JPH09235595A - Detergent composition for washing machine tub - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition for washing machine tub which contains dicyandiamide and hydrogen peroxide as essential components and, when necessary, an organic builder and/or an inorganic builder, thus can bleach and cleanse the fouling sticking to the inside of the washing machine tub without occurrence of irritant odor. SOLUTION: This composition contains (A) 0.1-60wt.%, calculated as the hydrogen peroxide formed, of hydrogen peroxide or a peroxide which can form hydrogen peroxide in an aqueous solution (for example, a sodium carbonate- hydrogen peroxide adduct at a molar ratio of sodium carbonate to hydrogen peroxide of 2/3, (B) 0.2-30wt.% of dicyandiamide, as essential components and the pH of the aqueous solution is 8-13. In addition, when necessary, the solution preferably contains 0.1-30wt.% of (C) an organic builder and/or an inorganic builder. The component C is, for example, metal salt of ethylenediaminetetraacetic acid or a metasilicate salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a peroxide-type washing machine tub cleaner composition which has no irritating odor and is capable of effectively bleaching and cleaning stains adhering to the inside of a washing machine tub.

[0002]

2. Description of the Related Art Generally, when a washing machine is used frequently, an unpleasant odor may be generated from the inside of the washing machine tub or a black stain may be attached to the laundry. This is because invisible parts such as the back of the washing tub are entangled with soap residue, undissolved detergent, water stains, sebum from the human body, and lint.
They are attached in the form of sludge or scale, and the attached matter is moldy and gives off an unpleasant odor. Further, the black stains on the laundry are those that adhere to the sludge or scale and sometimes fall off in the washing liquid and reattach to the laundry. This phenomenon is remarkable in the case of a fully automatic washing machine having a double tub, and even in the case of a two-tub type washing machine, stains are found in the washing tub or the dehydration tub. Since deposits generally adhere to invisible areas, it is not easy to remove them simply by mechanical operation.

Several proposals have already been made as a method for cleaning and removing the dirt generated in the washing machine tub. For example, there is a method of using a chlorine bleach containing sodium hypochlorite or sodium isocyanurate as a main component. Although this bleaching agent is excellent in bleaching power, it has a drawback in that it gives off a peculiar odor, makes the user uncomfortable, and may cause poisoning by chlorine gas depending on the method of use.
Further, chlorine-based bleaching agents may produce organic chlorine-based compounds as by-products, and it is desired to switch to bleaching agents that do not use chlorine-based compounds from the viewpoint of environmental protection.

On the other hand, peroxide type bleaching agents such as hydrogen peroxide, inorganic peroxides, organic peroxides, etc. have been proposed, but when used alone, they have a weak bleaching and detergency power against stains on deposits, and thus washing for washing machine tubs. Not enough as a drug. Therefore, various proposals have been made for improving the bleaching action by using a peroxide bleaching agent.
For example, in Japanese Unexamined Patent Publication No. 6-49488, a composition using tetraacetylethylenediamine, tetraacetylglycoluril, pentaacetylglycol, a peroxide and a surfactant is used as a detergent for soap stains to wash a washing machine. It is disclosed to be used for. However, the disclosed composition is not suitable for practical use because it does not have sufficient bleaching and detergency for adherent stains, and it often reacts with hydrogen peroxide to form a compound having an irritating odor. Have a problem.

Japanese Unexamined Patent Publication (Kokai) No. 52-110287 discloses a bleaching agent composition for fibers comprising a peroxide and cyanamide and / or metal cyanamide. The berthing power is not enough.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a detergent composition for a washing machine tub, which has no irritating odor and which can effectively bleach and wash deposit stains in the washing machine tub. .

[0007]

As a result of intensive studies on the above problems, the present inventors have found that dicyandiamide and hydrogen peroxide or peroxides that generate hydrogen peroxide in an aqueous solution are essential components, and if necessary, organic It was found that a composition containing a builder and / or an inorganic builder shows a dramatically high bleaching detergency against stains on deposits in a washing machine tank in a specific pH range, and has no irritating odor. It has been completed. Incidentally, one of the inventors of the present invention has previously mentioned in Japanese Patent Application No. 6-229044 that the composition of a peroxide and dicyandiamide for generating hydrogen peroxide has a pH of 8 to 8
When it was 13, it was confirmed that the effect of removing mold was excellent, but there is no description that the composition can be used for the application which is the subject of the present application.

[0008]

DETAILED DESCRIPTION OF THE INVENTION

As the (A) hydrogen peroxide, a commercially available hydrogen peroxide aqueous solution can be preferably used. The content of the hydrogen peroxide solution in the detergent composition for a washing machine tank of the present invention is generally 0.1.
-60% by weight, preferably 0.1-30% by weight,
More preferably, it is 0.1 to 10% by weight. From the practical viewpoint, 0.1 to 6% by weight is most preferable. If the content is less than this range, the bleaching detergency is low, and if it is more than this range, handling becomes difficult.

It is also possible to use a compound forming an adduct with hydrogen peroxide as a peroxide to generate hydrogen peroxide in an aqueous solution. As the compound forming an adduct with hydrogen peroxide, sodium carbonate hydrogen peroxide adduct obtained by adding sodium carbonate and hydrogen peroxide at a molar ratio of 2: 3, and sodium borate and hydrogen peroxide at a molar ratio of 1: Examples thereof include sodium borate hydrogen peroxide-hydrate added in 1 and sodium borate hydrogen peroxide adduct tetrahydrate. In the case of a compound forming an adduct with hydrogen peroxide, the amount of hydrogen peroxide produced by the dissociation of the adduct in an aqueous solution to be within the above range is used.

As the dicyandiamide (B), a commercially available solid or aqueous solution can be used. The content of component (B) is 0.2
% To 30% by weight, preferably 0.5 to 30% by weight, and more preferably 0.5% to 20% by weight. If the content is less than this range, there is no activating effect, and if the content is more than this range, it cannot be expected to enhance the effect any further.

(C) Dicyandiamide as an activator for activating hydrogen peroxide is used in combination with an organic builder and / or an inorganic builder, rather than used alone.
In addition, the effect of detergency is improved. As an organic builder, as a low molecular weight type, EDTA alkali metal salt, ED
Aminocarboxylic acid type builder represented by TA2 alkali metal salt and HEDTA alkali metal salt, alkali metal citrate, carboxymethyloxysuccinate, gluconic acid alkali metal salt, oxycarboxylic acid represented by glycolic acid alkali metal salt Type builder, 1-hydroxyethane-1,1-diphosphoric acid alkali metal salt, 2-phosphonobutanetricarboxylic acid phosphonic acid type builder represented by 1,2,4-alkali alkali metal salts, and high molecular weight type, Acrylate-vinyl sulfonate, acrylate-vinyl alcohol polymer, acrylate-methyl vinyl ether copolymer, 2-hydroxyacrylate-acrylate copolymer, 2-hydroxyacrylate-acrylate copolymer, malein Acid salt-vinyl alcohol Examples of the limer and inorganic builder are phosphate-based builders represented by tripolyphosphate, pyrophosphate, phosphate, metaphosphate, and hexametaphosphate, metasilicate, orthosilicate, JIS No. 1 silicate, JIS No. 2 silicic acid. Salt, JIS No. 3 silicate, sodium silicate, potassium silicate, lithium silicate, barium silicate, magnesium silicate,
A silicate builder represented by ammonium silicate, a borate, a boric acid builder represented by borax, a carbonate builder, a sulfate and the like are used, and among them, silicates are preferable. Further, these builders also have the effect of maintaining the activity of the activator stable for a long period of time.
The content of the component (C) is 0.1% to 30% by weight, preferably 0.5% to 20% by weight. If the content is less than this range, there is no synergistic effect with the activator, and use of more than this range cannot be expected to further enhance the effect.

Adjusting the pH of the detergent composition of the present invention is an essential condition for obtaining high bleaching detergency. The pH of the aqueous solution of the detergent composition or the aqueous solution in the washing machine tank in which the detergent composition is dissolved is usually 8 to 13, preferably 9 to 12, and more preferably 9 to 11.5. If the pH is lower than this range, the bleaching / cleaning action is low, and if it is higher than this range, the peroxide becomes unstable and handling as a detergent composition for a washing machine becomes difficult. Regarding the pH, when the detergent composition is used in the form of an aqueous solution, the undiluted solution is used. When the detergent composition is powder, 1% of the detergent composition is used.
Make an aqueous solution and measure its pH. An alkali agent may be added to adjust the pH, and examples of the alkali agent include caustic soda and caustic potash.

To the detergent composition for a washing machine of the present invention, a surfactant, an enzyme, a hydrotrope, a solvent, a bactericide, a fragrance, a coloring agent, a sequestering agent, etc. are appropriately added as optional components. can do.

The surfactant helps penetration of the detergent composition into stains on deposits, prevents recontamination of stains in the washing machine tub, and enhances the effect of bleaching and removing stains on deposits. it can. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters and amine oxides, and anionic surfactants such as soaps, alkyl sulfates and alkylbenzene sulfonates. The amount of the surfactant added is preferably 0.1% to 10% by weight in the entire washing machine tub cleaner composition.

Further, the enzyme effectively decomposes the stains of the organic matter adhering to the inside of the washing machine tub, so that the washing power of the detergent of the present invention can be further improved. Examples of the enzyme include proteolytic enzymes such as protease, lipolytic enzymes such as lipase, and sugar degrading enzymes such as amylase. The amount of enzyme added is preferably 0.05% to 5% by weight in the entire washing machine tank cleaning composition.

There are two possible ways to use the detergent composition for a washing machine tub of the present invention. One is to use the detergent in an aqueous solution state and evenly sprinkle it in the washing machine tub.
In addition, the part that cannot be seen is poured from the hole in the upper part of the dehydration tank to effectively bleach and clean the dirt. On the other hand, the powder or aqueous solution of the detergent composition is sprayed or poured on the peripheral portion of the rotary blade, and then water is poured to make it full of water. At this time, the effect is further promoted by using hot water such as remaining hot water in the bath.

[0017]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 Hydrogen peroxide aqueous solution, dicyandiamide, sodium hydroxide so that the hydrogen peroxide concentration was 3.0% by weight, the dicyandiamide concentration was 3.0% by weight, and the sodium hydroxide concentration was 1.0% by weight. Was mixed and dissolved in water to prepare a detergent composition for a washing machine tank. The pH of the composition was 10.9. Next, using the obtained detergent composition for a washing machine tub, a bleaching cleaning test and odor judgment of stains adhering to the inside of the washing machine tub were conducted as follows.

[I] <Bleaching cleaning test method and evaluation method for adhered stains> 1) Bleaching cleaning test method for adhered stains For a dewatering tank of a fully automatic washing machine that does not use a commercially available washing machine tank cleaning agent for a long period of time. The test liquid was directly sprayed on the stains adhering to the outside, and the bleaching cleaning power of the stains after standing for 1 hour was checked. 2) Evaluation method The degree of bleaching and washing was visually evaluated according to the following four levels. Bleaching Degree: ◎ Completely bleached. : ○ Bleached fairly well. : △ Bleached to some extent. : X Little or no bleaching.

[II] <Determination and Evaluation Method of Odor> 1) Odor Determination Method 10 panelists smelled the odor of the bleaching agent composition, and sensory evaluation was performed. 2) Odor evaluation method The odor was evaluated as follows. Evaluation: ○ Seven or more panelists did not feel any irritating odor or bad odor. : Δ 4 to 6 panelists felt an irritating odor or a bad odor. : X 7 or more panelists felt an irritating odor or a bad odor. Table 1 shows the results.

Example 2 Hydrogen peroxide concentration was 3.0% by weight, dicyandiamide concentration was 3.0% by weight, sodium orthosilicate concentration was 2.0% by weight.
A hydrogen peroxide aqueous solution, dicyandiamide, and sodium orthosilicate were mixed and dissolved in water to prepare a washing machine tank cleaning composition in the same manner as in Example 1. PH of composition is 1
0.7. Next, using the obtained detergent composition for a washing machine tank, a bleaching cleaning test for adhered stains and odor determination were performed in the same manner as in Example 1. The results are shown in Table 1.

Example 3 The hydrogen peroxide concentration was 3.0% by weight, the dicyandiamide concentration was 3.0% by weight, the EDTA4 soda concentration was 0.5% by weight, and the sodium hydroxide concentration was 1.0% by weight. Hydrogen peroxide solution, dicyandiamide, EDTA4 soda,
Sodium hydroxide was mixed and dissolved in water to prepare a detergent composition for a washing machine tank in the same manner as in Example 1. The pH of the composition is 10.
Nine. Next, using the obtained detergent composition for a washing machine tank, a bleaching cleaning test for adhered stains and odor determination were performed in the same manner as in Example 1. The results are shown in Table 1.

Example 4 A detergent composition for a washing machine tank was prepared in the same manner as in Example 1 except that hydrogen peroxide was changed to sodium carbonate hydrogen peroxide adduct. The amount of sodium carbonate hydrogen peroxide adduct used was adjusted so that the amount of hydrogen peroxide contained was 3%. PH of composition
Was 10.3. Next, using the obtained detergent composition for a washing machine tank, a bleaching cleaning test for adhered stains and odor determination were performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 A bleaching cleaning composition was prepared using sodium hypochlorite as shown in Table 1. Using the obtained bleaching / cleaning composition, a bleaching / cleaning test for adhering stains and odor determination were conducted in the same manner as in Example 1. The pH of the composition and the results are shown in Table 1. Bleachability was good, but chlorine odor was strong.

Comparative Example 2 A bleaching cleaning composition was prepared in the same manner as in Example 1 except that dicyandiamide was not used. Using the obtained bleaching / cleaning composition, a bleaching / cleaning test for adhering stains and odor determination were conducted in the same manner as in Example 1. The pH of the composition and the results are shown in Table 1. No bleach cleaning performance was observed.

Comparative Example 3 A bleaching cleaning composition was prepared in the same manner as in Example 1 except that tetraacetylethylenediamine was used instead of dicyandiamide. Using the obtained bleaching / cleaning composition, a bleaching / cleaning test for adhering stains and odor determination were conducted in the same manner as in Example 1. The pH of the composition and the results are shown in Table 1. The bleaching detergency was slightly reduced and the odor of organic acids was strong.

Comparative Example 4 A drifting detergent composition was prepared in the same manner as in Example 1 except that sodium hydroxide was not used. The pH of the composition is 6.8
Met. Using the obtained bleaching / cleaning composition, a bleaching / cleaning test for adhering stains and odor determination were conducted in the same manner as in Example 1. The results are shown in Table 1. Drift performance was not so much recognized.

[0028]

[Table 1]

Example 5 80.0% by weight of sodium hydrogencarbonate hydrogen peroxide adduct (about 19.0% by weight in terms of hydrogen peroxide), dicyandiamide 10.
A detergent composition for a washing machine tub comprising 0% by weight, 2.0% by weight of sodium dodecylbenzenesulfonate, and the remaining amount of sodium carbonate was prepared. The pH of a 1% aqueous solution of the composition obtained at this time was 10.3. Next, using the thus obtained cleaning composition, a bleaching cleaning test and odor judgment of stains adhering to the inside of the washing machine tub were carried out as follows.

[II] <Bleaching cleaning test method and evaluation method for adhered stains> 1) Bleaching cleaning test method for adhered stains For a long period of time without using a commercially available washing machine tank cleaning agent We used 3 fully automatic washing machines of the same type (operating time is almost the same). In addition, it was confirmed in advance that the pulsator of the rotary blade was removed and that the adhered stains were almost equal in all three units. 500 g of the washing machine tub cleaner composition of Example 5 was prepared, and one fully automatic washing machine tub prepared *
After spraying around the rotor blades, pouring warm water of about 40 ° C. to fill the water, leaving it for 2 hours, and then operating for 1 cycle at high water level. 2) Evaluation method Amount of stains peeled and dispersed when left for 2 hours, and 1
After the operation of the cycle was completed, the pearl sweater was removed again, and the remaining stain was visually evaluated. Table 2 shows the results. * By using the above-mentioned method of adding the detergent composition, the bleaching can be effectively performed because the gap between the outer tub and the washing / dehydrating tub, that is, the portion where dirt is attached, is filled with the washing liquid in a concentrated manner.

Example 6 10.0 parts by weight of sodium orthosilicate and 5.0 parts of EDTA4 soda based on 100 parts by weight of the detergent composition of Example 5.
A detergent composition for a washing machine tub comprising 1 part by weight was prepared. The pH of a 1% aqueous solution of the composition obtained at this time was 10.
It was 7. Next, using the obtained cleaning composition, a bleaching cleaning test for stains adhering to the inside of the washing machine tank was carried out in the same manner as in Example 5. The results are shown in Table 2.

Comparative Example 5 Sodium carbonate hydrogen peroxide adduct was 80.0% by weight (hydrogen peroxide equivalent 19.0% by weight), tetraacetylethylenediamine 10.0% by weight, sodium dodecylbenzenesulfonate 2.0% by weight. A bleaching cleaning composition consisting of the remaining amount of sodium carbonate was prepared. 1% of the composition obtained at this time
The pH of the aqueous solution was 10.3. Next, using the obtained bleaching cleaning composition, a bleaching cleaning test for adhered soil was conducted in the same manner as in Example 5. Table 2 shows the results.

[0033]

[Table 2]

[0034]

EFFECTS OF THE INVENTION According to the present invention, there is provided a washing machine tub cleaner composition which has no irritating odor and is excellent in bleaching detergency against stains adhering to the inside of the washing machine tub. The detergent composition for a washing machine tub of the present invention is used for washing in a fully automatic washing machine, outside the dehydration tub, on the upper part of the washing tub where normal washing water is not immersed, or on the back side of the washing tub of a two-tub type washing machine or the dehydration tub It is used for bleaching and cleaning the dirt adhering to.

Claims (5)

[Claims] 1. A (A) hydrogen peroxide or a peroxide which produces hydrogen peroxide in an aqueous solution is 0.1% to 60% by weight in terms of produced hydrogen peroxide, and (B) a dicyandiamide content is 0. A detergent composition for a washing machine tub, which contains 2% to 30% by weight as an essential component and has an aqueous solution having a pH of 8 to 13. 2. The (A) hydrogen peroxide or a peroxide that produces hydrogen peroxide in an aqueous solution is 0.1% to 60% by weight in terms of produced hydrogen peroxide, and the (B) dicyandiamide content is 0. 0.2% to 30% by weight, (C) 0.1% to 30% by weight of an organic builder and / or an inorganic builder are contained as essential components, and the pH of the aqueous solution is 8 to 13. A detergent composition for a washing machine tub. 3. The organic or inorganic builder is ethylenediaminetetraacetic acid (EDTA) metal salt, EDTA2 alkali metal salt, alkaline earth metal salt, nitriloacetic acid metal salt, citrate, carboxymethyloxysuccinate, tripolyphosphate, The detergent composition for a washing machine tub according to claim 2, which is a metasilicate, an orthosilicate, a borate, a carbonate or a sulfate. 4. The detergent composition for a washing machine tub according to claim 2, wherein the inorganic builder is a silicate. 5. The silicate is sodium silicate, potassium silicate, lithium silicate, barium silicate, magnesium silicate,
The detergent composition for a washing machine tub according to claim 4, wherein the detergent composition is selected from ammonium silicate.