JPH0119899B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a deodorant. In recent years, the factors that cause bad odors have become more and more complex.
As the technology to deal with this problem is extremely inadequate, there is currently no sign that odor pollution will improve. Conventional methods for deodorizing bad odors include activated carbon adsorption, catalytic combustion, ozone or chemical oxidation, neutralization, bacterial decomposition, and enzymatic methods, but all of them have low running costs. It has many drawbacks, such as being expensive, difficult to manage, lacking in sustainability, and having relatively low deodorizing efficiency. In particular, among these known deodorizing treatment methods, the method of decomposing malodorous gas using an oxidizing agent is the most effective, but it generally uses potassium dichromate, sulfuric acid, etc. as the agent, so be careful when handling it. This treatment method is not preferred for general use because of the high reaction temperature, the risk of secondary contamination due to chemicals, and the high reaction temperature. As a result of research into deodorants that do not have the above-mentioned drawbacks and exhibit excellent effects, the present inventors discovered that metal phthalocyanine, a metal complex with redox ability, has excellent performance. It has been found that particularly excellent performance can be imparted by introducing substituents or bonding to inorganic substances or polymeric substances. In other words, metal phthalocyanine has a high reaction rate and high decomposition rate when decomposing malodorous substances to make them odorless.
It has extremely advantageous properties as a deodorant, such as the ability to react at room temperature, the ability to react in an aqueous system, the ability to effectively use oxygen in the air, and the long life of the catalyst in a cycle reaction. It has been found that catalytic efficiency can be significantly increased by introducing groups or chemically bonding them to inorganic substances or polymeric compounds. As described above, the deodorant of the present invention introduces at least one or more substituents into metal phthalocyanine, or
Alternatively, at least one metal phthalocyanine bonded to an inorganic substance or a polymeric substance is used.The basic skeleton of metal phthalocyanine is shown as follows. Here, M is a metal ion or metal compound ion having redox ability, and Y represents hydrogen or a substituent. Examples of metals serving as metal ions represented by M in the basic skeleton include sodium, potassium, calcium, barium, tin, chromium, iron, cobalt, nickel, manganese, osmium, titanium, beryllium, molybdenum, and tungsten. Examples of metal compounds that become compound ions include hydroxides and halides of polyvalent metals among the above metals. Among these metals or metal compounds, metals are preferably used from the viewpoint of deodorizing effect, and among these, manganese, cobalt, and iron are particularly preferably used. Substituents used in the present invention include alkyl groups, substituted alkyl groups, halogen groups, nitro groups, amino groups, azo groups, thiocyanate groups, carboxyl groups, carbonyl chloride groups, carboxylamide groups, nitrile groups, hydroxyl groups, alkoxyl groups, In addition to phenoxyl groups, sulfonic acid groups, sulfonyl chloride groups, sulfonamide groups, thiol groups, chloromethyl groups, alkyl silicon groups, vinyl groups, etc.
There are alkali salts of carboxyl groups and sulfonic acid groups, and one or more of these are used, but among them, carboxyl groups, sulfonic acid groups or alkali salts thereof, amino groups, halogen groups, A hydroxyl group, etc. are used, and a carboxyl group, a sulfone group, or an alkali salt thereof, and an amino group are particularly preferably used.
Most preferably, a carboxyl group or a salt thereof or an amino group is used. Examples of inorganic substances or polymer compounds to be chemically bonded include inorganic substances such as silica gel and glass fiber, natural polymers and their derivatives such as cellulose, starch, gelatin, casein, and guar gum, polyvinyl alcohol, polyacrylic acid, and polymethacrylic acid. Acids and their metal salts or alkyl esters, polyacrylic or polymethacrylamides, polymono- or dialkylaminoacrylates or methacrylates, polyhydroxyalkyl acrylates or methacrylates, polyvinylpyrrolidone, polyethylene oxide, polyvinylsulfonic acids or their metal salts, polyvinyl esters, There are synthetic polymeric substances made of polystyrene, polyvinyl acetal, polyester, polyamide, amino resin, alkyd resin, etc., and copolymers thereof, and these are selected from those that react with and bond to the substituents of phthalocyanine, but preferably. teeth,
Polystyrene, polyvinyl alcohol, polyacrylic ester, polymethacrylic ester, and polyvinylamine are used, particularly preferably polystyrene and polyvinyl alcohol. The method of using the deodorant in the present invention is not particularly limited, but metal phthalocyanine having at least one or more substituents or having these substituents chemically bonded to an inorganic substance or a polymer compound, used dissolved or dispersed in water or organic liquid;
Alternatively, it can be used by being adsorbed onto a solid having adsorption ability such as activated carbon, sawdust, or zeolite, or by being attached or chemically bonded to pumice, foamed concrete, various fibers, leather, rubber, plastics, paper, pulp, etc. Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way. Example 1 150 ml of nitrobenzene was placed in a three-neck flask equipped with a stirrer and a reflux condenser, and 100 g of trimellitic anhydride, 300 g of urea, 10 g of ammonium molybdate, and 16.3 g of ferric chloride anhydride were added and stirred. , and heated at 160-170°C for 3 hours under reflux. After cooling, the precipitate was filtered and washed with methanol, dilute hydrochloric acid, and water in this order to obtain iron phthalocyanine carboxylic acid amide. Next, add 1 part of 30% caustic potassium solution to a 3-necked flask equipped with the same equipment as above.
The mixture was stirred and reacted under reflux at 100°C to cause hydrolysis. After cooling, hydrochloric acid was added to acidify to obtain iron phthalocyanine tetracarboxylic acid. This was finely pulverized, dispersed in water, and 20% adsorbed on activated carbon, which was then used as a deodorant supply sample. Example 2 In the same manner as in Example 1, trimellitic anhydride
Cobalt phthalocyanine octalcarboxylic acid was obtained by using 114 g of pyromellitic anhydride instead of 100 g and using cobalt chloride instead of ferric chloride. 20g of this powder in 1% caustic soda solution
Sodium bentonite dissolved in 800ml
When 200 g was added, a gel-like substance was obtained, which was used as a deodorant sample. Example 3 100 ml of benzene was placed in a three-necked flask having the same equipment as in Example 1, and 10 g of iron phthalocyanine tetracarboxylic acid obtained in Example 1, 30 ml of thionyl chloride, and 0.5 ml of pyridine were added, stirred, and heated. The mixture was reacted under reflux for 10 hours to form iron phthalocyanine having a carbonyl chloride group. Add 5 g of the carbonyl chloride group-containing iron phthalocyanine obtained above to a solution of 30 g of polystyrene in 300 ml of nitrobenzene, stir until homogeneous, cool to below 10°C in an ice bath, and then add anhydrous aluminum chloride. 10g was added and left to stand for 10 hours with stirring to obtain a gel-like reaction product. Next, this was poured into water to remove nitrobenzene by steam distillation, and after drying, the product was washed with methanol, a dilute alkaline solution, and then dilute hydrochloric acid to obtain polystyrene having iron phthalocyanine in the side chain. Obtained. This was further finely ground, dispersed in benzene, and 20% of this was adsorbed on a nonwoven fabric, which was used as a deodorant sample. Example 4 105 g of iron phthalocyanine having a carbonyl chloride group obtained in Example 3, 12 g of barium palladium sulfate, and 400 ml of xylene were placed in a flask equipped with a stirrer, hydrogen was blown in to perform Rosenmund reduction, and aldehyde groups were An iron phthalocyanine having the following properties was obtained. 1100ml of polyvinyl alcohol 10% aqueous solution and 30%
Mix 1100ml of sulfuric acid and warm to 40℃, and add the iron phthalocyanine having aldehyde groups obtained above.
51gr was added and reacted with stirring. The viscosity of the reaction system gradually increased and when it reached just before gelation, it was cooled, neutralized with 10% aqueous ammonia, precipitated by adding methanol, and dried. A sample was prepared by uniformly adhering 20 gr of the above product to 100 gr of asbestos. Example 5 In refluxing xylene containing 20 g of imidazole and 30 g of 3-chloropropyltrimethoxysilane, 100 g of 60-80 mesh silica gel dried at 150° C. was placed and refluxed for 3 hours. Next, this was filtered off, washed with dehydrated benzene and acetone, treated with ethylene oxide, further washed with acetone, and dried at 150°C to obtain a silica gel having 3-imidazolylpropyl groups on its surface. Further, this was placed in benzene from step 3, 5 g of iron tetraphenyl phthalocyanine was added, and the mixture was reacted at room temperature for 3 hours with stirring.The medium was then removed by decantation, washed several times with benzene, and then dried in vacuo. It was used as a test sample. Example 6 Put 180 g of nitrobenzene in the same container as in Example 1, add 40 g of 3-nitrophthalic anhydride, and urea.
Add 96g of anhydrous cupric chloride, 8g of anhydrous cupric chloride, and 3.2g of ammonium molybdate, heat, and react under reflux for 5.5 hours. Next, cool this and add water, methanol, 0.1
% caustic soda and 0.1N hydrochloric acid, and dried to obtain copper tetranitrophthalocyanine powder. 20.8g of this powder was suspended in 510g of water, 98g of sodium sulfide nonahydrate was added, and the mixture was stirred at 30°C for 3 hours and then at 60°C for 4 hours, resulting in a dark purple color.This was filtered off and the residue was dried to obtain tetraminophthalocyanine copper. powder was obtained. Next, add 20g of this powder to 100g of sawdust.
This was used as a test sample. Comparative Example 1 The same activated carbon used in Example 1 was used as a deodorant sample. Comparative Example 2 Iron phthalocyanine powder was dispersed in water, and 20% of this was adsorbed on the same activated carbon as in Example 1 to prepare a deodorant sample. Deodorizing Test 80 g of the deodorizing agents prepared in Examples 1 to 6 and Comparative Examples 1 to 2 were filled into the deodorizing bottle 1 shown in Figure 1 (in the case of Example 3, 80 g of the deodorizing nonwoven fabric). On the other hand, the malodorous gas that has passed through the air washing bottle 2 containing the odor-producing substance aqueous solution shown in the attached table is introduced into the deodorizing bottle 1 at a rate of 200 ml per minute.
After 24 hours, 10 people monitored the gas discharged from the deodorizing bottle 1 to determine whether or not the deodorizing state had been achieved. The results are shown in the attached table.

【table】

【table】 [Brief explanation of drawings]

1 shows a deodorizing test device for a deodorant according to the present invention. 1... Deodorizing bottle, 2... Air washing bottle, 3... Deodorant,
4...Aqueous solution of odoriferous substance, 5...Perforated plate.

Claims (1)

[Claims] 1. The following formula [In the formula, Y represents at least one carboxyl group and unsubstituted H. However, carboxyl groups in which Y is 4 or more are excluded. ] A deodorant containing metal phthalocyanine.