JP5243007B2 - Colored oxidant composition - Google Patents

Description

  The present invention relates to a colored oxidizer composition suitably used for a bleaching agent, a cleaning agent, a deodorant, a bactericidal disinfectant and the like.

  Halogen-based oxidants and oxygen-based oxidants (hereinafter sometimes referred to as oxidants) are used for bleach cleaning by oxidative decomposition of soil, deodorization and disease that prevents the generation of bad odor by preventing soil rot. It has functions such as sterilization and sterilization of bacteria and viruses that cause food poisoning, bleaching agent for washing, kitchen, dwelling, toilet, bath, cleaning agent, deodorant, sterilizing and disinfecting It is widely used as an active ingredient such as an agent.

  At that time, these drugs are colored by blending colorants such as pigments and dyes so that the application site can be easily visually recognized, or for the purpose of enhancing the texture of the product or obtaining a comfortable feeling of use. It is requested to do. However, since generally used colorants are inferior in oxidation resistance, when mixed with an oxidant or when the mixture is dissolved in water, the colorant reacts with the oxidant. Discoloration, discoloration, or decoloration has occurred, and there has been a problem that the coloring of chemicals such as bleaching agents, cleaning agents, deodorizing agents, and disinfecting disinfectants cannot be performed stably.

  For example, Patent Literature 1 and Patent Literature 2 propose an aqueous sodium hypochlorite solution containing copper phthalocyanine or ultramarine blue as a pigment, but have not yet achieved satisfactory coloring stability.

Japanese Patent Laid-Open No. 53-8604 JP 54-88889 A

  An object of the present invention is to provide a colored oxidant composition that is excellent in stability during storage and that can stably color an aqueous solution obtained when used by diluting or dissolving in water. .

As a result of intensive studies and studies to solve the above-mentioned problems, the present inventors have used the pigments represented by the chemical formulas (I) to (V) of Chemical Formulas 1 to 5 to achieve the intended result. The inventors have found that the object can be achieved and have completed the present invention.
That is, the present invention includes a halogen-based oxidizing agent or an oxygen-based oxidizing agent (excluding sodium percarbonate) and chemical formulas (I), (II), (III), (IV) ) Or a pigment represented by the chemical formula (V) and a surfactant.

  The colored oxidant composition of the present invention was able to stably maintain its coloring performance and oxidation performance even when stored for a long period of time, and was obtained even when diluted or dissolved in water during use. The coloring of the aqueous solution can be stably maintained for a long time. And when used for bleaching agents, cleaning agents, deodorants, disinfectants, etc., the application site can be easily seen, the texture of the product can be enhanced, and a comfortable feeling of use can be obtained. Therefore, it is suitable for washing, kitchen use, dwelling use, toilet use, bath use and the like.

  Typical halogen-based oxidizing agents used in the practice of the present invention include hypochlorites such as sodium hypochlorite and calcium hypochlorite, chlorinated isocyanuric acids such as sodium dichloroisocyanurate and trichloroisocyanuric acid. Halogenated hydantoins such as 1,3-dichloro-5,5-dimethylhydantoin, 1-bromo-3-chloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, etc. It is done.

Similarly, oxygen-based oxidizing agents other than sodium percarbonate include alkali metal persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, sodium hydrogen persulfate, potassium hydrogen persulfate, sodium perborate, perborate. Examples thereof include perborates such as calcium, hydrogen peroxide solution , and peracetic acid.

The pigment used in the practice of the present invention is a pigment represented by the chemical formulas (I) to (V).
CAS registration number and color index (Color) of the pigment represented by chemical formula (I)
Index, hereinafter CI or C.I. I. Is abbreviated as follows). Hereinafter, this pigment is abbreviated as “R-22”.
[CAS registration number]
・ 6448-95-9
[Color index (CI number, CI name)]
・ CI 12315
・ CI Pigment Red 22

The CAS registration number and color index of the pigment represented by the chemical formula (II) are as follows. Hereinafter, this pigment is abbreviated as “R-112”.
[CAS registration number]
・ 6535-46-2
[Color index (CI number, CI name)]
・ CI 12370
・ CI Pigment Red 112

The CAS registration number and color index of the pigment represented by the chemical formula (III) are as follows. Hereinafter, this pigment is abbreviated as “R-146”.
[CAS registration number]
・ 5280-68-2
[Color index (CI number, CI name)]
・ CI 12485
・ CI Pigment Red 146

The CAS registration number and color index of the pigment represented by the chemical formula (IV) are as follows. Hereinafter, this pigment is abbreviated as “Y-14”.
[CAS registration number]
・ 5468-75-7
[Color index (CI number, CI name)]
・ CI 21095
・ CI Pigment Yellow 14

The CAS registration number and color index of the pigment represented by the chemical formula (V) are as follows. Hereinafter, this pigment is abbreviated as “Y-83”.
[CAS registration number]
・ 5567-15-7
[Color index (CI number, CI name)]
・ CI 21108
・ CI Pigment Yellow 83

  These pigments can be used alone or in combination. Further, the content of the pigment blended in the colored oxidant composition of the present invention is not particularly limited, but a ratio of 0.001 to 20% by weight is preferable.

Examples of the surfactant used in the practice of the present invention include anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants, which are excellent in stability against oxidizing agents. In view of this, an anionic surfactant or a nonionic surfactant is preferred.
Examples of the anionic surfactants include alkyl sulfates, alkyl sulfate esters, olefin sulfonates, fatty acid salts, α-sulfo fatty acid salts, and the like. Sulfate is preferred.
Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyethylene glycols, sucrose fatty acid esters, etc., but polyoxyethylene alkyls are more stable against oxidizing agents. Ether is preferred.
These surfactants can be used alone or in combination.

These surfactants are used to disperse the pigment. That is, when the colored oxidant composition of the present invention is dissolved in water, the water can be colored by uniformly dispersing the water-insoluble pigment in the water. In addition, the use of a surfactant can enhance the cleaning effect.
The content of the surfactant blended in the colored oxidant composition of the present invention is not particularly limited, but a ratio of 0.05 to 20% by weight is preferable.

  The colored oxidant composition of the present invention is prepared by mixing the halogen-based oxidant or oxygen-based oxidant, the pigment represented by the chemical formulas (I) to (V), and a surfactant by a conventional method. Can be manufactured.

  The form of the colored oxidant composition of the present invention is liquid or solid. In the case of a solid, it can be formed into a molded product such as powder, granule, briquette or tablet.

  In the case of forming a molded product, it is possible to employ a method in which a powdery or granular raw material is pressed using a mortar. Or the method of mix | blending the raw material made into the paste form by mix | blending a fluidizing agent, press-cutting to arbitrary length, and shape | molding in a rod shape is employable.

  In the colored oxidant composition of the present invention, a foaming agent, an inorganic salt, a thickening polysaccharide and the like can be blended in order to adjust the dissolution rate.

The component of the foaming agent is not particularly limited as long as it generates carbon dioxide when contacted with water, but it is preferable to use a combination of carbonate and organic acid.
Examples of the carbonate include sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, sodium sesquicarbonate, sodium percarbonate and the like.
Examples of the organic acid include citric acid, tartaric acid, ascorbic acid, malic acid, fumaric acid, succinic acid, malonic acid, adipic acid, oxalic acid, and lactic acid.
These carbonates and organic acids can be used alone or in combination of two or more.

Examples of the inorganic salt include sodium sulfate, potassium sulfate, magnesium sulfate, and sodium chloride.
Examples of the thickening polysaccharide include carrageenan, guar gum, locust bean gum, alginic acid, alkali metal salt of alginic acid, carboxymethyl cellulose, alkali metal salt of carboxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these. In addition, the raw material and evaluation test method which were used in the Example and the comparative example are as follows.

[Oxidant]
・ Sodium dichloroisocyanurate: “SDIC-MG” manufactured by Shikoku Kasei Kogyo Co., Ltd.
・ Trichloroisocyanuric acid: “TICA-G” manufactured by Shikoku Kasei Kogyo Co., Ltd.
・ 1,3-Dichloro-5,5-dimethylhydantoin: “Dant Brom RW” manufactured by Lonza
1-Bromo-3-chloro-5,5-dimethylhydantoin: “Dantcroa RW” manufactured by Lonza
-Sodium hypochlorite aqueous solution: Reagent manufactured by Wako Pure Chemical Industries, specification value of 5% or more (actual measurement value of about 10%)
・ Calcium hypochlorite: Reagent manufactured by Wako Pure Chemical Industries, Ltd. ・ Potassium monohydrogen persulfate double salt: “Oxone ” manufactured by DuPont

[Colorant]
R-22 (pigment): “Scarlet G Conch” manufactured by Dainichi Seika Kogyo Co., Ltd.
R-112 (pigment): “Permanent Red GY” manufactured by Dainichi Seika Kogyo Co., Ltd.
R-146 (pigment): “Seika First Carmine 3870” manufactured by Dainichi Seika Kogyo Co., Ltd.
Y-14 (pigment): “Seika First Yellow 2200” manufactured by Dainichi Seika Kogyo Co., Ltd.
Y-83 (pigment): “Seika First Yellow 2700 (B)” manufactured by Dainichi Seika Kogyo Co., Ltd.
Acid Blue 9 (dye): Reagent manufactured by Tokyo Chemical Industry Co., Ltd. Direct Yellow 12 (dye): Reagent manufactured by Tokyo Chemical Industry Co., Ltd. Phthalocyanine blue (pigment): Reagent manufactured by Wako Pure Chemical Industries, Ltd. Ultramarine blue (pigment): Reagents manufactured by Hayashi Junyaku Kogyo Co., Ltd. (Note) Acid Blue 9, Direct Yellow 12, and phthalocyanine blue are dyes or pigments represented by the following chemical formulas (VI) to (VIII), respectively. Ultramarine blue is a silica-alumina based inorganic pigment.

[Surfactant]
・ Sodium lauryl sulfate: “Sinoline 90TK-N” manufactured by Shin Nippon Chemical Co., Ltd.
・ Polyoxyethylene alkyl ether: “DKS NL600P” manufactured by Daiichi Industry Co., Ltd.

[Solution modifier]
・ Succinic acid: Takeda Pharmaceutical Co., Ltd. ・ Fumaric acid: Kawasaki Kasei Kogyo Co., Ltd. ・ Sodium carbonate: Tokuyama Co., Ltd. ・ Sodium bicarbonate: Tokuyama Co., Ltd.
・ Sodium linear dodecylbenzenesulfonate: reagent manufactured by Tokyo Chemical Industry Co., Ltd. ・ 1-decanol: reagent manufactured by Wako Pure Chemical Industries, Ltd.

[Evaluation test]
The stability of the colored oxidant compositions prepared in Examples and Comparative Examples was evaluated from both aspects of coloring performance and oxidation performance. The test method is as follows. The dissolution described below includes the case of dilution.

(A) Stability of coloring performance when a colored oxidizer composition is dissolved in water (assuming use)
A sample solution was prepared by dissolving a predetermined amount of the sample in water to adjust the pigment concentration to about 10 ppm. For these sample liquids, the absorbance immediately after preparation and the absorbance after standing still for 72 hours at room temperature were measured using an ultraviolet-visible spectrophotometer, and the rate of decrease in absorbance after standing still sealed for 72 hours from these values (%) Was calculated to evaluate the color stability. It is determined that the smaller the numerical value, the less the sample fading and the better the coloring stability.
The wavelengths used for measuring the absorbance are as follows.
・ R-22: 560 nm
・ R-112: 570 nm
・ R-146: 560 nm
Y-14: 490 nm
・ Y-83: 450nm
・ Acid Blue 9: 630nm
・ Direct yellow 12: 420nm
・ Phthalocyanine blue: 720nm
・ Ultramarine blue: 700nm

(B) Stability of oxidation performance when the colored oxidant composition is dissolved in water (assuming use)
A sample solution was prepared by dissolving 1 g of a sample in 1000 ml of water. For these sample solutions, the active halogen concentration or active oxygen concentration (Note 1) in the sample solution was measured immediately after preparation and after standing still for 72 hours at room temperature, and the active halogen concentration or activity after standing for 72 hours from these values. The rate of decrease in oxygen concentration (%) was calculated to evaluate the stability of oxidation performance. It is determined that the smaller the value, the better the oxidation performance stability.
(Note 1) The active chlorine concentration or active oxygen concentration contained in the sample solution was measured as the effective chlorine concentration converted to chlorine by the hypo method. That is, after adding potassium iodide to the sample solution, acetic acid is added to make the solution acidic to liberate iodine from potassium iodide, and this is titrated with sodium thiosulfate, which is effective from the consumption of sodium thiosulfate. Chlorine concentration was calculated.

(C) Stability of coloring performance when the colored oxidizer composition is heated and humidified (assuming storage)
First, a predetermined amount of a sample before heating and humidification was measured, and the absorbance was measured in the same manner as in the above (A).
Subsequently, the sample was put in a polyethylene bag, sealed, stored in a thermostatic chamber controlled at 40 ° C./75% RH, and heated and humidified for 30 days. Thereafter, the absorbance of the sample taken out from the constant temperature and humidity chamber was measured in the same manner as before heating and humidification.
From these absorbance values, the rate of decrease in absorbance before and after warming and humidification was calculated to evaluate the stability of the coloring performance. It is determined that the smaller the numerical value, the less the color fading and the better the coloring performance.

(D) Stability of oxidation performance when the colored oxidizer composition is heated and humidified (assuming storage)
First, the content ratio (Note 2) of active halogen or active oxygen contained in a sample before performing warming and humidification was measured.
Next, the sample was heated and humidified in the same manner as in (C). After that, the content ratio of the active halogen or active oxygen contained in the sample taken out from the constant temperature and humidity chamber is measured in the same manner as before heating and humidification, and the content of the active halogen or active oxygen after warming and humidification is determined from those values. The reduction rate (%) of the ratio (Note 2) was calculated to evaluate the stability of oxidation performance. It is determined that the smaller the value, the better the oxidation performance stability.
(Note 2) Measurement of content ratio of active halogen or active oxygen contained in sample The content ratio of active halogen or active oxygen contained in the sample was measured as an effective chlorine content ratio converted to chlorine by the hypo method. That is, after putting a sample in water and adding potassium iodide, acetic acid is added to make the solution acidic to liberate iodine from potassium iodide, and this is titrated with sodium thiosulfate to consume sodium thiosulfate. From the above, the effective chlorine content was calculated.

[Example 1]
Sodium dichloroisocyanurate, R-22 and sodium lauryl sulfate were mixed to prepare a colored oxidizer composition having the composition shown in Table 1, and an evaluation test was performed. The test results obtained were as shown in Table 1.

[Examples 2 to 13 and Comparative Examples 1 to 4]
In the same manner as in Example 1, a colored oxidant composition having the composition shown in Table 1 was prepared, and an evaluation test was performed. The test results obtained were as shown in Table 1.

[Example 14 ]
A colored oxidizer composition 5 g prepared in Example 13 was filled in a mortar having a diameter of 20 mm and pressed at a surface pressure of 1.2 t / cm ² to prepare a molded product.
When the obtained molded product was subjected to an evaluation test, these test results were as shown in Table 1.

Example 15
A colored oxidant composition having the composition shown in Table 1 was prepared and pressure-extruded using a single screw extruder to produce a molded product having a diameter of 30 mm and a thickness of 10 mm.
When the obtained molded product was subjected to an evaluation test, these test results were as shown in Table 1.

[Comparative Examples 5-6]
A colored oxidant composition having the composition described in Table 1 was prepared, and a molded product was produced in the same manner as in Example 14, and an evaluation test was performed. The test results obtained were as shown in Table 1.

[Comparative Examples 7-8]
A colored oxidant composition having the composition described in Table 1 was prepared, and a molded product was produced in the same manner as in Example 15 and then an evaluation test was performed. The test results obtained were as shown in Table 1.

  According to the test results in Table 1, all the pigments used in the examples have excellent stability against the oxidizing agent, and can withstand long-term storage even when mixed with the oxidizing agent. It is accepted.

Example 16
One molded product prepared in Example 14 was dissolved in 15 liters of water to prepare a pale yellow bleach washing solution (effective chlorine concentration: about 70 ppm). When a ceramic cup with tea astringent adhered to this bleaching washing solution was immersed for 1 hour, the tea astringent was completely removed and a good bleaching washing effect was observed.

[Example 17 ]
After immersing the horse blood-contaminated cloth in the bleaching washing solution prepared in Example 16 for 15 minutes and rinsing with running water for 5 minutes, the whiteness of the contaminated cloth increased from 63 to 70, and blood stains almost disappeared. A bleaching and cleaning effect was recognized.

[Example 18 ]
One molded product prepared in Example 15 was dissolved in 2 liters of water to prepare a bleach washing solution (effective chlorine concentration: about 500 ppm). When the tea-stained cloth was immersed in this bleaching washing solution for 5 minutes and rinsed with running water for 5 minutes, the whiteness of the contaminated cloth increased from 40 to 68, and a good bleaching-cleaning effect was observed.

Claims (1)

Halogen-based oxidant or oxygen-based oxidant (excluding sodium percarbonate) and chemical formula (I), chemical formula (II), chemical formula (III), chemical formula (IV) or chemical formula (V) A colored oxidizer composition comprising a pigment represented by the formula (1) and a surfactant.