JPH0426899B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a deodorizing material. More specifically, it is highly effective in deodorizing odors emitted from fresh foods such as fruits, vegetables, seafood, and meat, and maintaining the freshness of these foods. It is a deodorizing agent that has an excellent deodorizing effect on bad odors generated from sources such as human waste, and other sources of bad odors that significantly impede the living environment. This invention relates to a deodorizing material that is extremely effective in deodorizing components with strong malodors such as aldehydes. [Prior Art] Activated carbon has been widely used as a means for removing bad odors. There are also methods of masking or neutralizing malodorous components with aromatic components, and many products are sold as household products. However, these methods are insufficiently effective;
It has not reached a satisfactory stage in terms of practicality.
This is because activated carbon has extremely low deodorizing ability against polar gases with small molecular weights, especially ammonia, which is one of the representative malodorous gases, and when the surface gets wet with water vapor, it becomes deactivated and its deodorizing effect decreases. It has the following drawback. Additionally, masking and neutralization using aromatic gases are basically methods that appeal to the human sense of smell, rather than deodorization, and have the disadvantage that once people get used to this method, they may become bothered by other odors. On the other hand, a deodorizer containing L-ascorbic acid and a ferrous compound (Japanese Patent Publication No. 61-43091) was proposed.
Although a certain improvement effect is recognized, the situation is still not fully satisfactory. This is because L-ascorbic acid, which maintains ferrous iron in an active state, is sensitive to light and heat and does not exhibit its full effect.In particular, if left in the air for a long period of time, it will become discolored, and ferrous iron will It has a fatal flaw in that it becomes oxidized to ferric iron, reducing its deodorizing effect. Another problem was that L-ascorbic acid was economically expensive. In addition, a deodorant containing ferrous sulfate and citric acid as main ingredients and a small amount of aluminum etc. has been proposed (Japanese Patent Application Laid-open No. 74629/1983), but it is difficult to retain ferrous ions for a long period of time. is difficult. In particular, when a deodorizing agent is applied to paper or fiber products, there is a drawback that the deodorizing effect progresses over time as browning progresses and oxidation of ferrous iron progresses, reducing the deodorizing effect. Under these circumstances, as living standards improve, there is a strong desire to make the living environment odor-free, and as the economy expands, social and industrial sources of odor are increasing year by year. There are calls for a cleaner environment, and there is a strong demand for a deodorizing material that is effective in removing bad odors. [Problems to be Solved by the Invention] The present invention is chemically stable for a long period of time, does not decompose, change in quality, change color, or reduce the deodorizing effect, and is resistant to light and heat. It is a deodorizing material that is strong and can be applied to base materials such as paper products, textile products, wood products, and inorganic products with good adhesion by impregnation or coating, and has a high degree of whiteness and has high commercial value. The purpose is to provide an industrially inexpensive deodorizing material that is highly effective in deodorizing ammonia, amines, hydrogen sulfide, mercaptans, aldehydes, etc., and is also harmless to the human body. shall be. [Means for solving the problems] The present invention has the following configuration. That is, the deodorizing agent of the present invention contains an oxycarboxylic acid compound having two or more carboxyl groups in the molecule, a ferrous salt, and ammonium sulfate or ammonium sulfite as the third component. The present invention will be explained in detail below. The deodorizing material of the present invention has two carboxyl groups in its molecule.
It is essential to blend an oxycarboxylic acid compound having at least 100% oxycarboxylic acid, a ferrous salt, and ammonium sulfate or ammonium sulfite as a third component.
In other words, with this configuration, ferrous ions exhibit significant stabilization against oxygen in the air,
It has light resistance and heat resistance, maintains the active state of ferrous ions for a long period of time, has good adhesion to paper products, textile products, wood products, inorganic substrates, etc., does not fall off, and has a deodorizing effect. It has been discovered that a deodorizing material with high whiteness and long-lasting durability and high commercial value can be obtained, and it exhibits an excellent effect in deodorizing bad odors such as ammonia and methyl mercaptan. In addition, even if sulfates or sulfites other than ammonium sulfate or ammonium sulfite have a deodorizing effect, compared to those containing ammonium sulfate or ammonium sulfite,
It is not preferable because the effect is small and the sustainability of the effect over a long period of time is clearly inferior. Two carboxyl groups are included in the molecules constituting the present invention.
An oxycarboxylic acid compound having two or more carboxyl groups is a compound that effectively suppresses the oxidation of iron ions and activates them through a chemical reaction with ferrous ions, and maintains two or more carboxyl groups in the molecule for the purpose of chelate formation. It is necessary. Further, the compound needs to have at least one hydroxyl group in the molecule. In other words, by having at least one hydroxyl group in the molecule, the chemically formed product of the oxycarboxylic acid compound and ferrous ion has high solubility in water, which makes it suitable for various uses as a deodorizing material product described later. Not only does it work effectively to give a certain shape, but also
It works effectively to exhibit a deodorizing effect even when used in a dry state. Two carboxyl groups are included in the molecules constituting the present invention.
Specific examples of oxycarboxylic acid compounds having more than one oxycarboxylic acid include tartaric acid, citric acid, and malic acid, in which some or all of the carboxyl groups of the compound are alkali metal salts, alkaline earth metal salts, or ammonium salts. It may be. These can also be used by appropriately mixing them. This compound has the advantage of being harmless to the human body, causing no environmental pollution, and being industrially inexpensive. On the other hand, the ferrous salt constituting other components of the deodorizing material of the present invention is a component that chemically reacts with malodorous gas and deodorizes it, and specific examples include ferrous sulfate, ferrous ammonium sulfate, etc. , ferrous chloride, ferrous nitrate, and the like. These ferrous salts may be used alone or as a mixture. In short, ferrous salt is required. Ferrous salts are usually prepared as 0.01 to 1 mol/water solution. The amount of oxycarboxylic acid compound (A) relative to ferrous salt (B) is (A)/(B)=
0.003/1 to 2/1 (mol/mol), preferably
The ratio is preferably 0.01/1 to 1.5/1 (mol/mol), more preferably 0.1/1 to 1/1 (mol/mol), from the viewpoint of long-term stabilization of ferrous ions and long-term sustainability of the deodorizing effect. If the amount of the oxycarboxylic acid compound is less than this range, it will be insufficient for long-term stabilization of ferrous ions and the objective cannot be achieved; Therefore, it is not economical. Ammonium sulfate or ammonium sulfite, which constitutes the third component of the present invention, is essential from the viewpoint of long-term sustainability of the deodorizing effect, whiteness and adhesiveness of the molded product to which the deodorizing stock solution has been applied. Ammonium sulfate and ammonium sulfite (C) have a ratio of (C)/(B)=0.05/1 to 10/to the ferrous salt (B).
1 (mol/mol), preferably 0.1/1 to 5/1 (mol/mol), more preferably 0.25/1 to 2/1
(mol/mol) is necessary to achieve the effects of the present invention. If it is less than this range, the effect is small, and if it exceeds this range, it is not economical. The deodorizing material stock solution obtained in this way can be used as it is, or after being diluted with water several times to several hundred times, by dropping, scattering, or spraying using a spray method or the like. In addition, the deodorizing material of the present invention can be applied to paper products such as paper and cardboard, textile products such as yarn, staples, cords, fabrics, knitted fabrics, cotton, felt, and non-woven fabrics, wood products such as sawdust, cannacum, wood products, and wall materials, and molecular materials. Porous stones such as sheaves and pumice, inorganic substrates such as clay plates,
It is used as a deodorizing material by impregnating, coating, or spraying a deodorizing stock solution on plant-based substrates such as loofah, rice hulls, and cellulose sponge, and then drying it to make a deodorizing material.
In addition, the active ingredient is once made into a powder form from the stock solution,
It may be used in the form of this powder. The deodorizing material of the present invention may be used in combination with activated carbon. The amount of deodorizing material to which the stock solution is applied in various usage forms is based on the dry solid weight of the deodorizing material and the retained weight.
It is 0.1-500% by weight. If it is less than this range, the effect of the present invention will not be sufficient, and if it exceeds this range, the retention of the deodorizing material will not be sufficient, which is not preferable. The deodorizing material of the present invention can be used in plastic buckets for garbage storage, waste and processing plants of food processing plants, animal rooms, pet shops, human waste processing plants, livestock farms, etc.
It is effective in deodorizing sources of bad odors such as slaughterhouses. Furthermore, products in various forms to which the deodorizing material stock solution of the present invention has been applied can be used as plastic bags for garbage and wall hangings for indoor deodorization, and can also be used in toilets, refrigerators, elderly living rooms, hospital rooms, conference rooms, smoking rooms, laboratories, It can be used as a deodorizing material in closed rooms such as medicine cabinets, cars, trains, and airplanes. In addition, it can also be used as part of bedding, such as comforters, mattresses, and pillows, especially for bedridden elderly people and physically disabled people, as well as indoor curtains and wall hangings. It is also used in feminine sanitary materials, gas masks, cigarette filters, stocking pads, vacuum cleaner filters, air filters, etc. Further, the deodorizing material of the present invention can be used for deodorizing fresh foods such as fruits, vegetables, seafood, meat, etc., and for preventing spoilage. It is also used for sanitary purposes such as hand towels due to its antibacterial properties. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. 1 Stability of deodorizing material (1) Whiteness of deodorizing material 2 ml of deodorizing stock solution was added to a filter paper (5A-12.5 cmφ manufactured by Toyo Roshi Co., Ltd.), air-dried, and the whiteness of the filter paper was measured. The device used was an SM color computer manufactured by Suga Test Instruments Co., Ltd., type SM-3.The whiteness was measured using the Hunter method based on whiteboard (100%) and blackboard (0%).The higher the number (%), the higher the whiteness. is high. (2) Qualitative analysis of iron ions Add 2 ml of deodorized stock solution and air-dry the filter paper 1x
The pieces cut into 5 cm pieces were placed in an aqueous N/10-potassium thiocyanate solution, and the degree of oxidation of iron ions was qualitatively analyzed based on the coloring of the filter paper. That is, those without coloring were classified as divalent, those colored deep brown as trivalent, those slightly colored as slightly oxidized, and those exhibiting a slight brown color as slightly oxidized. 2. Deodorizing effect Gas concentrations of ammonia, amines, hydrogen sulfur, methyl mercaptan, formalin, etc. were measured using gas detection tubes (manufactured by Gastech Co., Ltd. and Komyo Rikagaku Kogyo Co., Ltd.). Example 1 0.5 mol of ferrous sulfate, 0.5 mol of citric acid, and 0.5 mol of various inorganic salts as a third component were dissolved in water,
One stock solution of each was prepared. Also, one without the addition of a third component (Comparative Example 1)
was also adjusted at the same time. Two weeks after adding these solutions to round filter paper and preparing samples, the whiteness of the round filter paper and the oxidation state of iron ions were qualitatively analyzed and compared. It was as shown in Table 1. From Table 1, it can be seen that deodorizing materials to which ammonium sulfate and ammonium sulfite are added as the third component have a remarkable effect on improving whiteness and stabilizing iron ions. Although products containing other sulfates or sulfites have a deodorizing effect, none exceed those containing ammonium sulfate or ammonium sulfite. and,
This data is after two weeks, but in addition,
If the elapsed time was longer than that, the durability of the effects of those other than those containing ammonium sulfate and ammonium sulfite deteriorated significantly.

[Table] Example 2 An aqueous solution of 1 was prepared by adding 0.5 mol of ferrous sulfate, 0.5 mol of citric acid, and ammonium sulfate as a third component in various amounts. The molar ratio of ammonium sulfate to ferrous sulfate was 0/1 (Comparative Example 2), in the range of 0.05/1 to 5/1. 2 ml of these stock solutions were added to round filter paper and air-dried. The whiteness of the deodorized paper thus obtained was measured from immediately after sample preparation until 10 months later to determine changes over time. In addition, qualitative analysis of iron ions was conducted after 10 months. It was as shown in Table 2. From Table 2, it is recognized that the addition of ammonium sulfate as the third component has an excellent effect on improving whiteness and stabilizing iron ions. Furthermore, the stability of iron ions in the deodorizing solution after 10 months was significantly improved by adding ammonium sulfate. Furthermore, after 10 months had elapsed, the ammonia deodorizing effect of Comparative Example 2 and deodorizing paper with a molar ratio of ammonium sulfate and ferrous sulfate of 1.5/1 was investigated. That is, Comparative Example 2 and the deodorizing paper were pasted on the inner wall of No. 10 vacuum desiccator, and 0.5 ml of 3% ammonia water was added (initial ammonia concentration
1300ppm), ammonia concentration becomes 0ppm (approx.
180 minutes later) and further addition of aqueous ammonia in the same manner as above was repeated. The ammonia deodorizing ability (number of moles) at the point at which ammonia is no longer deodorized (breakthrough point) was 0.7 moles per mole of iron in the case of Comparative Example 2, and 4 moles in the case of the deodorizing paper.

[Table] Example 3 A deodorizing stock solution 1 was prepared containing 0.25 mol of ferrous sulfate, 0.25 mol of citric acid, and 0.3 mol of ammonium sulfate as the third component. At the same time, an aqueous solution (Comparative Example 3) was prepared in the same manner as above except that the third component was not contained. A nylon nonwoven fabric (fabric weight: 65 g/m ² ) was immersed in the deodorizing solution of the present invention and the aqueous solution of Comparative Example 3 for 30 minutes, dehydrated using a roller, and then dried at 100° C. for 3 minutes. Based on the weight increase of the nylon nonwoven fabric, iron ions are both 2.0 mmol (the size of the nylon nonwoven fabric
15 x 20 (cm)) was adsorbed. Regarding the nylon nonwoven fabric, the whiteness immediately after sample preparation and after 6 months, the results of qualitative analysis of iron ions, and the deodorizing effect of ammonia and trimethyl mercaptan are shown in Table 3.

[Table] From Table 3, it can be seen that the deodorizing cloth of the present invention has a high degree of whiteness even after being left for 6 months, has excellent stability of divalent iron ions, and has an excellent effect in deodorizing malodorous gas. [Effects of the Invention] The deodorizing material of the present invention is chemically stable for a long period of time, does not decompose, change color, or deteriorate its deodorizing effect, and is resistant to light and heat. Strong, especially paper products, textile products, wood products,
It can be applied to substrates such as inorganic products with good adhesion by containing or coating them. Moreover, it maintains its deodorizing activity for a long period of time in a state of high whiteness and high commercial value, and exhibits an extremely excellent deodorizing effect on bad odors such as ammonia, amines, hydrogen sulfide, mercaptans, and aldehydes.

Claims (1)

[Claims] 1. A deodorizing material containing an oxycarboxylic acid compound having two or more carboxyl groups in the molecule, a ferrous salt, and ammonium sulfate or ammonium sulfite as a third component.