JP2012111846A - Acidic antibacterial detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acidic antibacterial detergent composition excellent in washing effect relative to oily staining although it is an acidic detergent, having high antibacterial effect even when it is diluted and used, and having less problem of chemical cracks relative to a plastic resin product.SOLUTION: The acidic antibacterial detergent composition includes (A) an organic acid and/or its salt, (B) a betaine type amphoteric surfactant and (C) a cationic antibacterial agent as indispensable components, and has a pH of 4.0-5.5. The betaine type amphoteric surfactant (B) especially preferably contains one kind or more of betaine selected from alkylcarbo betaine, alkylamidecarbon betaine, alkylsulfo betaine, alkylhydroxy sulfobetaine, alkylamide sulfobetaine and alkylamidehydroxysulfo betaine.

Description

The present invention relates to an acidic antibacterial detergent composition useful for cleaning hard surfaces such as kitchens and bathrooms. More specifically, the present invention relates to an acidic antibacterial composition that is excellent in cleaning oily soil, has a high antibacterial effect, and has little effect on plastic resins. The present invention relates to a cleaning composition.

Residential dirt mainly includes water stains in kitchens and washstands that contain inorganic components such as silicon and calcium contained in tap water, bathroom stains that are mainly composed of fatty acid alkaline earth metal salts, and calcium phosphate. There are urine stone stains on the toilet as ingredients, denatured oil stains from cooking and tableware, and stains from hand sebum. Among these stains, it is known that an acidic detergent using an organic acid or the like is effective for washing water stains such as water stains, scale stains and urine stone stains. However, these acidic cleaning agents have a drawback in that they are less effective against oily stains such as modified oil stains and hand stains.

It is also known that bad odors and slime that occur near the drains of bathrooms, kitchens, etc. are caused by the growth of microorganisms such as bacteria and mold. Even if a cleaning agent or the like is used, there is a problem that it is diluted with the accumulated water and the growth of these microorganisms cannot be suppressed, resulting in bad odor and sliminess.

On the other hand, there are products of various materials such as tiles and stainless steel in residential facilities, and recently there are many plastic resin products molded with ABS resin or polystyrene resin. This plastic resin product has a problem of chemical cracks such as cracking of the resin, and development of a cleaning agent having less influence on the plastic resin product is also desired.

Patent Document 1 contains amphoteric surfactants, nonionic surfactants, polycarboxylates and the like as essential components, and has a pH of about 1 to about 5.5, preferably about 2 to about 4.5. A liquid composition is disclosed. The composition of this document has a problem of chemical cracking with respect to plastic resin products since it is recommended to use a polyalkylene alkyl ether-based compound even with a nonionic surfactant. In addition, Patent Document 1 does not describe antibacterial properties when diluted with water accumulated in a drain outlet. Patent Document 2 discloses an acetic acid odor reducing agent and acetic acid for an acetic acid-containing detergent composition for bathrooms and kitchens, comprising at least one compound selected from amine oxide type surfactants and carbobetaine type amphoteric surfactants. A method for reducing odor is disclosed, and Patent Document 3 discloses a cleaning composition containing acetic acid, a fruit fragrance, and a surfactant as essential components. It does not discuss antibacterial properties when diluted by the same method.

Japanese National Patent Publication No. 6-500581 JP 2001-354994 A Japanese Patent Laid-Open No. 2002-3886

An object of the present invention is to provide an acidic antibacterial detergent composition that has an excellent cleaning effect against oily soils, has a high antibacterial effect even when diluted, and has few problems of chemical cracking against plastic resin products. It is to provide.

The present invention has been found that the following constitution has an excellent effect for achieving the above-mentioned object.
(1) Contains (A) an organic acid and / or a salt thereof, (B) a betaine amphoteric surfactant, and (C) a cationic antibacterial agent as essential components, and has a pH of 4.0 to 5.5. An acidic antibacterial detergent composition characterized by that.
(2) (B) The betaine-type amphoteric surfactant is at least one selected from alkylcarbobetaines, alkylamidocarbobetaines, alkylsulfobetaines, alkylhydroxysulfobetaines, alkylamidosulfobetaines, and alkylamidohydroxysulfobetaines. (1) The acidic antibacterial cleaning composition according to (1).
(3) (C) The cationic antibacterial agent is one or more selected from gemini-type quaternary ammonium salts, polyhexamethylene biguanide salts, and polyhexamethylene guanidine salts (1) or (2) ) The acidic antibacterial detergent composition described.

The acidic antibacterial cleaning composition of the present invention can provide an acidic cleaning agent that is excellent in cleaning power against oily stains while being an acidic cleaning agent, has few problems of chemical cracks on plastic resin products, and has high antibacterial properties. . The acidic antibacterial detergent composition of the present invention is effective in preventing bad odors in drains such as kitchen sinks, bathrooms, and washstands with pooled water due to its high antibacterial properties.

The test device used for the chemical crack test of a plastic resin is shown.

Hereinafter, embodiments of the present invention will be specifically described.
Examples of the organic acid and / or salt thereof as component (A) of the acidic antibacterial cleaning composition of the present invention include glycolic acid, lactic acid, tartaric acid, malic acid, citric acid and other hydroxycarboxylic acids or salts thereof, ethylenediamine 4 Examples thereof include aminocarboxylic acids such as acetic acid or salts thereof, phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid and aminotrimethylenephosphonic acid or salts thereof, and lower carboxylic acids such as acetic acid or salts thereof. . Further, as salts of these organic acids, alkali metal salts such as sodium salts and potassium salts, alkanolamine salts such as monoethanolamine salts, diethanolamine salts, and triethanolamine salts, ammonium salts, and the like can be used.

The compounding quantity of this component (A) is 0.1-15 mass% normally in an acidic antibacterial detergent composition, Preferably it is 0.3-10 mass%. When the blending amount of the organic acid and / or salt thereof is less than 0.1% by mass, the cleaning effect on water stains such as scale stains and water stains, which are characteristic of the acidic cleaning agent, is poor, whereas from 15% by mass At most, the cleaning effect is not improved.

The surfactant which is the component (B) of the present invention comprises a betaine type amphoteric surfactant, and is an alkylbenzene sulfonate, α-olefin sulfonate, alkane sulfonate, polyoxyethylene alkyl ether sulfate, higher fatty acid salt. Nonionic surfactants typified by anionic surfactants such as polyoxyalkylene alkyl ether, polyoxyalkylene phenyl ether, polyoxyethylene alkenyl phenyl ether and the like are suitable for the acidic antibacterial detergent composition of the present invention. Absent. A high removal effect on oily soil in the acidic region, which is one of the characteristics of the acidic antibacterial detergent composition of the present invention, is achieved by using a betaine-type amphoteric surfactant as a surfactant. The effect is insufficient with the agent and the nonionic surfactant. Furthermore, the anionic surfactant reduces the antibacterial effect of the cationic antibacterial agent which is the component (C) of the present invention, and nonionic interfaces such as polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene alkylphenyl ether, etc. Since the active agent easily causes chemical cracks in plastic resins such as ABS and polystyrene, the acidic antibacterial detergent composition of the present invention contains an anionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene alkylphenyl. It is not preferred to use ether.

Examples of the (B) component betaine-type amphoteric surfactants include alkyl carbobetaines, alkylamide carbobetaines, alkylsulfobetaines, alkylhydroxysulfobetaines, alkylamidesulfobetaines, and alkylamidehydroxysulfobetaines.

More specifically, the amphoteric surfactants are lauryl-N, N-dimethylacetic acid betaine, coconut alkyl-N, N-dimethylacetic acid betaine, laurylamidopropyl-N, N-dimethylacetic acid betaine, coconut alkylamidopropyl- N, N-dimethylacetic acid betaine, coconut alkyl-N, N-dimethylsulfobetaine, lauryl-N, N-dimethyl-propylsulfobetaine, lauryl-N, N-dimethyl-2-hydroxypropylsulfobetaine, myristyl-N, N -Dimethyl-2-hydroxypropylsulfobetaine, palmityl-N, N-dimethyl-2-hydroxypropylsulfobetaine, alkylamidopropyl-N, N-dimethyl-propylsulfobetaine, coconut alkylamidopropyl-N, N-dimethylhydroxy Propylsulfo Among them, lauryl-N, N-dimethylacetate betaine, coconut alkyl-N, N-dimethylacetate betaine, laurylamidopropyl-N, N-dimethyl are particularly preferred in terms of detergency against oily soils in the acidic region. Preferred are betaine acetate and coconut alkylamidopropyl-N, N-dimethylacetate betaine.

The compounding quantity of this component (B) is 0.1-10 mass% normally in an acidic antibacterial detergent composition, Preferably it is 0.3-6 mass%. When the blending amount of the betaine type amphoteric surfactant is less than 0.1% by mass, the cleaning effect on the oily soil in the acidic region is poor. On the other hand, when it exceeds 10% by mass, the cleaning effect is not improved.

Examples of the cationic antibacterial agent (C) of the present invention include benzethonium chloride, benzalkonium chloride, gemini-type quaternary ammonium salt, polyhexamethylene biguanide salt, polyhexamethylene guanidine salt, polylysine and the like. Gemini-type quaternary ammonium salts, polyhexamethylene biguanide salts, and polyhexamethylene guanidine salts are preferred in that the antibacterial effect is unlikely to be reduced where there are organic stains. Specific examples of gemini-type quaternary ammonium salts include 1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butane dibromide.

The blending amount of this component (C) is not particularly limited, but there is about 100 to 500 ml of pooled water at the drain outlet of a kitchen sink or sink of a household kitchen, and an acidic antibacterial detergent composition is 1 to 1 at a time. It is preferable to blend so as to exhibit an effect when treated with 5 ml, that is, to exhibit an antibacterial effect even when the acidic antibacterial detergent composition is diluted at least 100 times, and 0.01 to 2 in the acidic antibacterial detergent composition It is preferable to mix by mass%.

It is important that the pH of the acidic antibacterial cleaning composition of the present invention is in the range of 4.0 to 5.5. When the pH is less than 4.0, the detergency against water stains such as water stains is sufficient, but the detergency against oily stains decreases. On the other hand, if the pH exceeds 5.5, the detergency against oily stains is sufficient, but the detergency against stains such as water stains is reduced, so it does not meet the object of the present invention. Moreover, it was recognized that the acidic antibacterial cleaning composition of the present invention is effective in exerting an antibacterial effect even when diluted with water accumulated in a drain outlet.

In the acidic antibacterial cleaning composition of the present invention, in addition to the above essential components, additives blended in a normal cleaning composition within a range not impairing the effects of the present invention, such as solvents, antifouling agents, hydrotropes An agent, a thickener, an abrasive, a fragrance, a pigment, and the like can be blended.

Examples of the solvent include lower alcohols such as ethanol and isopropanol, polyhydric alcohols such as ethylene glycol, isopropylene glycol, and glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether Tellurium, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, polyoxyethylene (P = 1-3) poly Oxypropylene (P = 1-4) glycol monoethyl ether (hereinafter, P represents the average number of moles added), polyoxyethylene (P = 1-2) polyoxypropylene (P = 1-4) glycol monobutyl ether , Propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, polyoxyethylene (P = 2 to 3) polyoxypropylene (P = 2 to 3) glycol dimethyl ether Polyoxyethylene (P = 2 to 4) glycol phenyl ether, phenyl carbitol, phenyl cellosolve, glycol ether-based solvents such as benzyl carbitol, other 3-methyl-4-methoxy butanol, methyl pyrrolidone.

These solvents are effective as foam control agents when used in containers such as triggers, squeeze foamers, etc., for the detergency improving agent for oily soils or the acidic antibacterial detergent composition of the present invention. Especially, glycol ether solvents Is preferred. The compounding quantity of these solvents is 15 mass% or less, Preferably it is 1-10 mass%.

As the antifouling agent blended in the acidic antibacterial detergent composition of the present invention, a cationic antifouling agent, an amphoteric antifouling agent, and a nonionic antifouling agent are preferable. Specific examples include acrylamide diallyldimethylammonium. Examples include chloride copolymer, cationized guar gum, polybetaine, PEG phosphate ester, PPG phosphate ester, glycerine phosphate ester, low molecular weight polyethylene glycol, polyvinyl alcohol, and amino-modified silicone.

Hydrotrope can be blended as a solubilizer for fragrances and solvents that are difficult to dissolve in water, or as a stabilizer or foam regulator for making the solution uniform. Specific examples include p-toluenesulfonic acid and m-xylene. Examples thereof include sulfonic acids or their salts, alkyl polyglycosides, and the like.

Thickeners include xanthan gum, cellulose derivatives, carrageenan, locust bean gum, polymeric polysaccharides such as alginates, high molecular weight polyacrylates and polyvinyl alcohol, among others, cationic xanthan gum, cationic Cationic thickeners such as cellulose derivatives and nonionic thickeners such as polyvinyl alcohol are preferred.

As abrasives, silica or porous silica, aluminum oxide, titanium oxide, aluminosilicate, silicon carbide, quartz sand, sand, shells and other natural pulverized products, mica powder, quartzite, diatomaceous earth, kaolinite, halloysite, montmorillonite, illite Vermiculite can be used.

The fragrance is not particularly limited, but examples thereof include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, aliphatic ethers and aromatic ethers. Oxides such as ethers, aliphatic oxides, terpene oxides, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, thioaldehydes, aldehydes such as aromatic aldehydes, aliphatic ketones, terpene ketones, hydrogenation Ketones such as aromatic ketones, aliphatic cyclic ketones, non-benzene ketones, aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, aromatics Acids such as aromatic carboxylic acids, acid amides, aliphatic lactones, macrocyclic lactones Lactones such as terpene lactone, hydrogenated aromatic lactone, aromatic lactone, aliphatic ester, furan carboxylic acid ester, aliphatic cyclic carboxylic acid ester, cyclohexyl carboxylic acid ester, terpene carboxylic acid ester, aromatic carboxylic acid Synthetic and natural fragrances such as esters such as acid esters, nitrogen-containing compounds such as nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, and indoles can be mentioned, and these include one kind or two or more kinds. It can be used by mixing.

Examples of fragrances that can be used specifically include a list of fragrance raw materials used as fragrances, for example, “synthetic fragrance chemistry and product knowledge”, Motoichi Into, Kagaku Kogyo Nippo (1996), It can be seen in the Japan Fragrance Association edition, Asakura Shoten (1989), etc., and each of them is cited as a part of the disclosure of this specification.

Examples of the dosage form of the acidic antibacterial detergent composition of the present invention include aqueous solutions and aqueous dispersions, and various dosage forms such as bottles, trigger sprays, squeeze foamers, and aerosols can be used. It is not limited to.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated still in detail, this invention is not limited to these Examples. Prior to the examples, first, test methods in the examples will be described.

(1) Oil stain cleaning power 0.5 part of a curing agent containing Cobalt Tallate is added to 9.5 parts of commercially available salad oil and stirred at room temperature for 2 hours to prepare a dirt solution. This solution is evenly applied to a stainless steel piece (5 × 9 cm), and then heat treated at a temperature of 100 to 110 ° C. for 20 minutes to form a model oil stain piece. (Oil stain amount 0.1 ± 0.05g / sheet)
Urethane sponge (6 × 9 × 3 cm) squeezed tightly by moistening water using a detergency tester after 2 ml of detergent solution is evenly dropped on this model oil stain piece and left at room temperature for 2 minutes. And rub 5 times with a load of 570 g. The washed model oil stain pieces were washed with water and air-dried, the weight was measured, and the oil removal rate after washing was calculated by the following formula to obtain the detergency.
Detergency (%) = (W2−W0) / (W1−W0) × 100
W0: Weight of the stainless steel piece W1: Weight of the model oil stain piece before washing W2: Weight of the model oil stain piece after washing air drying The evaluation criteria of the cleaning power were as follows.
○: Detergency is 70% or more Δ: Detergency is 50% or more and less than 70% ×: Detergency is less than 50%

(2) Water red stain cleaning power A piece of stainless steel (3 × 8 cm) was attached to the sink portion of a general household cooking table, and the actual stain was collected without washing the portion for one week. This was immersed in a detergent solution for 2 minutes, washed with water, air-dried, and visually evaluated according to the following criteria.
○: Dirt was almost removed.
Δ: About half of the dirt was removed.
X: Dirt was hardly removed.

(3) Detergent stain cleaning power General household table stains are sprayed twice using a trigger sprayer (approx. 0.7cc per discharge) and 5 times back and forth with a dry cloth. By rubbing, the detergency against hand dirt was visually evaluated according to the following criteria.
○: Dirt was almost removed.
Δ: About half of the dirt was removed.
X: Dirt was hardly removed.

(4) Plastic resin chemical crack test A specimen of ABS resin and polystyrene resin having a width of 5 cm, a length of 10 cm, and a thickness of 2 mm is attached in an arch shape to a tester of d = 9.6 cm as shown in FIG. The test of applying 1 ml of the cleaning solution after covering the whole with tissue paper and allowing to stand at room temperature for 1 day was repeated for 7 days. The state of the resin surface after 7 days was visually evaluated according to the following criteria.
○: Neither cracked nor whitened.
Δ: Whitened.
X: It broke.

(5) Antibacterial test
Make a 100-fold dilution of the antimicrobial composition in SCD medium. 10 ml of 100-fold diluted solution is inoculated with 0.1 ml of kitchen drainage (with slime generated) and cultured at 25 ° C for 3 days. did.
○: Growth of bacteria is not observed at 100-fold dilution.
×: Growth of bacteria is observed at 100-fold dilution

<Test 1>
Acidic antibacterial detergent compositions shown in Table 1 were prepared, and the detergency against oil stains and water stains was evaluated. The pH was adjusted with sodium hydroxide.

From the results shown in Table 1, when the pH of the acidic antibacterial detergent composition is less than 4.0, the cleaning ability against water stains is sufficient, but the cleaning ability against oily stains is reduced. On the other hand, when the pH exceeded 5.5, the detergency against oily soil was sufficient, but a decrease in detergency against water stains was observed. The compositions of Examples 1 and 2 which are acidic antibacterial detergents of the present invention showed good detergency against both oil stains and water stains.

<Test 2>
The acidic antibacterial detergent composition shown in Table 2 was prepared, and the detergency against oil stains and water stains was evaluated.

1: Average carbon number of alkyl group 14
2: Oxyethylene average addition mole number 2
3: Average number of carbon atoms of alkyl group: 10, Average number of moles of oxyethylene added: 8

From the results shown in Table 2, the compositions of Examples 3 and 4 showed good detergency for both oil stains and water stains, but Comparative Example 4 in which an anionic surfactant was added. The composition of Comparative Example 6 in which the composition of No. 5 and the nonionic surfactant were blended had insufficient detergency against oil stains.

<Test 3>
Acidic antibacterial detergent compositions shown in Table 3 were prepared, and the detergency against oil stains and water stains, the ABS resin chemical crack test, and the antibacterial test were evaluated.

1: Average carbon number of alkyl group 14
2: Oxyethylene average addition mole number 3
3: Average carbon number of alkyl group: 12, oxyethylene average addition mole number: 12

As shown in Table 3, the compositions of Examples 5 and 6 showed good results in all of the detergency against oil stains and water stains, the ABS resin chemical crack test, and the antibacterial property test. The compositions of Comparative Examples 7 and 8 blended with the surfactant and the composition of Comparative Example 9 blended with the nonionic surfactant failed to obtain good results in all of these tests.

<Test 4>
The acidic antibacterial detergent composition shown in Table 4 was prepared, and the cleaning ability against hand dirt, the chemical crack test of the polystyrene resin and the antibacterial test were evaluated.

1: Using MIRATAIN CBS manufactured by Rhodia Nikka Co., Ltd.

As shown in Table 4, the compositions of Examples 7 to 9 had good results in cleaning power against hand dirt, chemical crack test of polystyrene resin, and antibacterial test.

The acidic antibacterial detergent composition of the present invention can be used for a wide range of cleaning and antibacterial applications.

Claims (3)

(A) An organic acid and / or salt thereof, (B) a betaine amphoteric surfactant, (C) a cationic antibacterial agent as essential components, and a pH of 4.0 to 5.5 An acidic antibacterial detergent composition. (B) The betaine type amphoteric surfactant contains at least one selected from alkyl carbobetaines, alkylamide carbobetaines, alkylsulfobetaines, alkylhydroxysulfobetaines, alkylamidesulfobetaines, and alkylamidehydroxysulfobetaines. The acidic antibacterial cleaning composition according to claim 1, wherein (C) The cationic antibacterial agent contains at least one selected from gemini-type quaternary ammonium salts, polyhexamethylene biguanide salts, and polyhexamethylene guanidine salts. Cleaning composition.