JP2008013611A - Bleaching detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxygen-based bleaching detergent composition that exhibits excellent bleaching and deterging properties. <P>SOLUTION: The bleaching detergent composition comprises a persulfate salt and/or a hydrogen persulfate salt (for example, potassium hydrogen persulfate), a carbonate salt and/or a hydrogen carbonate salt (for example, sodium carbonate) and a solid inorganic acid (for example, sulfamic acid) and optionally a perborate salt (for example, sodium perborate monohydrate). The use of the solid inorganic acid, particularly sulfamic acid, as the acid, enhances solubility and foaming properties compared with the case that an organic acid is used, and gives the bleaching detergent composition exhibiting persistent and enhanced bleaching effects. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a bleaching detergent composition that is suitably used for washing various articles having a hard surface, in particular, bleaching and washing organic stains, molds, bacteria, and the like deposited on the bottom of a container.

  Bleaching detergents are used to remove soils such as mold, calcium phosphate and other inorganic substances and proteins generated in toilets, drain pipes, bathrooms, baths and the like. Bleach cleaning agents can be roughly classified into chlorine and oxygen. Chlorine bleaching detergents contain sodium hypochlorite, sodium chlorcyanurate, etc. as bleaching components, and have a stronger bleaching, washing, and mold removal effect than oxygen bleaching detergents. However, chlorinated bleach cleaners generate a specific unpleasant odor, that is, a chlorine odor, and generate harmful chlorine gas when mixed with acidic substances. There is a need for improvement.

On the other hand, oxygen bleach detergents contain inorganic peroxides (persulfates, hydrogen persulfates, perborates, percarbonates, percarbonates, etc.) as bleaching components. The effect, especially the bleaching effect at low temperatures, does not reach the chlorine bleach detergent. Therefore, it has been studied to add a bleach activator (tetraacetylethylenediamine, pentaacetylglucose, nonanoyloxybenzenesulfonic acid, decanoyloxybenzoic acid, etc.) for the purpose of enhancing the bleaching effect (for example, patents) Reference 1 and 2). In the field of solid detergents, studies have also been made on controlling the solubility and foamability of solid agents in order to improve the cleaning effect (see, for example, Patent Document 3).
JP 05-287298 A Japanese Patent Laid-Open No. 08-269494 JP 07-109499 A

  Therefore, an object of the present invention is to provide a bleaching detergent composition excellent in bleaching and detergency.

  As a result of intensive studies in view of the problems of the prior art, the present inventors contain persulfate and / or hydrogen persulfate, carbonate and / or hydrogen carbonate, and a solid inorganic acid, In bleach detergent compositions optionally containing perborate, the use of solid inorganic acids as acids, especially sulfamic acid, makes the composition more soluble and foaming than when organic acids are used. The present invention has been completed by finding that the property is improved and the bleaching effect is enhanced. The enhancement effect of the bleaching effect does not depend on foaming alone. This is because the present inventors have confirmed that the bleaching action of the solution after completion of foaming that is not affected by foaming is also enhanced. Therefore, according to the present invention, the bleaching action is enhanced not only by the foaming action resulting from the use of sulfamic acid but also by some factor other than foaming.

That is, the present invention provides the following composition.
Item 1. A bleaching detergent composition comprising a persulfate and / or a hydrogen persulfate, a carbonate and / or a hydrogen carbonate, and a solid inorganic acid, optionally containing a perborate.
Item 2. Item 2. The composition according to Item 1, wherein the solid inorganic acid is sulfamic acid.
Item 3. Item 3. The composition according to Item 1 or 2, wherein the composition is a tablet.
Item 4. Item 4. The composition according to any one of Items 1 to 3, which contains a perborate.
Item 5. Item 4. The composition according to any one of Items 1 to 3, wherein the perborate-containing weight is 0 to 1.5 when the sum of the persulfate-containing weight and the hydrogen persulfate-containing weight is 1.
Item 6. Item 6. The composition according to any one of Items 1 to 5, wherein the hydrogen persulfate is potassium hydrogen persulfate.
Item 7. Item 7. The composition according to any one of Items 1 to 6, wherein the perborate is sodium perborate.
Item 8. Item 8. The composition according to any one of Items 1 to 7, wherein the carbonate is sodium carbonate.

  The present invention contains persulfate and / or hydrogen persulfate, carbonate and / or hydrogen carbonate, and solid inorganic acid as essential components, and optionally contains perborate. Persulfates, hydrogen persulfates (peroxohydrogensulfates) and perborates (peroxyborate) are used as oxygen-based bleaching components in the bleaching field. In the composition of the present invention, the total content of the three salts is preferably 1 to 60% by weight, more preferably 5 to 50% by weight, and most preferably 10 to 35% by weight. Is the amount. When the present invention does not contain perborate, the sum of persulfate and hydrogen persulfate applies to the above range.

  Since perborate has a low dissolution rate, it is easy to control the solubility of the composition and to maintain the bleaching effect for a long time by blending it. Therefore, in the present invention, it is preferable to use a perborate in combination with persulfate and / or hydrogen persulfate, that is, a composition containing both salts. When the present invention contains a perborate, the perborate content is preferably the perborate-containing weight when the sum of the persulfate-containing weight and the hydrogen persulfate-containing weight is 1. Is an amount that results in ˜1.5, more preferably 0 to 1.1, even more preferably 0.3 to 1.1, and most preferably 0.3 to 0.8. In these ranges, the bleaching action is particularly high. Further, when the perborate content is within these ranges, it is advantageous in terms of moldability and shape retention, particularly in that the tablet can be easily formed and the tablet has an appropriate hardness.

  Persulfate and hydrogen persulfate can be used alone or in combination of two or more. Specific examples of the persulfate include potassium persulfate, sodium persulfate, and ammonium persulfate. Specific examples of the hydrogen persulfate include sodium hydrogen persulfate, potassium hydrogen persulfate, and ammonium hydrogen persulfate. Among the persulfates and hydrogen persulfates, potassium persulfate and potassium hydrogen persulfate are preferable, and potassium persulfate is more preferable. Potassium salts are superior to other salts in terms of solubility, and are also superior to ammonium salts in terms of color tone and odor. Furthermore, potassium hydrogen persulfate is superior to potassium persulfate in terms of stability as a raw material and stability in the composition.

Perborate can be used alone or in combination of two or more. Specific examples of the perborate include sodium perborate, ammonium perborate, potassium perborate, and hydrates thereof. Preferred perborate salts are sodium perborate tetrahydrate (NaBO ₃ · 4H ₂ O), sodium perborate monohydrate (NaBO ₃ · 1H ₂ O), and more preferred is perborate. Sodium monohydrate. Since sodium perborate monohydrate has less water content than tetrahydrate, it has four advantages in terms of stability as a raw material, stability of a composition containing this, and moldability when molding the composition. Superior to hydrates.

  The present invention contains carbonate and / or bicarbonate in addition to persulfate and / or hydrogen sulfate. The content of carbonate and / or bicarbonate in the composition of the present invention is preferably 5 to 50% by weight, more preferably 15 to 35% by weight. The carbonate and / or bicarbonate can be used singly or in combination of two or more. By blending carbonate and / or bicarbonate, the product of the present invention can be dissolved while the carbonate and / or bicarbonate reacts with the acid to generate carbon dioxide and foam well. Specific examples of the carbonate and bicarbonate include sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and the like, and sodium carbonate and sodium bicarbonate are preferable. In particular, sodium carbonate is most preferable because it can easily make the solution liquid alkaline even in a small amount, so that the bleaching effect is enhanced, it is easily available, and it is inexpensive.

  The present invention further contains a solid inorganic acid. Here, the solid means a solid at room temperature. Since the acid reacts with the carbonate and / or bicarbonate to generate carbon dioxide when the product of the present invention is put into water, the present invention has foaming properties. Since the water is agitated by foaming, the cleaning efficiency is improved. The solid inorganic acid content in the composition of the present invention is preferably 5 to 40% by weight, more preferably 10 to 25% by weight. The solid inorganic acid can be used alone or in combination of two or more. Specific examples of the solid inorganic acid include sulfamic acid. Sulfamic acid has not only strong foaming properties but also improved bleaching properties compared to organic acids. Here, although the improvement of bleaching property may be attributed to foaming, the present inventors have confirmed that not only foaming but also some other action by sulfamic acid is made in Examples and the like described later.

  In the present invention, in addition to the above-described persulfate, hydrogen persulfate, perborate, carbonate, bicarbonate, solid inorganic acid, bleach activator (for example, tetraacetylethylenediamine, pentaacetylglucose, Nonanoyloxybenzenesulfonic acid, decanoyloxybenzoic acid, etc.), weight adjusting agent (eg, sodium sulfate, magnesium sulfate, calcium sulfate, calcium chloride, magnesium chloride, etc.), binder (eg, polyethylene glycol (especially having a molecular weight of 4000 to 10,000). Preferred), polyoxyethylene stearyl ether, polyvinyl pyrrolidone, etc.), sugars (eg starch, glucose, fructose, maltose, lactose etc.), sugar alcohols (eg sorbitol, maltitol, erythritol etc.), celluloses (eg Carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, etc.)), lubricants (eg, stearates (eg, sodium stearate, magnesium stearate, calcium stearate, etc.), talc, paraffin wax, etc.), perfumes, coloring agents, etc. It is preferable to add.

  Further, in the present invention, components other than those usually used in the bleaching detergent can be blended as long as the effects of the present invention are not impaired. Such components include excipients (eg, sodium sulfate, sodium chloride, calcium sulfate, magnesium sulfate, etc.), abrasives (eg, calcium carbonate, aluminum oxide, etc.), other non-chlorine bleaching components (eg, sodium percarbonate) , Thiourea dioxide, sodium perphosphate, etc.), organic acids (eg, citric acid, malic acid, fumaric acid, succinic acid, tartaric acid, etc.), bactericides (eg, quaternary ammonium salts (eg, benzalkonium chloride, etc.)) ), Metal chelating agents (eg diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid salt, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid salt, hydroxyethylethylenediaminetriacetic acid, hydroxyethylethylenediaminetriacetic acid salt, glycol etherdiamine tetraacetic acid, glycol etherdiamine tetraacetic acid salt) , Nito (B) triacetic acid, nitrilotriacetate, etc.), surfactant (eg, α-olefin sulfonate, alkyl sulfate, alkylbenzene sulfonate, polyoxyethylene alkyl ether, etc.), disintegrant (eg, agar, gelatin, corn starch, Crystal cellulose and the like) and cleaning enzymes (eg, protease, lipase, amylase, cellulase, etc.).

  The composition of the present invention can be produced by a method generally used in the field of solid bleaching agents, cleaning agents, and bleaching cleaners. Usually, powders or granules of each component are mixed and formed into a desired shape by means of granulation, tableting, kneading extrusion molding or the like. At this time, if necessary, a binder, a lubricant, and the like can be blended and molded. When washing or bleaching the bottom of toilet bowls, water tanks, etc., when the bleaching detergent sinks to the bottom when it is poured into water, the bottom is efficiently washed and removed by foaming and dissolution of the bleaching detergent. Since bleaching can be performed, the bleaching detergent composition of the present invention preferably has a specific gravity of 1 or more. In the case of a composition having such a specific gravity, it is preferable to add a weight adjusting agent such as sodium sulfate, magnesium sulfate, calcium sulfate, or other sulfates, calcium chloride, magnesium chloride, etc. As long as it has an effect of adjusting the specific gravity as long as it is not inhibited, it is not particularly limited thereto.

  The form of the composition of the present invention can be appropriately changed according to the use, purpose and the like. Examples thereof include powders, fine granules, tablets (including tablets), block agents, and the like. Considering handling, fine granules, tablets and block agents are preferable, and tablets are particularly preferable.

  The composition of the present invention is useful for washing and bleaching dirt (such as mold darkening due to mold, yellowing due to protein, urine, and slimming) adhering to a hard surface. For example, it can be used for cleaning and bleaching dirt such as toilets, water tanks, drain pipes, bathrooms, bath tubs, tableware, water bottles, pots, washstands, vases, and washing tubs. The method of use and the amount of use of the composition of the present invention can be appropriately set according to the application, purpose and the like. For example, when it is used for a general toilet having a puddle, it is preferable to use about 10 to 50 g of the composition of the present invention. Moreover, when using it for the storage tank of a flush toilet, it is preferable to use it as an in-tank bleach cleaning agent, and to use about 5-25g of compositions of this invention with respect to 1L of water of a storage tank.

  Since the composition of the present invention usually has a structure in which an object to be washed by bleaching (for example, a toilet bowl) stores water, it may be added to the water stored in the object one or more times. Moreover, when using for the bleach washing | cleaning target object which does not store water, it is also possible to add water after throwing the composition of this invention into a bleach cleaning target object. Since the composition of the present invention is excellent in foaming properties, the effect can be obtained even in a short time for bleaching and washing, but since the bleaching and washing effect is improved or sustained even after the foaming is completed, the bleaching and washing time is longer. It is effective. A preferred bleaching and washing time is 2 minutes to 72 hours, more preferably 10 minutes to 24 hours, after the composition of the present invention is contacted with water. Usually, after bleaching and washing, if necessary, water is poured to remove the dirt.

  The present invention is more excellent in foaming and bleaching properties than an oxygen bleaching detergent containing an organic acid. In particular, since the present invention is also excellent in comparing the bleachability after the completion of foaming, the bleachability of the present invention is due to the improvement of the bleaching efficiency due to the improvement of the foamability (that is, the bleachability depending on foaming). Not only that, the bleaching property is exhibited by some other action.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention in detail, this invention is not limited to these.

  In Examples, Comparative Examples and Formulation Examples, Oxone (made by DuPont; containing 43% by weight of potassium hydrogen persulfate) as potassium hydrogen persulfate, and Perbon (Mitsubishi Gas Chemical Co., Ltd .; sodium perborate monohydrate) as sodium perborate. 93% by weight of Japanese product) was used. Moreover, sodium dichloroisocyanurate (trade name Highlight 60S, manufactured by Nissan Chemical Co., Ltd., containing 98% by weight of sodium dichloroisocyanurate) was used as a chlorine-based bleaching component.

  In addition, the usage-amount of the said component shown by the following table | surface is the compounding quantity as said product, and the compounding quantity of an active ingredient (potassium hydrogen persulfate, sodium perborate monohydrate, sodium dichloroisocyanurate). is not.

  Further, in the following Examples, Comparative Examples and Formulation Examples, tests were conducted by the following production methods and measurement methods unless otherwise specified.

Manufacture of tablets Each powdered bleach (Oxone, Perbon, Highlight 60S, etc. ), solid acid (sulfamic acid, citric acid, malic acid, fumaric acid, succinic acid), carbonate (sodium carbonate, etc. ), weight adjustment Add a certain amount of agent (sodium sulfate (sodium sulfate), etc.), binder (polyethylene glycol 6000P, etc. ), and other ingredients as required, and put 25 g into a cylindrical tool (Fig. 1). The upper punch was pressed down at 900 kg / cm ² ) to make tablets. The tablet has a diameter of about 4 cm, a height of about 1.5 cm, and a shape in which the center of the upper surface is depressed (FIG. 2).

Measurement of bleaching rate 2 L of tap water is put into a 2 L beaker and maintained at 15 ° C. (height from the bottom surface to the water surface is about 15 cm). Three pieces of 3 cm square tea-stained cloth (EMPA167, manufactured by Nippon Materials) are prepared, and each color difference is measured with a color difference meter (CR-300, manufactured by MINOLTA). Prepare three pieces of black-stained tea cloth with a color difference measured at the end of the yarn, and pinch the other end of the yarn to place the tea-stained fabric in water. The cloth is placed about 1 cm above the bottom of the container and close to the container wall, that is, where the influence of foam generated by the test substance is small. The line connecting the cloths is an equilateral triangle. Into this beaker, 1 test substance (25 g tablet or 25 g of non-molded powder mixture) is placed so that it is located in the center of the bottom, left for 30 minutes, and then the tea-stained cloth is taken out and rinsed with tap water. This tea-stained cloth is dried for 30 minutes in a blown low-temperature dryer (50 ° C.). After 30 minutes, the fabric is removed from the dryer and the color difference of each fabric is measured. The obtained color difference (CD _n ) and the color difference (CD ₀ ) of the tea-stained cloth before the test are applied to the following calculation formula to calculate the bleaching rate of each cloth.

Bleaching rate (%) = 100 × (CD ₀ −CD _n ) / CD ₀
The bleaching rate shown in the following table is a value obtained by adding the bleaching rates of the respective fabrics and dividing the sum by the number of the fabrics, that is, an average value of the bleaching rates of the three tea-stained fabrics. Hereinafter, when expressed as a bleaching rate, the average value of the aforementioned bleaching rate is shown. The “relative bleaching degree” refers to the relative bleaching rate of each test substance when the bleaching rate of the chlorine bleach is set to 100.

Measurement of the bleaching rate after complete dissolution The measurement is carried out with a more diluted solution than in the case of measuring the bleaching rate described above. That is, 6 L of tap water is put into a 10 L container and maintained at 15 ° C. (height from the bottom surface to the water surface is about 12 cm). As in the measurement of the bleaching rate, three tea-stained cloths are placed in water, and one test substance (25 g tablet or 25 g non-molded powder mixture) is added. The time when the test substance is completely dissolved is set to 0 minute, the cloth is taken out after a predetermined time, and the color difference is measured in the same manner as in the case of measuring the bleaching rate to calculate the bleaching rate.

Measurement of pH The pH is measured in parallel with the measurement of the bleaching rate. The pH when the test substance is completely dissolved is measured with a pH meter (D-52, manufactured by Horiba). In the field of oxygen bleaching agents, the pH at which the bleaching effect is maximized differs depending on the type of soil to be bleached, but it is generally known that the higher the pH, the higher the bleaching power.

Measurement of dissolution time In parallel with the measurement of the bleaching rate, the time until the test substance is completely dissolved is measured in increments of 5 seconds.

Examples and Comparative Examples
Test 1
Tablets were produced with the composition shown in Table 1, and the bleaching rate, pH and dissolution time were measured.

  When the perborate content relative to the sum of the persulfate content and the hydrogen persulfate content is between 0 (A1) and 1.1 (A5), the same bleaching power as the chlorine bleach (B2) is obtained. It was confirmed that In the test of B3, the test substance was not completely dissolved after 30 minutes, and about 2-3% remained undissolved.

Test 2
Tablets were produced with the composition shown in Table 2, and the bleaching rate, pH and dissolution time were measured. The dissolution concentrations of A3 and B2 are the dissolution concentrations (25 g / 2L) according to the above measurement of the bleaching rate, but the dissolution concentrations of A11 to A13 are 25 g / 4 L, 25 g / 1 L and 25 g / 0.67 L, respectively. It is.

  A11 to A13 showed a good bleaching rate even when the dissolution concentration was changed, and the pH was not greatly lowered.

Test 3
Tablets were produced with the compositions shown in Table 3, and the bleaching rate, pH and dissolution time were measured. The amount of acid in B4 to B7 was such that the pH of the solution in which the tablet was dissolved was approximately 9.1.

  In this test, it was shown that the product of the present invention has a higher bleaching rate than the organic acid compounded product under the conditions of the same pH at the time of dissolution and the same amount of the compound.

Test 4
Tablets were produced with the compositions shown in Table 4, and the dissolution time and the bleaching rate after complete dissolution were measured. The dissolution concentration is 25 g / 6L.

  Since the bleaching rate of the organic acid-containing composition (B6) was about 70% after 180 minutes and after 240 minutes, the maximum bleaching rate was about 70%. In contrast, since the bleaching rate of the composition of the present invention containing sulfamic acid was 85.1% after 240 minutes, the maximum bleaching rate was at least 85.1%. It was also expected that the composition of the present invention showed a higher bleaching rate when the bleaching rate was measured later than 240 minutes later. In addition, when B4, B5, B7 to B11 tablets were used and tested under the same conditions, the same tendency as B6 was confirmed, indicating that the maximum bleaching rate of A3 is superior to these test substances. It was.

  Therefore, the composition of the present invention was superior to the organic acid-containing composition in the method of leaving the tablet after it was put in, that is, the bleaching washing action by so-called leaving. In addition, since the composition of this invention has a foaming power stronger than an organic acid containing composition, it is superior to an organic acid containing composition also in the bleaching detergency of the initial stage of input.

  In this test, since the bleaching rate is measured after the tablet is completely dissolved, the bleaching improvement effect obtained by the water stirring phenomenon due to foaming does not contribute to the measured bleaching rate. Therefore, it was confirmed by this test that sulfamic acid has some action other than the foaming action in bleaching, and exerts a bleaching power superior to that of organic acid by this action.

Test 5
Tablets were produced with the compositions shown in Table 5. Using these tablets in the puddle part of a flush toilet (C730, manufactured by TOTO) that is actually used in a general household (family of four) and has not been cleaned for 2 months, The bleaching detergency against side dirt was evaluated. Evaluation is allowed to stand for 2 hours after charging the tablet, visually confirming the degree of soil removal after flowing water once and the presence or absence of remaining dirt, and then visually confirming the presence or absence of dirt remaining after flowing water once. In the same manner, it was performed by visually confirming the presence or absence of dirt after flowing water once. The evaluation criteria are as follows.

<Degree of stain removal by one washing>
◎: More than 80% of dirt is removed ○: More than 50% of dirt is less than 80% △: More than 30% of dirt is removed ×: Less than 30% of dirt is removed < Presence or absence of dirt>
◎: Dirt was almost removed by washing once ○: Dirt was almost removed by washing twice △: Dirt was almost removed by washing 3 times ×: Dirt was hardly removed by washing 3 times The

  From this test, it was confirmed that the bleaching detergency of the present invention was higher than that of the organic acid-containing bleaching detergency even in actual use. The present invention was particularly strong against draft stains in comparison with organic acid-containing bleach cleaners.

Formulation Example A bleaching detergent composition in the form of a tablet having the composition shown in Table 6 was prepared in the same manner as in Examples.

  The present invention is useful in the field of bleach detergents.

FIG. 1 shows a schematic cross-sectional view of a tool used when producing tablets in Examples, Comparative Examples and Formulation Examples. FIG. 2 shows a photograph of a tablet produced as A1 in the examples.

Claims (8)

A bleaching detergent composition comprising a persulfate and / or a hydrogen persulfate, a carbonate and / or a hydrogen carbonate, and a solid inorganic acid, optionally containing a perborate. The composition according to claim 1, wherein the solid inorganic acid is sulfamic acid. The composition according to claim 1 or 2, wherein the composition is in the form of a tablet. The composition according to any one of claims 1 to 3, comprising a perborate. The composition according to any one of claims 1 to 3, wherein the perborate-containing weight is 0 to 1.5 when the sum of the persulfate-containing weight and the hydrogen persulfate-containing weight is 1. The composition according to claim 1, wherein the hydrogen persulfate is potassium hydrogen persulfate. The composition according to any one of claims 1 to 6, wherein the perborate is sodium perborate. The composition according to any one of claims 1 to 7, wherein the carbonate is sodium carbonate.

Images