JP5603057B2 - Cleaning composition for washing tub - Google Patents

Description

  The present invention relates to a cleaning composition for a washing tub, and more particularly to a cleaning composition for a washing tub having an excellent fungicidal effect against mold generated in the washing tub.

  Dirt generated on the back side of the washing tub is composed of microorganisms such as mold, yeast, bacteria, and detergent-derived components, and clothing-derived components such as lint and sebum, which causes odors from the washing machine and is released. Dirt can cause problems such as contamination of clothes during washing. This phenomenon is particularly likely to occur in a fully automatic washing machine that also serves as a dewatering basket.

  Thus, it is considered that the reason why dirt easily occurs in the washing tub of the fully automatic washing machine is that the washing water tends to remain on the back side of the washing tub, and mold and fungus contamination are likely to occur. There are reports that mold stains in the washing tub cause not only clothing contamination but also allergic dermatitis.

  As for dirt on the back of the washing tub, especially in a fully automatic washing machine, it is not possible to directly observe the situation where the dirt is attached, and the washing machine is not disassembled in the part where the dirt is attached. Since it cannot be touched as much as possible, the removal of dirt is not easy and requires a great deal of labor. Therefore, a composition containing mainly an oxygen-based or chlorine-based bleach as a cleaning agent for a washing machine tub has been proposed.

  Among these, as an example using an oxygen-based bleach, a washing method for washing tubs using sodium percarbonate is known (for example, see Patent Document 1). However, this method does not provide a sufficient cleaning effect, and the fungicidal effect against mold is insufficient.

  On the other hand, as an example using a chlorine bleach, a composition mainly composed of sodium hypochlorite and chlorinated cyanuric acid has been proposed (see, for example, Patent Document 2 and Patent Document 3). This chlorine bleach has a certain effect on mold due to its strong oxidizing power, but it is still not satisfactory.

  For example, when washing a washing tub, not only mold but also its spores are not sufficiently killed, mold is generated again from the spores that remain slightly during washing, and propagates on the back of the washing tub. Causes contamination.

JP 9-235595 A JP 59-71399 A JP 2001-335799 A

  Accordingly, an object of the present invention is to provide a cleaning composition for a washing tub that has an excellent removal effect against dirt generated on the back side of the washing tub, particularly mold and spores thereof.

  In view of the above circumstances, the present inventors have intensively studied to obtain a detergent composition having a high fungicidal effect on fungi and their spores, in addition to dirt such as detergent-derived components, lint, sebum and other clothing-derived components. As a result, it was found that by combining a hypochlorite and a specific polymer, a cleaning composition having a very high fungicidal effect as well as an excellent cleaning effect against dirt can be obtained, and the present invention has been achieved.

  That is, the present invention is a washing tub cleaning composition comprising an alkali metal hypochlorite and an acrylic acid polymer.

  The present invention also relates to washing a washing tub characterized by storing water up to a high water level in the washing tub and then adding 1% or more of the washing tub cleaning composition to the stored water. Is the method.

  According to the present invention, dirt generated on the back side of the washing tub can be efficiently removed, and an excellent fungicidal effect is exerted particularly against mold. Furthermore, after using the cleaning composition of the present invention, there is an effect that stains are less likely to adhere to the back side of the washing tub.

  Therefore, the present invention removes dirt and the like on the back side of the washing tub, kills the mold and its spores, and eliminates the problem that the remaining mold or its spores are propagated again on the back side of the washing tub and recontaminated. The frequency of washing the washing tub can be reduced.

  The detergent composition for a washing tub of the present invention comprises an alkali metal hypochlorite and an acrylic acid polymer as active ingredients.

  Examples of the alkali metal hypochlorite used in the present invention include sodium hypochlorite and potassium hypochlorite, and sodium hypochlorite is particularly preferred. As this sodium hypochlorite, sodium hypochlorite and equimolar sodium chloride are mixed in production, but sodium hypochlorite containing a large amount of sodium chloride may impair storage stability. It is preferable to use one in which sodium chloride has been reduced in advance.

  These alkali metal hypochlorites have not only bactericidal properties but also an oxidizing power that softens, dissolves and decomposes proteins and fats and oils. It exhibits a strong sterilizing and cleaning power.

  The blending amount of the alkali metal hypochlorite in the cleaning composition of the present invention is 0.1 to 5% by mass (hereinafter simply indicated as “%”), preferably 0.5% of the total cleaning composition. -4%, more preferably 1.0-3.5%. If it is added more than 5%, good stability may not be obtained, and if it is less than 0.1%, sufficient bleaching washing effect may not be exhibited.

  Examples of the acrylic acid polymer used in the present invention include polyacrylates having an average molecular weight of 1,000 to 100,000, or salts of maleic acrylate copolymers having an average molecular weight of 1,000 to 100,000. Preferred examples of these salts include potassium salts and sodium salts. Among these, polyacrylic acid sodium salt is preferably used because it does not affect the stability of alkali metal hypochlorite.

The blending amount of the acrylic acid polymer in the cleaning composition of the present invention is 0.1 to 10% of the total cleaning composition, preferably 0.1 to 5%, more preferably 0.5 to 3. %. The addition of 10% or more is not desirable because it may impair the stability of the alkali metal hypochlorite, and if less than 0.1%, a good effect may not be obtained, which is not preferred.

  In addition to the above essential components, a surfactant is preferably added to the cleaning composition of the present invention. As the surfactant to be used, a surfactant conventionally used as a cleaning agent can be exemplified, but preferably a nonionic surfactant, an anionic surfactant, an amphoteric surfactant or a combination thereof can be used. .

  Among the above surfactants, nonionic surfactants include polyoxyethylene alkyl or alkenyl ethers having an alkyl group having 10 to 18 carbon atoms and an average addition mole number of ethylene oxide of 2 to 30, and polyoxyethylene poly (ethylene oxide). Oxypropylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, methoxy polyoxyethylene alkanoate having an alkyl group having 10 to 20 carbon atoms and an average addition mole number of ethylene oxide of 1 to 30, A higher fatty acid alkanolamide having 10 to 20 carbon atoms, an alkyl group having 8 to 18 carbon atoms, an alkyl polyglucoside having an average addition mole number of 1 to 3 glucose units, and an alkyl group having 10 to 14 carbon atoms, Average addition mode of glycerin units It can be mentioned alkyl glyceryl ether, etc. having 1 to 3. The nonionic surfactant in the composition of the present invention may be used alone or in combination of two or more.

Examples of the anionic surfactant include α-olefin sulfonate (AOS), alkane sulfonic acid, saturated or unsaturated C _{12 to} C ₁₈ fatty acid soap, C _{8 to} C ₁₈ fatty acid methyl ester sulfonate, and polyoxyethylene. Alkyl sulfates can be used.

  Further, as amphoteric surfactants, alkylcarbobetaines, alkyldimethylamine oxides, alkylamidopropylamine oxides, alkylsulfobetaines, alkylamidohydroxysulfobetaines, alkylamidoamine type betaines, alkylimidazoline type betaines, and the like can be incorporated. A seed or a mixture of two or more may be used. Of these, alkyldimethylamine oxide, particularly lauryldimethylamine oxide and decyldimethylamine oxide are preferably used from the viewpoint of detergency and stability of alkali metal hypochlorite.

  The amount of the surfactant added is preferably in the range of 0.1 to 5%, more preferably 0.3 to 1% in the cleaning composition.

  Furthermore, the cleaning composition of the present invention may contain an alkali metal hydroxide as a component that improves the stability of the alkali metal hypochlorite. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and sodium hydroxide is particularly preferable. This addition amount is preferably in the range of 0.5 to 3%.

  Furthermore, a hydrotrope agent can be mix | blended with the cleaning composition of this invention. Examples of the hydrotrope used include toluene sulfonate, xylene sulfonate, cumene sulfonate, and naphthalene sulfonate having a benzene ring. Among these, sodium metaxylene sulfonate is preferable. is there. The blending amount of the hydrotrope is preferably in the range of 0.1 to 3%, more preferably 0.3 to 1.5% in the cleaning composition.

  In the cleaning composition of the present invention, optional components other than those described above can be blended within a range that does not impair the good stability and effect of the alkali metal hypochlorite. Such optional components include tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid, aminocarboxylic acid, hydroxyaminocarboxylic acid, citric acid, malic acid and other hydroxycarboxylic acids, cyclocarboxylic acid, phosphonic acid, ether carboxylic acid Oxalic acid, maleic acid, alkali metal salts or derivatives thereof, organic carboxylic acid polymers, chelating agents such as polysaccharide oxides, solvents such as ethanol, rust preventives such as sodium metasilicate, fragrances, deodorants, etc. Can be mentioned.

  Washing the washing tub using the product of the present invention may be performed in substantially the same manner as a conventionally known method for using a washing tub cleaning composition, but when water is stored in the washing machine at a “high water level” ( It is preferably added in such an amount that the concentration of the product of the present invention is 1% or more when full). For example, if the amount of water is 50 liters when the water is stored at “high water level”, after adding 500 g or more of the present invention product, water is supplied to “high water level” and then the standard cycle (washing → rinsing) The washing tub can be washed by operating for one cycle by dehydration.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.

Example 1
Detergent composition for washing tub:
The detergent composition for a washing tub of the present invention (the present products 1 and 2) was prepared according to the following formulation. About the obtained detergent composition for washing tubs, the fungicidal property, bactericidal property, and anti-reattachment property were tested by the following method. Table 2 shows the results of the fungicidal test, Table 3 shows the results of the sterilization test, and Table 4 shows the results of the reattachment prevention test.

(How to)

( performance test )
(1) Mold-killing test A mold-killing test was conducted as follows using Cladosporium sphaerospermum HMRC 3008 strain as a test mold.

Test method (a) Preparation of test spore solution Test mold is inoculated into potato dextrose agar medium, cultured at 25 ° C for 1 week, and adjusted with sterilized water so that the number of spores is 10 ⁷ / mL. It was.

(B) Preparation of test sample Test samples were prepared using sterilized water so that the concentration of each product of the present invention was 1% and 5%.

(C) Inoculation and culture of test spore solution 10 mL of each prepared test sample was put in a test tube, and 0.1 mL each of the test spore solution was inoculated therein. 15 minutes after inoculation, this solution was inoculated on an agar medium and cultured at 25 ° C. for 5 days. Colonies formed after the culture were counted and converted to the number of spores. As a comparative product, sterilized physiological saline was used, and the same test was performed. The results are shown in Table 2.

(2) Bactericidal test A sterilizing test was performed as follows using Staphylococcus aureus NBRC 12732 strain.

Test method (a) Preparation of test bacterial solution Inoculate the test bacteria on a standard agar medium, and after culturing at 25 ° C for 1 week, adjust the number of bacteria to 10 ⁷ / mL using sterilized water. did.

(B) Preparation of test sample Test samples were prepared using sterilized water so that the concentration of each product of the present invention was 1% and 5%.

(C) Inoculation and culture of test bacterial solution 10 mL of each prepared test sample was placed in a test tube, and 0.1 mL of each of the test bacterial solution was inoculated therein. 15 minutes after inoculation, this solution was inoculated on a standard agar medium and cultured at 25 ° C. for 5 days. The colonies formed after the culture were counted and the number of viable bacteria was converted. As a comparative product, sterilized physiological saline was used, and the same test was performed. The results are shown in Table 3.

(3) Re-adhesion prevention test A re-adhesion prevention test was performed as follows using Cladosporium sphaerospermum HMRC 3008 strain as a test mold.

Test method (a) Preparation of test spore solution Test mold is inoculated into potato dextrose agar medium, cultured at 25 ° C for 1 week, and adjusted with sterilized water so that the number of spores is 10 ⁶ / mL. It was.

(B) Preparation of test sample Test samples were prepared using sterilized water so that the concentration of each product of the present invention was 1% and 5%.

(C) Dropping and measurement of the number of mold spores 1 mL of each test sample prepared inoculated with 0.1 mL of the test spore solution was dropped on the top of a slide glass inclined at 45 degrees. After dripping, mold spores adhering to any 9 points on the slide glass were counted visually with a microscope, and the mold spores remaining rate was calculated by the following formula. A comparative product prepared with sterile physiological saline was used. The results are shown in Table 4.

Mold spore survival rate (%) = Na / Nb × 100
Na: Average number of remaining mold spores at 9 points in the slide glass onto which the product of the present invention was dropped Nb: Average number of remaining mold spores at 9 points in the slide glass onto which the comparative product was dropped

(4) Detergent residue removal test A detergent residue removal test was conducted as follows.

(A) Model detergent residue 5 g of calcium acetate, 1.5 g of magnesium nitrate and 5 g of soap are dissolved in 500 ml of water, the precipitated metal soap is filtered, dissolved in 200 ml of isopropyl alcohol, and 1 g of artificial sebum is added. In addition, an artificial detergent residue was used.

(B) Preparation of test piece A micro detergent glass (76 × 26 mm, thickness: 0.9 to 1.2 mm) was coated with model detergent waste having the following prescription to a thickness of 0.1 to 0.2 mm. The test piece was dried all day and night in a constant temperature bath at 40 ° C.

(C) Detergent debris removal test The test piece was taken out after being immersed in a 1% aqueous solution and a 5% aqueous solution of the present invention for 15 minutes, sufficiently washed with ion-exchanged water and dried, and the detergent debris removal rate was determined by the following formula . In addition, what was immersed only in the ion-exchange water which does not put this invention product was made into the comparison product. The results are shown in Table 5.

Detergent residue removal rate (%) = (Wa−Wb) / (Wa−Wc) × 100
Wa: Weight of test piece before immersion
Wb: Weight of the test piece after immersion
Wc: Weight of micro slide glass before adhering detergent residue (5) Bleach test A bleach test was performed as follows.

(A) Bleaching test A contaminated cloth (EMPA # 115, manufactured by Testfabric) cut to 5 cm x 5 cm is dipped in a 1% aqueous solution and a 5% aqueous solution of the present invention for 15 minutes, washed thoroughly with ion-exchanged water, and dried. It was. Subsequently, the reflectance was measured with a digital white photometer (manufactured by Tokyo Denshoku Co., Ltd.) to determine the bleaching rate. In addition, what was immersed only in the ion-exchange water which does not put this invention product was made into the comparison product. The results are shown in Table 6.

Bleaching rate (%) = (Bs−Bc) / (Bw−Bc) × 100
Bs: Lightness value of the contaminated cloth after immersion
Bc: Lightness value of the original contaminated cloth
Bw: Lightness value of EMPA # 115 soaked in bleach for 1 hour (white cloth)

(Result)

  As shown in Tables 2 and 3, the washing tub cleaning composition of the present invention had excellent fungicidal and bactericidal effects. Further, as shown in Table 4, the product of the present invention had an anti-redeposition effect.

  Furthermore, as shown in Tables 5 and 6, the laundry tub cleaning composition of the present invention had excellent detergent residue removal and bleaching effects.

  According to the present invention, dirt generated on the back side of the washing tub can be efficiently removed, and an excellent fungicidal effect is exerted particularly against mold. Furthermore, after using the cleaning composition of the present invention, there is an effect that stains are less likely to adhere to the back side of the washing tub.

Therefore, the present invention can be used as a detergent composition for a washing tub which can mold and sterilize mold and its spores as well as removing dirt on the back side of the washing tub.

Claims (6)

A detergent composition for a washing tub comprising an alkali metal hypochlorite , an acrylic acid polymer , an alkyldimethylamine oxide, and a hydrotrope .   The detergent composition for a washing tub according to claim 1, wherein the acrylic acid polymer has an average molecular weight of 1,000 to 100,000.   The cleaning composition for a washing tub according to claim 1 or 2, wherein the acrylic polymer is a salt of polyacrylic acid or a salt of acrylic acid maleic acid copolymer. 4. The washing tub according to claim 1, wherein the content of alkali metal hypochlorite is 0.1 to 5 % by mass and the amount of acrylic polymer is 0.1 to 5% by mass. Cleaning composition.   The detergent composition for a washing tub according to any one of claims 1 to 4, further comprising an alkali metal hydroxide.   After water is stored up to a high water level in the washing tub, 1% or more of the washing tub cleaning composition according to any one of claims 1 to 5 is added to the stored water. How to wash the washing tub.