance of sulfur-type odor (for example, methyl mercaptan) are not inhibited.

According to a preferred embodiment of the present invention, the compound in which the alkylsulfonic acid and / or arylsulfonic acid is represented by the following chemical structural formula:
R ¹ —SO ₃ H (1)
(Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, preferably 6 to 10 carbon atoms, or an amine group having 1 to 6 carbon atoms), or a derivative thereof. Is preferred. Examples of alkyl sulfonic acid and aryl sulfonic acid compounds include benzene sulfonic acid, benzene sulfonic acid monohydrate, methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butyl sulfonic acid, pentyl sulfonic acid, hexyl sulfonic acid, 4 -Biphenyl sulfonic acid, 1, 2- ethane disulfonic acid, and mixtures thereof are mentioned, More preferably, it is benzenesulfonic acid. Examples of derivatives of alkylsulfonic acid and arylsulfonic acid include 1,4-butanediol dimethanesulfonate, n-butyl p-toluenesulfonate, 2-butynyl p-toluenesulfonate, p-toluenesulfonic acid 3- Butynyl, 2,5-dimethylbenzenesulfonic acid dihydrate, ethyl benzenesulfonate, ethyl 2-hydroxyethylsulfonate, ethyl methanesulfonate, ethyl p-toluenesulfonate, ethylene glycol bis-pt toluenesulfonate , Toluenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, and mixtures thereof.

According to a preferred embodiment of the present invention, the compound in which the alkylsulfonic acid and / or arylsulfonic acid is represented by the following chemical structural formula:
R ²
> N—R ⁴ —SO ₃ H (2)
R ³
(In the formula, R ² and R ³ each independently represent a hydrogen atom, an amine group, a hydroxyl group, a sulfonic acid group, or a hydrocarbon group having 1 to 6 carbon atoms or 5 to 14 carbon atoms, preferably 6 to 6 carbon atoms). 10, wherein at least one hydrogen atom of the alkyl group and aryl group may be replaced by a hydroxyl group, an amine group, or a sulfonic acid group, and R ² and R ³ are bonded to each other. R ⁴ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 5 to 14 carbon atoms, preferably 6 to 10 carbon atoms, and at least one hydrogen atom of the alkyl group and the aryl group. May be substituted with a hydroxyl group, an amine group, or a sulfonic acid group.) Or a derivative thereof. Examples of aminosulfonic acid and aminoalkylsulfonic acid and aminoarylsulfonic acid include aminomethanesulfonic acid, aminoethanesulfonic acid, aminopropanesulfonic acid, m-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, sulfanilic acid, 8-amino-2-naphthalenesulfonic acid, 5-amino-2-naphthalenesulfonic acid, 6-amino-1-naphthalenesulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 1-aminonaphthalene-5-sulfonic acid, 5-aminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid, aminoamyl sulfonic acid, N-phenylaminomethanesulfonic acid, and mixtures thereof, more preferably aminoethanesulfonic acid and amino Methanesulfonic acid . Examples of aminoalkyl sulfonic acid and aminoaryl sulfonic acid derivatives include 5- (2-aminoethylamino) -1-naphthalenesulfonic acid, 5-amino-2-[(p-aminophenyl) amino] benzenesulfonic acid 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 4-amino-2-methylbenzene-1 -Sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 2-aminotoluene-5-sulfonic acid, 5-amino-2-methylbenzene Sulfonic acid, 2-amino-1,5-naphthalene disulfonic acid, 7-amino-1,3,6-naphthalene trisulfonic acid, -Amino-2-naphthol-4-sulfonic acid, 6-amino-1-naphthol-3-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 4-amino-4'-nitrostilbene-2, 2'-disulfonic acid, 2-amino-4-nitrotoluene-5-sulfonic acid, 4-amino-2-nitrotoluene-3-sulfonic acid, 2-aminopyridine-5-sulfonic acid, 2-amino-5-pyridinesulfone Acid, 3-amino-2-pyridinesulfonic acid, 4-aminopyridine-3-sulfonic acid, 6-amino-2-pyridinesulfonic acid, 4-aminotoluene-3-sulfonic acid, 3-[(1,1- Dimethyl-2-hydroxyethyl) amino] -2-hydroxypropanesulfonic acid, aniline-2,4-disulfonic acid, 8-anilino-1-naphthalenesulfonic acid, 8-a Nilino-1-naphthalenesulfonic acid, 2-anilinonanaphthalene-6-sulfonic acid, p-anisidine-2-sulfonic acid, p-anisidine-3-sulfonic acid, 1H-benzimidazole-2-sulfonic acid, N, N -Bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, 2- (N-cyclohexylamino) ethanesulfonic acid, N-cyclohexyl-2-aminoethanesulfonic acid, N-cyclohexyl-3-aminopropanesulfonic acid, 2,5-diamino-1,3-benzenedisulfonic acid, 4,4′-diamino-2,2′-biphenyldisulfonic acid, 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid, 1-diazo 2-naphthol-4-sulfonic acid, 5-dimethylamino-1-naphthalenesulfonic acid, N-ethyl-N-benzyla Phosphorus-3′-sulfonic acid, p-hydroxyazobenzene-p′-sulfonic acid, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid monohydrate, 3-pyridinesulfonic acid, ammonium 2-methylarylsulfonate 1-anilinonanaphthalene-8-sulfonic acid, 2-anilinonaphthalene-6-sulfonic acid, benzotriazole-4-sulfonic acid, 4-benzoylamide-4′-aminostilbene-2,2′-disulfonic acid Hydrates, 3-pyridinesulfonic acid, 4,4′-diaminostilbene-2,2′-disulfonic acid, diammonium imidodisulfonic acid, α- (N-ethylanilino) -m-toluenesulfonic acid, 1,1- Di (aminoethyl) ethanesulfonic acid, 1,1-diaminomethanesulfonic acid, 1,1-diaminopropanesulfonic acid, 1,2-diaminopropanesulfonic acid, 2-amino-1,5-naphthalenedisulfonic acid, 2-amino-1,4-benzenesulfonic acid, 4-amino-5-methoxy-2-methylbenzenesulfonic acid, 2- Amino-5-methylbenzene-1-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 1-amino-3,8-naphthalenedisulfone Acid, 3-amino-1,5-naphthalenedisulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 4-amino-1-naphthalenesulfonic acid, 6-amino-1-naphthalenesulfonic acid, 5-amino-1- Naphthalenesulfonic acid, 1-amino-8-naphthalenesulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfuric acid Acid, 8-aminonaphthalene-1-sulfonic acid, 7-amino-1,3,6-naphthalene trisulfonic acid, 8-amino-1-naphthol-3,6-disulfonic acid, 4-amino-5-naphthol-2 , 7-disulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 1-amino-5-naphthol-7-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, aniline-2, 5-disulfonic acid, azolitmine, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, 4,4-bis (4-amino-1-naphthylazo) -2,2-stilbene disulfonic acid, 4 , 4-Diaminostilbene-2,2-disulfonic acid, metanilic acid, 1-naphthylamino-6-sulfonic acid, 4-nitroaniline-2-sulfonic acid, trypan blue , Diaminobenzene sulfonic acid, 4,4-diaminostilbene-2,2-disulfonic acid, and mixtures thereof.

  According to a preferred embodiment of the present invention, the alkyl sulfonic acid and / or aryl sulfonic acid is preferably a derivative of aminoethane sulfonic acid, examples of such compounds include aminoethane sulfonic acid (taurine), N , N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid (BES), N-cyclohexyl-2-aminoethanesulfonic acid (CHES), 2- [4- (2-hydroxyethyl) -1-piperazinyl ] Ethanesulfonic acid (HEPES), 2-morpholinoethanesulfonic acid monohydrate (MES), piperazine-1,4-bis (2-ethanesulfonic acid) (PIPES), piperazine-1,4-bis (2) -Ethanesulfonic acid) sesquisodium salt monohydrate (PIPES sesquisodium), N-tris (hydroxy Etc. chill) methyl-2-aminoethanesulfonic acid (TES) and the like.

  According to a preferred embodiment of the present invention, the alkyl sulfonic acid and / or aryl sulfonic acid is preferably a derivative of aminopropane sulfonic acid, and examples of such compounds include aminopropane sulfonic acid, N-cyclohexyl- 3-aminopropanesulfonic acid (CAPS), 3- [4- (2-hydroxyethyl) -1-piperazinyl] propanesulfonic acid (EPPS), 2-hydroxy-3- [4- (2-hydroxyethyl) -1 -Piperazinyl] propanesulfonic acid monohydrate (HEPPSO), 3-morpholinopropanesulfonic acid (MOPS), 2-hydroxy-3-morpholinopropanesulfonic acid (MOPSO), piperazine-1,4-bis (2-hydroxy- 3-propanesulfonic acid) dihydrate (POPSO), N-tris ( Dorokishimechiru) methyl-3-amino-propanesulfonic acid (TAPS), and 2-hydroxy -N- tris (hydroxymethyl) methyl-3-amino-propanesulfonic acid (TAPSO) and the like.

  According to a particularly preferred embodiment of the present invention, taurine (aminoethanesulfonic acid) can be most suitably used as the acid component. Taurine is a food additive used as a flavoring ingredient in seasonings. In the United States, taurine is also used as a nutritional enhancer for infant formula. It is a substance with excellent safety. Furthermore, it has excellent biodegradability, low accumulation, and even if it flows out, the burden on the environment is extremely small. Furthermore, since it is an acid that neutralizes and deodorizes nitrogen-based odors, it has an advantage that it can be applied to metallic articles and plated articles without hesitation because of its low metal corrosiveness. In addition, it can be used by mixing with low-concentration copper salt and zinc salt, which are coexisting components, in any proportion, and by using it together with sulfate and gluconate that are also adopted as food additives, An extremely safe cleaning agent can be obtained.

  According to a preferred embodiment of the present invention, the alkyl sulfonic acid and / or aryl sulfonic acid or a derivative thereof is preferably contained in an amount of 0.5 mM or more, more preferably 0.5 mM to 120 mM, and still more preferably. 1 mM to 100 mM.

  The surfactant component used in the cleaning agent of the present invention can be used by selecting one or more kinds from nonionic surfactants and / or non-carboxylate anionic surfactants. Since these surfactants have little interaction (chelation or insoluble salt formation) with coexisting Cu ions or Zn ions, it is possible to provide a cleaning agent that effectively exhibits the deodorizing effect and deodorizing effect of the component. .

  According to a preferred embodiment of the present invention, the surfactant component preferably has a hydrocarbon chain having 7 or more carbon atoms. By using such a surfactant, it is possible to effectively infiltrate the cleaning agent and spread it even in a place where water does not come into contact and the odor-causing substance is likely to accumulate in a normal use mode. . More preferably, it is 9-20, More preferably, it is 10-16.

  According to a preferred embodiment of the present invention, polyethylene glycol type and polyhydric alcohol type can be suitably used as the nonionic surfactant. Specifically, as the polyethylene glycol type, higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide One or more types selected from ethylene oxide adducts, fat and oil ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, and the like can be used. Examples of the polyhydric alcohol type include fatty acid ester of glycerol, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, alkyl ether of polyhydric alcohol, fatty acid amide of alkanolamines, etc. More than one type can be selected and used.

  According to a preferred embodiment of the present invention, sulfate ester salts, sulfonate salts, and phosphate ester salts can be suitably used as the anionic surfactant.

  According to a further preferred embodiment of the present invention, as the anionic surfactant component, an alkyl sulfate ester salt, a polyoxyethylene alkyl ether sulfate ester salt, an alkyl benzene sulfonate salt, an alkyl naphthalene sulfonate salt, or an alkyl diphenyl ether disulfonate salt is used. From the above, one or more types can be selected and used.

  According to a preferred embodiment of the present invention, the surfactant component is preferably contained in an amount of 0.1 wt% or more, more preferably 0.1 wt% to 10 wt%, further preferably 0.5 wt% to 6 wt%. It is.

  The solvent component used in the cleaning agent of the present invention is water. According to a preferred aspect of the present invention, the solvent is an alcohol having 2 or 3 carbon atoms for the purpose of imparting preservability to prevent microbial fouling of the detergent and imparting the permeability of the detergent to gaps and porous members. Can further be included. The alcohol content is preferably 1 to 40% by weight, more preferably 3 to 25% by weight, and still more preferably 5 to 15% by weight with respect to the total amount of the cleaning agent. Within such a range, deterioration does not occur even if the application site is a resin member, it is excellent in the above-mentioned storage stability and permeability, and precipitation of other coexisting components that are dissolved can be effectively prevented and long-term stability is achieved. Also excellent.

  According to a preferred embodiment of the present invention, the cleaning agent preferably has a pH of 3-10, more preferably a pH of 4-9. A cleaning agent having such a pH range has no problem with irritation to the human body, and there is no fear of fouling the applied member. The pH range may be realized by adjusting the concentration of the salt component and the acid component, or may be adjusted to the above pH range by adding a pH adjusting agent after adjusting to a desired salt component and acid component concentration. As such a pH adjuster, an inorganic oxo acid or hydroxide can be preferably used. According to a more preferred embodiment of the present invention, the pH of the cleaning agent is more preferably in the range of 4 to 9, more preferably in the range of 4.5 to 7, in view of skin irritation, safety, effects of members, and the like. In particular, when an amphoteric amino group-containing sulfonic acid compound (aminosulfonic acid) is used as the deodorant component, it is preferable that the pH of the solution is set near the isoelectric point of aminosulfonic acid. In this case, a preferred range is ± 1.0 of the isoelectric point of aminosulfonic acid. The smaller the difference between the pH of the solution and the isoelectric point of aminosulfonic acid, the less dissociation of aminosulfonic acid, so that the interaction with metal ions can be minimized. By designing the cleaning agent in this way, it is possible to maximize the deodorizing / deodorizing effect of the low-concentration metal ions and to freely design the deodorizing effect.

Applications and methods of use According to a preferred embodiment of the present invention, the cleaning agent of the present invention can be used to remove stains in places where water does not come into contact in normal use, particularly cleaning or washing using water such as washing or washing. It is preferably used for difficult parts and articles. Such a site may be present around water, such as a toilet, bathroom, or kitchen. Specifically, in a toilet, a clearance generated in a portion where the western toilet bowl and the floor contact, a clearance generated in a portion where the western toilet and the wall contact, a clearance generated in the toilet seat and the toilet seat mounting surface, a toilet lid In the gap between the toilet seat and the toilet seat, the gap between the local cleaning device and the toilet seat mounting surface, the gap between the toilet seat and the tank, Clearance generated, clearance generated in moving parts such as portable toilet lids and toilet seat mounting parts, local cleaning device nozzles, clearance generated in the joints of panel type building materials used as flooring and wall finishing materials, cement joints, etc. Is mentioned. In the bathroom, the back of the aprons of the bathtub and the panel material that makes up the wall, in the washroom, the gap between the washbasin and the wall, in the kitchen, in the grilled grill, around the drain, around the drain, For example, the gap between the system kitchen and the wall. Such parts and articles tend to accumulate odor-causing substances such as sebum, urine / sweat, excrement, cooking oil and food waste, and further, the odors generated by alteration of the causative substances will be infiltrated. While it tends to be a source of odor drifting in the space, if a coloring mark remains due to the use of a cleaning agent, it remains without being washed away, and the aesthetics are greatly impaired. Therefore, by using the cleaning agent of the present invention for the above-mentioned parts and articles, the effect of preventing the generation of odor can be directly exhibited in the generation source without leaving a coloring mark at the application site, and at the same time, the cause It can also exert a deodorizing effect that eliminates the odor generated and stained by the alteration of the substance. Therefore, an excellent deodorizing effect is exhibited without impairing the aesthetic appearance of the application location. The cleaning agent of the present invention is particularly suitable for cleaning, deodorizing and deodorizing toilets, bathrooms, kitchens and pet products. The application method of the cleaning agent may be performed by a known method such as spraying or coating, and is not limited. The cleaning agent of the present invention may be left as it is after being applied to the target site, or may be wiped up with a fiber material such as woven fabric, non-woven fabric, or paper after application. Alternatively, the target portion may be wiped after the fiber material is preliminarily impregnated with the cleaning agent. Further, after applying the cleaning agent, the application site may be wiped dry, wiped with water, or rubbed and rinsed with a cleaning tool such as a sponge or brush, and then the cleaning agent is applied again and left as it is.
However, it is needless to say that the cleaning agent of the present invention may be used in a place where water contacts in a normal use mode. Moreover, it can also be used by the method similar to a general residential synthetic detergent.

  Arbitrary methods, such as spraying and application | coating, can be utilized for the preferable application method of a cleaning agent. A spray type such as trigger spray or aerosol spray is preferable in order to efficiently distribute the cleaning agent to the target site such as the article and the gap formed by the article and to exert its function. The spray type cleaning agent which filled the cleaning agent of this invention in the container provided with the spraying apparatus can be utilized suitably. In particular, a trigger spray that includes a container filled with a liquid agent and a spray device that is manually driven and in which the spray apparatus can be attached to and detached from the container is preferable because the liquid agent can be refilled and is economical. When it is desired to apply the cleaning agent to tile joints, floors and walls, toilets and urinals as a whole, a spraying device with a large spray pattern diameter or a spraying device with a large spray amount is preferable. Specifically, the spray pattern diameter is preferably 10 cm or more. The spray pattern diameter here is sprayed from a position 20 cm away from the tip of the spraying device toward the paper having excellent water absorption, and the area where the liquid agent is adhered is visually determined, and the longest diameter cm is measured with a ruler. It shows the determined spray pattern diameter. The spray amount of the trigger spray is preferably 0.1 to 3.0 g in one stroke. If it is 0.1 g or less, the number of sprays for spraying the amount necessary for cleaning, deodorizing and deodorizing increases, and the operation in use becomes inconvenient. If it is 3.0 g or more, the spray amount increases locally, and the effects of the present invention are hardly exhibited. The spray amount of the cleaning agent of the present invention necessary for cleaning, deodorizing and deodorizing varies depending on the size of the target site and the amount and type of components in the liquid composition, but is usually 0.1 g to 10 g. In particular, when the cleaning agent is suitable for an article or a gap formed by the article, a spraying device having a variable spray pattern diameter is preferable. In addition, when it is desired to effectively retain the cleaning agent at the application site, a spraying device having a mechanism capable of discharging the cleaning agent in the form of foam is preferable.

Another preferable application method of the cleaning agent is a method of wiping the target site after impregnating the cleaning agent with a fiber material such as woven fabric, non-woven fabric or paper in advance. The cleaning agent of the present invention filled in the container is impregnated into the fiber material by the user and applied to the target site. Alternatively, a user can use an impregnated body obtained by impregnating a fiber material with a cleaning agent and sealed with a resin film or a laminate film.

The present invention will be described in more detail by the following examples, but the present invention is not limited to these examples.
Examples 1-33 (reference examples)
(1) Preparation of deodorant The following were prepared as a raw material of a deodorant.
Salt component , copper gluconate, zinc gluconate
Acid component , aminoethanesulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, sulfanilic acid, amidosulfuric acid, p-toluenesulfonic acid, 2- [4- (2-hydroxyethyl) -1-piperazinyl)] ethanesulfonic acid ( HEPES)
・ 3-morpholinopropanesulfonic acid (MOPS)
N-tris (hydroxymethyl) methyl-3-aminopropanesulfonic acid (TAPS)
・ Phosphoric acid (used for comparison)
・ Citric acid (used for comparative example)
・ Glycine (used for comparative example)
pH adjuster / sodium hydroxide
Solvent , water, 2-propanol, ethanol

  Solvents having the compositions shown in Tables 1 to 3 were prepared as solvents. Various salt components and acid components were added to this solvent so as to have concentrations (mM) shown in Tables 1 to 3, and mixed. Furthermore, in Examples 20 to 33, a pH adjuster was added to the obtained solution to adjust the pH of the solution to 5 ± 0.5. In this way, deodorants having various compositions were obtained.

(2) Evaluation of deodorant About the obtained various deodorizers, the evaluation test shown below was done.

Evaluation 1: Deodorization test For each of the deodorizers of Examples 1 to 33, an evaluation test of deodorization performance based on inhibition of enzyme activity was performed as follows. First, a sealed glass container having a diameter of 40φ × 75 mm and a capacity of 60 mL was prepared. To this glass container, 0.15 g of an aqueous solution of 1500 ppm urease (manufactured by Wako Pure Chemical Industries, Ltd., Nata beans, 80 to 150 units / mg) and 1 g of the deodorizer of Examples 1 to 33 were added and mixed for 1 hour. Next, 2 g of 10% urea water was added, and the ammonia odor generated from the container after 24 hours was evaluated by a sensory test based on the following odor intensity standards. In the sensory test, those having an odor intensity of 2 or less were evaluated as “G” (good), and those having an odor intensity of 2 or more were evaluated as “NG” (not good). The results were as shown in Tables 1-4.
Odor intensity 5: Smell clearly understandable Odor intensity 4: Smell understandable when smelled well Odor intensity 3: Somehow understandable odor intensity 2: Almost no odor Odor intensity 1: No odor at all

Evaluation 2: Deodorization test 1 (TMA)
About each deodorizer of Examples 1-33, the deodorizing test of the trimethylamine (TMA) was done as follows. A trimethylamine aqueous solution was injected into a 5 L tedra bag so that the initial concentration was 15 ppm, 1.0 g of deodorant was injected, pure air was charged, and the trimethylamine concentration after 5 minutes was measured by a detection method. Using the obtained trimethylamine concentration and the trimethylamine initial concentration measured in advance by the detection method, the deodorization rate (%) for trimethylamine was calculated based on the following formula.
Deodorization rate (%) = [( _{CTMA0− CTMA1} ) / _CTMA0 ] × 100
(In the formula, _CTMA0 is the initial concentration of trimethylamine, and _CTMA1 is the concentration of trimethylamine after 5 minutes have passed since the deodorant was added)
Then, those having a trimethylamine deodorization rate of 60% or more were evaluated as “G” (good), and those having 60% or less were evaluated as “NG” (not good). The results were as shown in Tables 1-3.

Evaluation 3: Deodorization test 2 (MM)
About each deodorizer of Examples 20-33, the deodorization test of methyl mercaptan (MM) was done as follows. 10 ppm methyl mercaptan and 2.44 g of deodorant were injected into a 5 L tedra bag, and the methyl mercaptan concentration after 5 minutes was measured by a detector tube method. Using the obtained methyl mercaptan concentration and the initial methyl mercaptan concentration measured in advance by the detection method, the deodorization rate (%) for methyl mercaptan was calculated based on the following formula.
Deodorization rate _{(%) = [(C MM0} -C MM1) / C MM0] × 100
(In the formula, _CMM0 is the initial concentration of methyl mercaptan, and _CMM1 is the concentration of methyl mercaptan after 5 minutes have passed since the deodorant was added.)
A methyl mercaptan deodorization rate of 30% or more was evaluated as “G” (good), and a value of 30% or less was evaluated as “NG” (not good). The results were as shown in Table 3.

Evaluation 4: Deodorization test for toilets For each of the deodorizers in Examples 1, 7, 19 and 20, the deodorant performance evaluation for toilets was conducted by 20 monitors who answered that there was a clearly unpleasant odor in the toilet space. It was. First, the deodorizer was filled in a container with a trigger type spray pump (Z-305 series, manufactured by Mitani Valve Co., Ltd.). Subsequently, the deodorizer was sprayed once each from a distance of 10 cm to a gap generated between the toilet seat and the toilet seat mounting surface and a gap generated at a portion where the Western toilet bowl and the floor surface contact each other. Moreover, the deodorizer was sprayed 3 times from the distance of 50 cm toward the water storage part in a Western style toilet bowl. Furthermore, the deodorizer was sprayed five times from the position of the height of 150 cm at the toilet entrance toward the front toilet space. Changes in odor intensity in the toilet space after spraying were evaluated by a sensory test based on the same odor intensity standards as in Evaluation 1 over one week. Then, compared with the odor intensity of the target odor before applying the deodorant (that is, at the start of the test), the odor intensity of the target odor after one week has been reduced by 2 points or more as “G” (good). The case where the odor intensity was not reduced or was reduced by less than 2 points was evaluated as “NG” (not good) (determined by the average value of 20 monitors). The results were as shown in Tables 1, 2, and 4.

Evaluation 5: Deodorization test for nursing use About each deodorant of Examples 4, 8, 19 and 20, use of care recipient by 20 monitors who answered that there was an unpleasant odor in the home where elderly people need nursing care Deodorant performance evaluation was performed on the futon. First, the deodorizer was filled in a container with a trigger type spray pump (Z-305 series, manufactured by Mitani Valve Co., Ltd.). Next, the deodorant was sprayed once from a distance of 10 cm to the futon. Further, once every two days, a deodorant was sprayed from a distance of 50 cm so that the liquid agent was evenly distributed over the entire futon. The change in odor intensity in the space where the futon was placed after spraying was evaluated by a sensory test based on the same odor intensity standard as in Evaluation 1 over one week. Then, compared with the odor intensity of an unpleasant odor before applying the deodorant (that is, at the start of the test), the odor intensity after one week has been reduced by 1 point or more as “G” (good), odor Those in which the intensity did not decrease or decreased by less than 1 point were evaluated as “NG” (not good) (determined by the average value of 20 monitors). The results were as shown in Tables 1, 2, and 4.

Evaluation 6: Colorability evaluation test For each of the deodorizers of Examples 1, 17, and 20, an undesirable colorability evaluation test was performed as follows. First, a white cotton cloth was soaked in a deodorant, pulled up and then air-dried. Subsequently, the change in color tone was visually confirmed as compared with a cotton cloth which was subjected to the same operation as described above using water instead of the deodorizer. Then, “G” (good) indicates that there is almost no change in color tone compared to a cotton cloth that has been subjected to the same operation with water, and “NG” (not good) indicates that the color change is confirmed. evaluated. The results are as shown in Tables 1, 2, and 4. In the deodorant of Example 17 of the comparative example, the cotton cloth was colored light blue.

Examples 34-58 (Examples)
(1) Adjustment of cleaning agent The following were prepared as raw materials for the cleaning agent.
Salt component , copper gluconate, copper sulfate, pentahydrate, zinc lactate, trihydrate
Acid component・ Aminoethanesulfonic acid ・ Aminobenzenesulfonic acid ・ Benzenesulfonic acid ・ 2- [4- (2-hydroxyethyl) -1-piperazinyl] ethanesulfonic acid (HEPES)
・ Amidosulfuric acid
Surfactant component / polyoxyethylene alkyl ether sulfate ester salt: R (C: 12 to 15), degree of polymerization of ethylene oxide (3E.O)
Polyoxyethylene polyoxypropylene glycol copolymer 1: polyoxyethylene (25) polyoxypropylene glycol (30)
Polyoxyethylene polyoxypropylene glycol copolymer 2: polyoxyethylene (160) polyoxypropylene glycol (30)
-Polyoxyethylene polyoxypropylene glycol copolymer 3: polyoxyethylene (150) polyoxypropylene glycol (35)
Sucrose fatty acid ester: Chemical formula C ₂₇ H ₅₂ O ₁₂
Polyoxyethylene alkyl ether R (C: 12-14), degree of polymerization of ethylene oxide (12E.O)
-Palm oil fatty acid diethanolamide-Sodium dodecylbenzene sulfonate-Polyoxyethylene alkyl ether phosphate ester: R (C: 8-12), Degree of polymerization of ethylene oxide (2-4E.O)
pH adjuster / sodium hydroxide
Solvent , water, ethanol

  Deodorants having the compositions shown in Table 5 and Table 6 were prepared by adding and mixing a salt component, an acid component, and a surfactant to a solvent. In Example 45, a pH adjusting agent was added to the obtained solution to adjust the pH of the solution to 6 ± 0.5.

(2) Evaluation of cleaning agents The tests of the above evaluations 1 to 4 and 6 and the following evaluations 7 to 9 were performed. The results are shown in Tables 5 and 6.

Evaluation 7: Detergency evaluation test-1
About each cleaning agent of Examples 35, 37, and 42, the evaluation test of the washing | cleaning property was done as follows. In a 2 L beaker, a polypropylene test piece (*) adhering pseudo-fouling was vertically immersed for 3 minutes in 840 ml of an aqueous solution in which a detergent was dissolved at 5% by weight, which was stirred at 200 rpm, and washed. . After immersing, rinsing with ion-exchanged water, drying, and the washing rate was calculated according to the following formula from the change in the amount of dirt adhering to the test piece before and after washing.
Cleaning rate (%) = [(W0−W1) / W0] × 100
(W0 is the amount of dirt adhering to the specimen before washing, and W1 is the amount of dirt adhering to the specimen after washing)
Then, those having a cleaning rate of 30% or more were evaluated as “G” (good), and those having a cleaning rate of less than 30% were evaluated as “NG” (not good).
* Method for preparing a polypropylene test piece with pseudo-fouling A polypropylene plate was immersed for 2 seconds in 60 ml of chloroform in which 10 g of beef tallow, 10 g of soybean oil, 0.25 g of monoolein, and 0.10 g of oil red were dissolved. It was made to dry at 10 degreeC for 10 hours.

Evaluation 8: Detergency evaluation test-2
About each cleaning agent of Examples 34-58, the washability evaluation test was done as follows. It was wiped with a wiping cloth impregnated with 5 g of liquid agent (BEMOT M-3 manufactured by Ozu Sangyo Co., Ltd.), and it was confirmed by appearance whether or not the pseudo dirt was removed. The case where the pseudo filth was removed was designated as “G” (good), and the case where the pseudo filth remained was designated as NG (not good).
* Method for preparing a polypropylene test piece with pseudo-fouling A polypropylene plate was immersed for 2 seconds in 60 ml of chloroform in which 10 g of beef tallow, 10 g of soybean oil, 0.25 g of monoolein, and 0.10 g of oil red were dissolved. It was made to dry at 10 degreeC for 10 hours.

Evaluation 9: Toilet Cleanability Evaluation Test For each of the cleaning agents of Examples 37 and 42, the toilet cleanability was evaluated by 20 monitors. First, the cleaning agent was filled in a container with a trigger type spray pump (YT-97-FX, manufactured by Yoshino Kogyo Co., Ltd.). Next, after the cleaning agent was sprayed twice on the toilet paper folded in quadruplicate, the outside of the toilet (the toilet surface where washing water does not flow) was blown up. It was visually confirmed whether or not the adhered dirt could be removed. Those with 14 or more respondents who answered “removed” were judged as “G” (good), and those with 13 or less were judged as “NG”.

Claims (15)

  An alkylsulfonic acid having 1 to 6 carbon atoms which may be substituted with a salt of copper (II) ion and / or zinc ion and at least one selected from the group consisting of an amine group, an imine group and a hydroxyl group, At least one acid component selected from the group consisting of arylsulfonic acids having 5 to 14 carbon atoms, amidosulfuric acid, and derivatives thereof, a non-carboxylate type anionic surfactant, and / or a nonionic surfactant A cleaning agent comprising at least one surfactant component selected from agents and water as a solvent, wherein the salt is contained in an amount of more than 0.001 mM and less than 10 mM. The cleaning agent according to claim 1, wherein LD _{50 of the} salt is 300 mg / kg or more.   The cleaning agent according to claim 1 or 2, wherein the salt is selected from the group consisting of gluconate, sulfate, malate, and lactate.   The cleaning agent according to any one of claims 1 to 3, wherein the salt is a gluconate. The cleaning agent according to any one of claims 1 to 4, wherein the salt is contained in an amount of 0.005 mM to 5 mM.
Cleaning agent. Compound group in which the alkylsulfonic acid and / or arylsulfonic acid is represented by the following chemical structural formula:
R ¹ —SO ₃ H (1)
(Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or an amine group having 1 to 6 carbon atoms),
R ²
> N—R ⁴ —SO ₃ H (2)
R ³
(Wherein R ² and R ³ are each independently a hydrogen atom, an amine group, a hydroxyl group, a sulfonic acid group, or a hydrocarbon group having 1 to 6 carbon atoms or an aryl group having 5 to 14 carbon atoms, However, at least one hydrogen atom of the alkyl group and aryl group may be substituted with a hydroxyl group, an amine group, or a sulfonic acid group, and R ² and R ³ may be bonded to each other to form a ring. R ⁴ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 5 to 14 carbon atoms, and at least one hydrogen atom of the alkyl group and aryl group is substituted with a hydroxyl group, an amine group, or a sulfonic acid group. The deodorant according to any one of claims 1 to 5, which is selected from:   The cleaning agent according to claim 6, wherein the acid component is aminoethanesulfonic acid.   The cleaning agent according to any one of claims 1 to 7, wherein the acid component is contained in an amount of 0.5 mM or more.   The cleaning agent according to any one of claims 1 to 7, wherein the acid component is contained in an amount of 0.5 mM to 120 mM.   The cleaning agent according to any one of claims 1 to 9, which has a pH of 3 to 10.   The cleaning agent according to any one of claims 1 to 10, further comprising an alcohol having 2 or 3 carbon atoms as a solvent.   The cleaning agent according to any one of claims 1 to 11, which is used in a place where water does not contact in a normal use mode.   The cleaning agent according to any one of claims 1 to 11, which is used as a source of odor generation around water.   The usage method of a cleaning agent which comprises the step which applies the cleaning agent as described in any one of Claims 1-11 to the location which water does not contact in a normal use aspect.   The method of Claim 14 that the location which water does not contact in the said normal use aspect exists in the odor generating source around water.