JPH045078B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Fields) In addition to bleaching fibers, the present invention can be used for household and commercial purposes for bleaching, cleaning, and hygiene purposes, such as removing various bacteria and alleviating putrid odors (organic substances). The present invention relates to a bleach composition for commercial use. The present invention is characterized by improving the viscosity and detergency of a bleaching agent containing hypochlorite as a main component, as well as achieving excellent odor mitigation. (Prior Art) A technique for imparting viscosity to a hypochlorite bleach composition itself is described in, for example, Japanese Patent Application No. 58-234099 filed by the same applicant as the present invention. This is a bleaching agent that basically contains a specific Seviolite mineral and two types of surfactants. In addition, the use of sodium aralsulfonate as a surfactant for hypochlorite was established in 1973.
-24786, and the use of alkyldimethylamine oxide is also described in JP-A-56-90897 and JP-B-45-7970. The combination use in the form is described in JP-A-55-50097 and JP-A-57-61099, each of which belongs to the known technology. (Problems to be solved by the invention) The above-mentioned Japanese Patent Application No. 58-234099 has the following problems:
It is opaque, and the sepiolite itself has a clay color (ocher color), making the appearance unfavorable. This is not limited to sepiolite, but also bentonite, zeolite, calcite, talc, sericite, other salts, inorganic substances such as tripolyphosphoric acid, silicates, polycarboxylic acid salts (acrylic acid, maleic acid, etc.), and even xanthan gum, locust bean. The same applies when rubber-like substances such as gum, gum arabic, and gum karaya are used. In addition, hypochlorite is a strongly acidic aqueous substance, is alkaline, and has strong hydrolyzing power, so that it does not cause a practical drop in effective chlorine over a wide temperature range of -10℃ to 50℃ for a long period of time. It was extremely difficult to do so. Furthermore, the above-mentioned use of sodium alkyl sulfonate as a surfactant for hypochlorite, use of alkyl methyl amine oxide, and use of these together in some form, all of which What these technologies have in common is that they merely add detergent elements for the purpose of improving permeability and bleaching power, and are unsatisfactory in increasing viscosity (thickening), clarifying, and improving odor. It was hot. Incidentally, regarding odor improvement,
As described in Japanese Patent Application Laid-open No. 52-69445,
There were products that simply contained fragrances. The present invention aims to solve the above-mentioned conventional problems, namely, a new bleach composition that has excellent bleaching power and cleaning power, has improved odor and viscosity problems, and is easy to use. It is something that provides something. (Means for Solving the Problems) The present invention provides an aqueous solution of hypochlorite containing 1 to 7.5% by weight of available chlorine and 0.1 to 4% by weight of an alkali metal hydroxide salt to an aqueous solution of hypochlorite. For an aqueous solution of hypochlorite designed to contain sodium chloride within 1.5% by weight, including the sodium chloride contained in itself, add an alkyl sulfonate represented by the following general formula (1) and a hypochlorite represented by the following general formula (2). The former 1
A bleaching agent composition characterized in that 2 to 11.2% by weight of a surfactant is mixed with the latter at a ratio of 0.5 to 5.02 times by weight. General formula (1) R-SO ₃ M The alkyl sulfonate is a sulfonic acid obtained by sulfonation with chlorosulfonic acid. And the sodium monosulfonate content is at least 70% by weight. R is a _C15 to _C18 alkyl group or alkenyl group M is Na, K, _NH4 , alkanolamine residue General formula (2) R ₁ is a C ₈ to C ₁₈ alkyl group or alkenyl group R ₂ is a C ₁ to C ₄ alkyl group or (CH ₂ CH ₂ O)
nH (n = positive integer from 1 to 10) (Effect) A bleach composition as shown in Table 1 below was prototyped,
We conducted quality tests on each.

【table】

[Table] Based on Table 1 above, available chlorine, viscosity, appearance change,
It was confirmed that the samples of the present invention were superior in each category of chlorine odor. Next, if you graph the viscosity change over time,
This is as shown in Figure 1. The graph was calculated based on the following formula. Effective chlorine reduction rate = value immediately after production - value after time / value immediately after production x 100% This confirmed that the viscosity of the sample of the present invention remained stable over time. Next, we made prototype bleach compositions using sodium alkylsulfonate obtained from secondary paraffin, which was sulfonated with acid and sulfuric anhydride. conducted a test. As shown in Table 2 below, the results were confirmed to be superior to conventional ones.

【table】

[Table] Next, we tested changes in viscosity, available chlorine, and appearance depending on the AO/SSA blending ratio and NaCl content. The results are shown in Table 3 below.

【table】

[Table] Note: Amount of available chlorine; per 6%. Appearance: Same evaluation method as in Table 1 Next, a performance test regarding bleaching power was conducted.
The results are shown in Table 4 below.

[Table] Based on the above bleaching power test, after 20 minutes, after 40 minutes,
In all cases after 70 minutes, it was confirmed that the products of the present invention were superior. Next, we conducted the following performance test regarding sterilization power. Mold and bacteria were uniformly cultured, each sample was sprayed (15 ml/min), and the surface mold removal rate after a predetermined period of time was estimated (10 mold samples were prepared, and the estimated value was the average of the samples). ) Cultivation conditions: Mold growing in home bathrooms was collected using the stamp method, and molds such as Aspcrgillus Niger and Clados
purium claduspurioides, PhomaSP,
Five types of fungi, Rhodoturula and Aureobasidium Pullulans, were stamped on potato dextrose agar containing 45 μs/ml of chloramphenicol as a separation medium, and cultured at 30°C and 80% RH for one month (area: approximately 100 cm ² ). . The results are shown in Table 5 below.

[Table] From the results in Table 5 above, the present invention can be used for 180 seconds, 300 seconds,
It was confirmed that an excellent mold removal rate was exhibited in any case of 600 seconds. Next, a sensory test regarding smell was conducted.
The results are shown in Table 6 below.

【table】

[Table] (Examples) Specific examples of the present invention will be described in detail as follows. The present invention can be used as a surfactant for an aqueous solution of hypochlorite designed to contain 1 to 7.5% by weight of available chlorine and 1.5% by weight of sodium chloride as a blended metal. SSA (alkyl sulfonate) and AO (alkyl amine oxide) are used in a specific ratio (weight ratio), and as an alkaline substance, especially sodium hydroxide is used at 0.1
It is characterized by containing ~4% by weight. The present invention thus provides viscosity, stability, detergency,
This makes it possible to produce a bleach composition that is improved in terms of clarity and odor. In other words, sodium hypochlorite itself has an available chlorine content of about 12% by weight, and if sodium chloride is used within at least 2% by weight, preferably 1.5% by weight, it becomes a surfactant. The SSA used as a secondary paraffin is an alkali salt (preferably soda salt) containing at least 70% by weight of monosulfonic acid made from secondary paraffin and chlorosulfonic acid, and a linear alkyl type in which the alkyl of AO is C ₁₂ to _{C 18} . A total of 2 to 11.2% by weight of AO at a ratio of 0.5 to 5.02 times the weight of SSA is blended, and 0.1 to 4% by weight of an alkali metal hydroxide (preferably sodium hydroxide) is blended. The bleaching agent obtained by Conventionally, it has been common practice to use sodium hypochlorite containing salts such as sodium chloride, sodium pyrophosphate, sodium acrylate, sodium carbonate, and sodium silicate. Although it is widely known that reducing the sodium chloride in sodium hypochlorite stabilizes the available chlorine itself, it does not contribute in any way to the desired viscosity improvement. The invention uses only such low salt (sodium chloride) sodium hypochlorite and, as a surfactant, a (C ₁₅ -C ₁₈ ) alkali metal salt of secondary paraffin sulfonated by the chlorsulfone method. It has been discovered that (Na, K, etc.) can be particularly blended with dialkylamine oxide in a specific ratio to exhibit thickening, stability, and odor improving effects. SSA produced by the chlorosulfonation method produces 3 to 5% sodium chloride as a byproduct, but this small amount of halogenated molecules (chlorine) coexists with hypochlorite and contributes to viscosity and stability. However, unlike fuming sulfuric acid, sulfuric anhydride does not solubilize sodium sulfate-containing substances and lacks long-term stability. concerned
SSA has the general formula R-SO ₃ M (R is C ₁₅ ~
C ₁₈ ) alkyl group or group, M is Na, K,
These are alkanolamine residues such as NH ₄ , monoethanolamine, triethanolamine, and monoisopropanolamine. ), furthermore, the sulfonation of secondary paraffin reduces the viscosity unless the SSA contains at least 70% monosulfonic acid. When the amount of disulfonic acid is large, the anti-hydrolysis and anti-oxidation properties are excellent, but the desired effects of the present invention cannot be expected. On the other hand, the alkylamine oxide used in combination is represented by the following general formula. R ₁ is a C ₈ to C ₁₈ alkyl group or alkenyl group R ₂ is a C ₁ to C ₄ alkyl group or (CH ₂ CH ₂ O)
nH (n=a positive number of 1 to 10) Further, R ₂ is particularly preferably a C ₁₂ to _{C 18} lararu, coconut alkyl, myristyl, or alkyl group, and R ₂ is preferably a methyl group or a hydroxyethyl group.
In particular, when R ₁ is C ₁₅ or more, it is possible to control the foaming property of the SSA to an extent higher than necessary, so that it can be used for applications where foaming is not preferred. SSA and AO are the former 1 (weight) and the latter
It is necessary to mix in a ratio of 0.5 to 5.02 (by weight). In particular, SSA must be no more than 2.5% in the composition. This is because if the lid is closed, the liquid will become cloudy and lose stability. The total amount of surfactant is 2 to 11.2% by weight, and if it deviates from this range, it will lack stability and show signs of thinning. Moreover, unnecessary foaming is promoted and post-processing becomes complicated. In addition to these surfactants, polyoxyethylene alkyl ether sulfate, alkyl diphenyl oxide disulfonate, polyoxyethylene nonyl phenylether sulfate, polyoxine ethylene alkyl ether sulfate sulfonate, polyoxine ethylene alkyl ether sulfate Anionic systems such as ester sulfonates and alkyl phosphates, nonionic systems such as polyoxyethylene fatty acid alkanolamides and polyoxyethylene alkyl phenol ethers, amphoteric systems such as imidazolinine salts and bedaine salts, beef tallow ammonium salts (dialkyl dimethyl ammonium chloride) ,
Benzalkonium chloride, polyoxyethylene monoalkyldimethylammonium methosulfate, monoalkyldiethoxymethylammonium chloride) may also be contained within the above blending percentage. In any case, alkali metal hydroxide salts, especially soda salts, are used to maintain the pH at 11 or higher.
It is necessary to use 0.1 to 4%, preferably 0.1 to 3%, of potassium salt etc. in order to ensure the stability of the hypochlorite. In addition, the composition of the present invention includes various fragrances, pigments, binders, fluorescent agents, bactericides, salts (halogenated salts, phosphates, silicates, borates, carbonates, organic acid salts, etc.) and abrasives (polymers). , kaolin,
Calcite, corundum, talc, etc.), cyclodextrin, terpenoids, zeolites, molecular sieves, etc., as well as oxygen bleaches (sodium borate, sodium percarbonate, H ₂ O ₂ ), Reducing agent (hypo,
sulfites, hydrosulfites), activated carbon,
High molecular weight polymers, oligomers (sodium acrylate, acrylic bluff starch, cationized starch, etherified starch), oxidized preservatives (ascorbic acid,
It can also be used in combination with anti-oxidant reactants such as tocopherol, BHA, BHT, EPA). The quality setting conditions for the composition of the present invention are as follows: 1 to 7.5% by weight, especially 3 to 6% by weight, as available chlorine, a reduction rate of available chlorine of 25% by weight or less after 1 year at room temperature, and a viscosity at 20°C (B-type viscometer). ) 200cp or more and 800cp or less, especially 300 to 600cp, appearance is completely transparent in the temperature range of -5 to 60℃, and the service life is guaranteed to be more than 1.5 years. The bleach composition thus obtained has a wide variety of uses. Used as a bleach for household and commercial cleaning; as a sanitary use in hospitals, food industries, and food service facilities; as a deodorizer in toilets, sewers, garbage disposals, etc.
It can be used as a one-liquid type cleaning agent for storage sheds, fish tanks, swimming pools, etc., and as a cleaning agent for kitchens, clothing, and homes. (Effects of the Invention) The gist of the present invention is a bleach composition as described in the claims, and since the present invention adopts such a configuration, hypochlorous acid, whose use has been limited in the past, It becomes possible to provide a bleach composition that has significantly improved viscosity, which is a drawback of salt and alkaline agents, has a cleaning function, and has improved odor. Therefore, it is particularly suitable for use in fields for the purpose of cleaning, bleaching, sterilization, deodorization, etc., especially for interior decoration, food equipment, women's and women's underwear, hospital patient clothing, bedding, infant clothing, tableware, etc. Are suitable. Furthermore, since the bleach composition of the present invention has a medium viscosity, it can also be used by being filled into trickle spray devices such as sprayers (hand type), nozzles, and syringes. Since phenomena such as dripping and spillage are effectively avoided, the purpose of use can be achieved safely and economically.

[Brief explanation of drawings]

FIG. 1 is a graph showing viscosity changes.

Claims (1)

[Claims] 1. 1 to 7.5% by weight of available chlorine and 0.1 to 7.5% of alkali metal hydroxide in an aqueous solution of hypochlorite.
4% by weight, an alkyl sulfonate represented by the following general formula (1) for an aqueous solution of hypochlorite designed to contain sodium chloride within 1.5% by weight, including that contained in the hypochlorite itself. and an alkylamine oxide represented by the following general formula (2) in a ratio of 0.5 to 5.02 times by weight of the latter to 1 of the former in a ratio of 2 to 11.2% by weight. Bleach composition. General formula (1) R-SO ₃ M The alkyl sulfonate is a sulfonic acid obtained by sulfonation with chlorosulfonic acid. And the sodium monosulfonate content is at least 70% by weight. R is a _C15 to _C18 alkyl group or alkenyl group M is Na, K, _NH4 , alkanolamine residue General formula (2) R ₁ is a C ₈ to C ₁₈ alkyl group or alkenyl group R ₂ is a C ₁ to C ₄ alkyl group or (CH ₂ CH ₂ O)
nH (n=positive integer from 1 to 10).