JPS6297555A - Deodorant - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a deodorizing agent that makes malodorous substances odorless.

In recent years, the factors that generate bad odors have become more complex year by year, but the technology to deal with them is extremely inadequate, so the current situation is that there is no sign that bad odor pollution will improve.

As conventional deodorization treatment methods for bad odors, activated carbon adsorption methods, catalytic combustion methods, oxidation methods using ozone or chemicals, neutralization methods, bacterial decomposition methods, enzyme methods, etc. are known. However, all of them have many drawbacks, such as high running costs, difficulty in management, poor sustainability, and relatively low deodorizing efficiency.

Among the above-mentioned known deodorizing treatment methods, the method of decomposing malodorous gases using oxidizing agents is the most effective, but since potassium dichromate, sulfuric acid, etc. are generally used as agents, care must be taken when handling them. There is a risk of secondary contamination due to chemicals, and the reaction temperature is high.
This treatment method is not preferred for general use.

The present invention has been made in order to eliminate the above-mentioned drawbacks, and aims to provide a deodorant that can decompose malodorous substances in a short time and is improved in terms of practicality.

As a result of research on deodorants, the present inventors obtained the following knowledge. Metal porphyrins and metal porphyrazines, which are metal complexes with redox ability, act as catalysts and have the property of decomposing malodorous substances to make them odorless. Among metal porphyrazines, metal phthalocyanine has particularly excellent properties. For example, it has a high reaction rate and high decomposition rate, the reaction proceeds at room temperature, it can react in an aqueous system, and it uses oxygen in the air effectively. It has extremely advantageous properties as a deodorizer, such as the fact that it can be used in a cyclic reaction and has a long catalyst life. Furthermore, catalytic efficiency is improved by bonding metal phthalocyanine to a polymer compound.

The deodorant of the present invention, which was developed based on this knowledge, contains a polymeric metal complex in which a metal phthalocyanine derivative is bonded to a polymeric compound.

The metal phthalocyanine derivative is represented by the following formula.

M is a metal atom, such as iron, cobalt, copper, nickel,
There are manganese, osminium, titanium, molybdenum, tungsten, etc. Among them, iron and cobalt are preferable.
At least one of Y represents a substituent and the remainder represents a hydrogen atom. Examples of the substituent include an alkyl group, a substituted alkyl group, a halogen group, a nitro group, an amine group, an azo group, a thiocyanate group, a carboxyl group, and a carbonyl chloride group. group, aldehyde group, carboxylamide group, nitrile group, hydroxyl group, alkoxyl group, phenoxydyl group, sulfonic acid group,
In addition to sulfonyl chloride groups, sulfonamide groups, thiol groups, chloromethyl groups, alkyl silicon groups, vinyl groups, etc., there are also alkali salts of carboxyl groups and sulfonic acid groups.

Examples of the polymer compound to which the metal phthalocyanine derivative is bound include natural organic polymers such as polyvinyl alcohol, polyacrylic acid or polymethacrylic acid, metal salts or alkyl esters thereof, polyacrylic or polymethacrylamide, mono- or dialkylamino Acrylates or methacrylates, polyhydroxyalkyl acrylates or methacrylates, polyvinylpyrrolidone, polyethylene oxide, polyvinylsulfonic acid or its metal salts, polyvinyl esters,
polystyrene, polyvinyl acetal, polyester,
Polyamides, amino resins, alkyd resins, etc. and copolymers thereof are used, and those that react with and bond to the substituents of porphyrazine are selected, but polystyrene, polyvinyl alcohol, polyacrylic acid esters, polymethacrylates are preferably used. Ugly esters 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 it may be used by dissolving or dispersing a polymeric metal complex in water or an organic liquid, or using activated carbon, sawdust, zeolite, bentonite, etc. with adsorption capacity. It can be adsorbed onto solid materials such as pumice, foamed concrete, various fibers, leather,
It is used by being attached or chemically bonded to rubber, plastics, paper, pulp, etc.

Example 1 150 ml of nitrobenzene was placed in a three-roof 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 18.3 g of ferric chloride anhydride were added and stirred. , and heated at 160-170° C. for 3 hours while refluxing.

After cooling, the precipitate was filtered and mixed with methanol, f! Washed with hydrochloric acid and water in this order to obtain iron phthalocyanine tetracarboxylic acid amide.Next, this was placed in a three-bottle flask equipped with the same equipment as above, along with 11 oz of a 3 oz aqueous potassium hydroxide solution, stirred, and refluxed at 100°C. The mixture was reacted and hydrolyzed while cooling, and after cooling, it was acidified by adding hydrochloric acid to obtain iron phthalocyanine tetracarboxylic acid.

10 benzene in a three-loaf flask equipped with the same equipment as above.
hl, the obtained iron phthalocyanine tetracarboxylic acid tag, 301 l of thionyl chloride, and 0.51 l of pyridine were added, stirred and heated, and reacted under reflux for 10 hours to form iron phthalocyanine having a carbonyl chloride group. To a solution of 30 g of polystyrene in nitrobenzene 3001, 5 g of the iron phthalocyanine obtained above, which softens the carbonyl chloride group, is added, and the mixture is stirred and dissolved until uniform. Next, the mixture was cooled to 10° C. or lower using an aqueous solution, 10 g of anhydrous aluminum chloride was added, and the mixture was left to stand for 10 hours with stirring to obtain a gel-like reaction product. This was poured into water and nitrobenzene was removed by steam distillation, and after drying, the product was washed with methanol, a dilute alkaline solution in that order, and further washed with dilute hydrochloric acid to obtain polystyrene having iron phthalocyanine in the side chain. . After pulverizing it even more finely, it is poured into benzene and dispersed.

A deodorant sample was obtained by adsorbing 20% of this onto a nonwoven fabric.

Example 2 150 g of iron phthalocyanine having a carbonyl chloride group obtained in Example 1 and 12 g of barium palladium sulfate,
400 ml of xylene was placed in each flask equipped with a stirrer, and hydrogen was blown into the flask to perform Rosenmund reduction to obtain iron phthalocyanine having an aldehyde group.

1100 ml of 10% polyvinyl alcohol aqueous solution and 30
%iiiW11100ml was mixed and heated to 40°C,
51 g of the iron phthalocyanine having an aldehyde group obtained above was added to this and reacted with stirring.The viscosity of the zero reaction system gradually increased, and when it reached just before gelation, it was cooled.
After neutralizing with 10% aqueous ammonia, methanol was added to precipitate and dry. As a result, polyvinyl alcohol to which iron phthalocyanine was bound was obtained.
A deodorant sample was prepared by uniformly applying 20 gr of the above product to 0 gr.

Example 3 Nitrobenzene 1501 was placed in a three-bottle flask equipped with a stirrer and a reflux condenser, and 114 g of pyromellitic anhydride, 300 g of urea, and 1 ammonium molybdate were added.
0 g and 18.3 g of ferric chloride anhydride were added and stirred.
The mixture was heated at 60-170° C. for 3 hours under reflux. After cooling, the precipitate was filtered, washed in the order of methanol, dilute hydrochloric acid, and water, and then placed in a three-loaf flask equipped with the same equipment as above, along with one liter of a 30% aqueous solution of potassium hydroxide, and stirred.
The mixture was reacted and hydrolyzed under reflux at 100°C, and after cooling, hydrochloric acid was added to acidify the mixture to obtain iron phthalocyanine octacarboxylic acid.

20 g of finely ground powder is dissolved in a 1% caustic soda solution. The primarily swollen viscose rayon is immersed in this solution for about 5 hours with stirring. Neutralize the solution with dilute hydrochloric acid, wash with water, and dehydrate and dry. As a result, a deodorant in which iron phthalocyanine octacarboxylic acid was bonded to rayon fiber, which is a polymeric material, was obtained, which was used as a deodorant sample.

Comparative example 1 Activated carbon was used as a deodorant sample.

Comparative Example 2 Iron phthalocyanine powder obtained by a conventional method was dispersed in water, and 20% of this was adsorbed on activated carbon to prepare a deodorant sample.

In the performance test, a sensitivity test was conducted using the apparatus shown in FIG.

Examples 1 to 3 and Comparative Example 1 were placed in the deodorizing box l shown in Figure 1.
- 80g of deodorant sample 3 prepared in Comparative Example 2 was filled in each container, held down with a perforated plate 5, and then plugged. On the other hand, a malodorous substance aqueous solution 4 shown in the table below is put into the air washing bottle 2. Air is sent from the open end of the tube, passes through the malodorous substance aqueous solution 4, and introduces the malodorous gas into the deodorizing box l at a rate of 2001 per minute, where it is deodorized with the deodorizing agent 3. 1hr, 5hr from the start of introduction
, after 2 ahr, the exhaust air from deodorizing box 1 is
The status of deodorization was determined by the name monitor. The results are shown in the table below.

Table 1 The deodorization results were displayed as follows.

5: No odor at all 4: Almost no odor 3: Slight odor 2: Odor 1: Strong odor The polystyrene with iron-2-talocyanine attached to its side chain shown in Example 1 has a catalytic activity as a deodorizing agent. 6 For example, iron phthalocyanine tetracarboxylic acid decomposes easily at the same time as it decomposes
Even when connected to 2, it retains 60% of its activity,
The stability of iron phthalocyanine itself can be significantly increased by binding it to a polymer.

As explained above, since the deodorant of the present invention decomposes malodorous substances through catalytic action, it is not decomposed by itself, and has a long lifespan as a deodorant. are doing. In addition, there is no risk of secondary contamination due to chemicals and it is easy to handle.

In addition, since the deodorant of the present invention is a polymeric substance, it can be used in the form of fibers, films, chips, etc. itself, copolymerized substances with other polymeric substances, or blended substances with other polymeric substances. It can also be mixed into paper materials that can be formed into rubber, powder, or object structures. It can also be mixed into paints and the like. Therefore, depending on the shape, it can be used for all kinds of polymer materials currently used, such as clothing, bedding, carpets, building materials, filters for air purification equipment and sewage treatment equipment, packaging materials, containers, and automobile interior parts. It is possible to have a deodorizing function.

[Brief explanation of drawings]

FIG. 1 is a diagram showing an apparatus for testing the deodorizing performance of a deodorant. 1... Deodorizing bottle 2... Air washing bottle 3...
・Deodorant 4,,,,, Malodorous substance aqueous solution 541.
Perforated plate patent applicant Kama Shirai Earth Clean Co., Ltd. Nichiki Carbide Kogyo Co., Ltd. Figure 1

Claims (1)

[Claims] 1. Metal phthalocyanine derivative of the following formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, M is a metal atom, at least one Y represents a substituent, and the remainder represents a hydrogen atom] A deodorizer containing a polymeric metal complex that is bound to a polymeric compound.