JPH11236598A - Detergent composition for washing machine vessel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent compsn. which has no corrosiveness, is safe, does not emit an unpleasant odor, and exhibits an enhanced bleaching power by incorporating an acid anhydride and hydrogen peroxide or a peroxide which generates hydrogen peroxide in an aq. soln. into the same. SOLUTION: This compsn. is prepd. by compounding 0.1-90 wt.%, pref. 1-70 wt. %, hydrogen peroxide or peroxide which generates hydrogen peroxide in an aq. soln., 4-90 wt.%, pref. 8-50 wt.%, acid anhydride having a particle size of 0.001-2 mm, and optionally 0.01-40 wt.%, pref. 0.1-20 wt.%, pH indicator (e. g. Methyl Red, Bromocresol Purple, Bromothymol Blue, or Phenol Red), a buffering agent (e.g. sodium hydroxide or potassium hydroxide), 1-20 wt.% anionic or nonionic surfactant, and other additives such as an enzyme, a sequestering agent, a pH modifier, an inorg. salt, an antimicrobial agent. an antiseptic, a perfume, a pigment, a dye, and a plasticizer in a wt. ratio of the peroxide to the acid anhydride of (2/3)-(19/1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition used for removing dirt attached to a tub wall of a washing machine and mold generated on the tub wall.

[0002]

2. Description of the Related Art In recent years, fully automatic washing machines have been widely used in ordinary households, and large-sized washing machines have become widespread for business use in coin launderettes and the like. These washing machines not only automatically supply water to the washing tub when washing is put into the washing tub but also perform washing. In many cases, there are an inner tub (hereinafter simply referred to as a washing tub) which also serves as a centrifugal dehydration tub and a washing tub, and an outer tub.

When a fatty acid-based detergent is used as a detergent in the above-described washing machine, metal polyvalent ions such as calcium and magnesium contained in water react with fatty acid ions of the detergent, Salt, which does not dissolve in water, is made and adheres to the washing tub of a washing machine as metal soap, and is often deposited and accumulated particularly in complicated places that are not accessible from the outside. The deposits described above are called soap stains, and organic dirt, oils and fats, mineral oil, soil, lint, etc. removed from the laundry are inevitably contained in the production process, so that mold,
Bacteria inhabit, and become black and dirty, and generate a bad smell. At times, they come off and cause problems such as reattachment to laundry.

[0004] Conventionally, as a detergent for removing soap stains, for example, Japanese Patent Publication No. 57-61328, Japanese Patent Application Laid-Open No.
Japanese Patent Application Laid-Open No. 7-169409 discloses a sodium hypochlorite solution. However, sodium hypochlorite is highly corrosive to metals and rubber. Rubber gaskets and packings used in washing tubs of washing machines, aluminum, cast iron, stainless steel parts, etc. There was a problem of strong corrosion.

[0005] As a countermeasure, an oxygen-based soap stain detergent has been proposed. For example, JP-A-6-49488 discloses a combination of an inorganic peroxide, a surfactant and a bleaching activator. A composition is disclosed. However, the use of the above-mentioned cleaning agent generates a gas that gives an unpleasant odor when used, and in particular, when the lid of the washing machine is opened, a strong odor is generated, which is a problem.

[0006] Further, currently available detergents for soap stains (or for mold removal) do not immediately exhibit performance regardless of chlorine-based or oxygen-based detergents and are dissolved in a washing tub for a certain period of time. In addition, there is a defect that the bleaching and washing cannot be completed because it is not possible to visually check the soil in the tub due to the structure of the washing machine.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and is free of corrosiveness, is safe, does not generate an unpleasant odor, and has a high bleaching power. Provided is a washing agent for a washing machine tub having: Still another object of the present invention is to provide a washing machine tub cleaning agent having an instruction function to notify the completion of bleaching.

[0008]

According to the first aspect of the present invention,
A detergent composition for a washing machine tub, comprising a hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution, and an acid anhydride.

The above-mentioned hydrogen peroxide or a peroxide that produces hydrogen peroxide in an aqueous solution is a component that exerts bleaching power. Examples of the peroxide that produces hydrogen peroxide in an aqueous solution include sodium peroxocarbonate, Sodium perborate,
Sodium tripolyphosphate hydrogen peroxide adduct, sodium pyrophosphate hydrogen peroxide adduct, urea hydrogen peroxide adduct and the like, among these, low toxicity, stability, in terms of low temperature bleaching effect, Sodium peroxocarbonate is particularly preferred.

The amount of hydrogen peroxide or the peroxide that forms hydrogen peroxide in an aqueous solution is preferably 0.1 to 90% by weight, more preferably 0.1 to 90% by weight, based on the detergent composition for washing machine tubs.
1 to 70% by weight. If the amount is less than 0.1% by weight, a sufficient bleaching effect cannot be obtained. If the amount exceeds 90% by weight, even if the amount is increased, the corresponding bleaching effect cannot be obtained, which is uneconomical.

The above-mentioned acid anhydride is not particularly limited as long as it does not generate an unpleasant odor and is used as a bleach activator of a detergent composition for a washing machine tub. Examples thereof include succinic anhydride and glutaric anhydride. , Maleic anhydride, itaconic anhydride, pyromellitic anhydride, trimellitic anhydride, methyl phthalic anhydride, phthalic anhydride, naphthalic anhydride, cyclohexanedicarboxylic anhydride, spiculic anhydride, etc., among others, succinic anhydride, Glutaric anhydride, maleic anhydride, itaconic anhydride, pyromellitic anhydride and trimellitic anhydride are preferred.

The amount of the acid anhydride to be added is preferably from 4 to 90% by weight, more preferably from 8 to 50% by weight, in the detergent composition for washing machine tubs. If the amount is less than 4% by weight, a sufficient bleaching effect cannot be obtained, and if it exceeds 90% by weight, a bleaching effect corresponding to an increase in weight cannot be obtained, which is uneconomical.

According to a second aspect of the present invention, there is provided a detergent composition for a washing machine tub, comprising sodium peroxocarbonate and succinic anhydride, wherein the weight ratio of the sodium peroxocarbonate to succinic anhydride is 2/3 to 2/3. 19/1 is a detergent composition for a washing machine tub. In the invention according to claim 2, succinic peroxide is generated as a bleaching active species from sodium peroxocarbonate and succinic anhydride, but in order for this succinic peroxide to exhibit high bleaching power, it is necessary to use a detergent composition. It is necessary that the aqueous solution (ie, the water in the washing tub) be in an alkaline or neutral region. Therefore, when the weight ratio of sodium peroxocarbonate to succinic anhydride is less than 2/3, the aqueous solution of the detergent composition is in an acidic region, so that it is difficult to obtain high bleaching power, and more than 19/1. When the amount of succinic anhydride becomes relatively small, the sufficient bleaching activation power decreases.

In the second aspect of the present invention, there are two types of usage. That is, one is a method in which the detergent composition is made into an aqueous solution state and sprinkled directly on dirt in a washing machine tub (usage method 1). The other is a method in which powder of the detergent composition is directly poured into a washing machine tub, and then poured with water to make it full, soaked and bleached for washing (use method 2). When used in the above usage method 2, in order to dissolve the powder in water quickly, it is simple and efficient to operate the washing machine and agitate the water with the rotary wings. The particle diameter of succinic acid is preferably in the range of 0.001 mm to 2 mm. When the particle diameter exceeds 2 mm, the particles settle on the bottom surface of the washing machine tub, and the surface inside the washing machine tub is easily damaged by the rotation of the rotating blades. On the other hand, particles having a particle diameter of less than 0.001 mm are liable to be scattered or agglomerated during use, making handling difficult.

According to a fourth aspect of the present invention, there is provided the detergent composition for a washing machine tub according to the first, second or third aspect, further comprising p
A detergent composition for a washing machine tub, comprising an H indicator.

The above pH indicator is used as an indicator when the bleaching of the detergent composition for a washing machine tub is completed, and the reaction mechanism of the indicator is as follows. In the washing tub, hydrogen peroxide, or peroxide that generates hydrogen peroxide in aqueous solution,
When dosed with the acid anhydride, the hydrogen peroxide or peroxide that forms hydrogen peroxide in aqueous solution quickly dissolves first, and the water in the washing tub exhibits an alkaline pH of 9-10. Next, hydrogen peroxide reacts with the acid anhydride to generate peracid, which is a bleaching active species, and bleaches stains such as mold to generate an acid. Therefore, as the bleaching proceeds, the pH of the water in the washing tub gradually shifts to acidic, and finally the pH becomes 3
~ 6 acidic.

The reaction between hydrogen peroxide and an acid anhydride results in a pH of 6
, The bleaching and washing is almost completed. Therefore,
The pH indicator used in the present invention is preferably an indicator that changes color at the above pH, and for example, methyl red, bromocresol purple, bromothymol blue, phenol red and the like are preferable.

The amount of the pH indicator to be added is preferably 0.01 to 40% by weight, more preferably 0.1 to 40% by weight in the detergent composition for a washing machine tub according to claim 1, 2 or 3. 20% by weight. If it is less than 0.01% by weight, it is difficult to confirm a color change. Further, if the amount exceeds 40% by weight, no color change corresponding to an increase in the amount is observed, which is uneconomical.

The washing composition for a washing machine tub of the present invention (the invention according to claims 1 to 4) can further enhance the effect of confirming the bleaching and washing of the indicator by adding a buffering agent for adjusting the pH. Examples of these buffers include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; ammonium hydroxide or amine derivatives such as mono, di, and triethanolamine; sodium carbonate, potassium carbonate and the like. Alkali metal carbonates; alkali metal orthophosphates such as sodium orthophosphate and potassium orthophosphate; alkali metal silicates such as sodium silicate and potassium silicate; silicates such as ammonium silicate. The buffer for adjusting the pH is selected according to the type of peroxide used, and the pH at which the optimum
Used to adjust the amount.

The detergent composition for a washing machine tub according to the present invention may contain a surfactant in order to enhance detergency. Examples of the surfactant include anionic surfactants such as soap, alkyl sulfate, and alkylbenzene sulfonate; and nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, and amine oxide. The amount of these surfactants to be added is preferably 1 to 20% by weight of the detergent composition for a washing machine tub of the present invention.

In addition to the above-mentioned components, the detergent composition for washing machine tubs of the present invention may optionally contain enzymes, sequestering agents, pH adjusters, inorganic salts, antibacterial agents, preservatives, Additives such as fragrances, pigments, dyes and plasticizers can be used.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The embodiments of the present invention will be described below.
This will be described in more detail. (Examples 1 to 3)Example 1 As a peroxide that generates hydrogen peroxide in aqueous solution,
Sodium oxocarbonate (manufactured by Nippon Peroxide Co., Ltd.
Name "PC-M": Na_TwoCO_Three・ 1.5H_TwoO _Two),acid
Succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name
"Ricacid SA"), methyl red as pH indicator
(Manufactured by Nacalai Tesque, Inc.) in the mixing ratio shown in Table 1.
By mixing, a detergent composition was obtained.

Example 2 A cleaning composition was obtained in the same manner as in Example 1 except that glutaric anhydride (manufactured by Shin Nihon Rika) was used as the acid anhydride.

Example 3 A cleaning composition was obtained in the same manner as in Example 1 except that bromocresol purple (manufactured by Nacalai Tesque) was used as a pH indicator. The mixing ratio of these cleaning compositions,
And water p in the washing tub based on the evaluation method described below.
Table 1 shows the evaluation results of H, the degree of washing, the odor, and the color change.

(Examples 4 to 6) Examples 4 and 5 Succinic anhydride (trade name "Licacid S" manufactured by Shin Nippon Rika Co., Ltd.)
A ”) is ground in an agate mortar and then sifted.
Particles having a particle diameter of 0.01 mm to 0.5 mm were selected, and sodium peroxocarbonate (trade name “PC-M”: Na-Peroxide Co., Ltd., Na:
₂ CO ₃ .1.5H ₂ O ₂ ) to obtain a detergent composition.

In the same manner as in Example 6 , particles having a particle diameter of 0.5 mm to 1.0 mm were selected and mixed with sodium peroxocarbonate according to the composition shown in Table 2 to obtain a detergent composition. Table 2 shows the compounding ratios of these detergent compositions, and the evaluation results of the degree of washing in the washing tub and the odor based on the evaluation method described later.

Comparative Examples 1-4 Comparative Example 1 A cleaning composition was obtained in the same manner as in Example 1, except that no peroxide for generating hydrogen peroxide was used in the aqueous solution.

Comparative Example 2 A cleaning composition was obtained in the same manner as in Example 1 except that no acid anhydride was used.

COMPARATIVE EXAMPLE 3 Except that tetraacetylethylenediamine (manufactured by Hoechst Industries) was used as the bleach activator,
A cleaning composition was obtained in the same manner as in Example 1.

Comparative Example 4 A commercially available chlorine bleach was used. Table 1 shows the compounding ratios of these detergent compositions, and the evaluation results of the pH of the water in the washing tub, the degree of cleaning, the odor, and the color change based on the evaluation method described below.

(Comparative Examples 5 and 6) Comparative Example 5 A cleaning composition was prepared in the same manner as in Examples 4 to 6, except that tetraacetylethylenediamine (manufactured by Hoechst Industries) was used instead of succinic anhydride. Obtained.

Comparative Example 6 A cleaning composition was obtained in the same manner as in Examples 4 and 5, except that the mixing ratio was changed. Table 2 shows the mixing ratios of these cleaning compositions, and the evaluation results of the degree of cleaning and the odor.

[0033]

[Table 1]

[Table 2]

(Evaluation Method) Evaluation was performed using a fully automatic washing machine in which black-brown mold and the like adhered to the outer and inner walls of the washing tub. Put 50 liters of water at a water temperature of 15 ° C into the washing tub,
After 200 g of the detergent compositions obtained in Examples and Comparative Examples were charged, the water tank was rotated for 10 seconds to be in a dispersed state and left for 1 hour. Thereafter, the mixture was stirred for 10 minutes, the outer and inner walls of the washing tub of the fully automatic washing machine were disassembled, and the degree of washing was visually observed.
The evaluation of the PH value was performed when the water tank was rotated for 2 minutes to obtain a dispersion state, and the state was allowed to stand for 1 hour.

The evaluation of the degree of cleaning was performed in the following stages. × mark: not removed at all. △ mark: Slightly removed. ○ mark: considerably removed. ◎: Completely removed.

The evaluation of the odor was carried out in the following stages 30 minutes after the start of washing. X: smells very unpleasant. △ mark: Slightly unpleasant odor.印: no odor

The color change was evaluated by visually checking whether the color change was caused by the pH indicator after standing for 1 hour.

[0038]

Since the present invention is constructed as described above, it has no peculiar chlorine odor or organic acid odor, and has a safe and high bleaching cleaning power for use in a washing machine tub. In addition, it has a function to notify the completion of bleach washing by color change,
A very easy-to-use detergent composition for a washing machine tub can be provided.

Claims (4)

[Claims] 1. A cleaning composition for a washing machine tub, comprising a hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution, and an acid anhydride. 2. A detergent composition for a washing machine tub comprising sodium peroxocarbonate and succinic anhydride, wherein the weight ratio of the sodium peroxocarbonate to succinic anhydride is 2/2.
A detergent composition for a washing machine tub, wherein the composition is 3 to 19/1. 3. The particles of succinic anhydride having a particle size of 0.001 m
3. The cleaning composition for a washing machine tub according to claim 2, which has a range of m to 2 mm. 4. The cleaning composition for a washing machine tub according to claim 1, further comprising a PH indicator.