JPH0126301B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical field of the invention] The present invention relates to a deodorizing material and a method for producing the same.
More specifically, a deodorizing aqueous solution containing a water-soluble deodorizing component extracted from plants is brought into contact with a resin that has a highly water-absorbing function or a base material such as a fiber that has it on its surface, and the deodorizing component is introduced into the resin. The present invention relates to an absorbed deodorizing material and a method for producing the same. [Technical background of the invention and its problems] The shapes of deodorants currently used are mainly water-based and alcohol-based aerosol types, plastic types, gel types, sublimation types, pomander types, solid types, It can be divided into one drop type, liquid injection type, and powder type for biological agents. Aerosol type deodorants are used by spraying,
It is suitable for deodorizing both localized and large spaces, but when used in places where it comes into contact with people or food, it is absolutely necessary that it be harmless. However, if used for a long time, the non-volatile deodorizing ingredients will adhere to the utensils and contaminate them. Certain deodorants (e.g. glyoxal), in solid or powder form, dry to a highly hygroscopic mass, and although their remarkable properties make them excellent and easy to use, the deodorant It is generally known that it is difficult to powderize it alone, and that special technology is required to powder it (Japanese Patent Application Laid-Open No. 49-35542).
issue). Moreover, the solid type, liquid injection type, and powder type are suitable for local deodorization, but are not suitable for deodorizing large spaces due to their usage form. There are also deodorizing methods that use physical adsorption without using deodorants, such as methods that adsorb odor gases on porous surfaces such as activated carbon or zeolite, but they are not suitable for local deodorization. Although it can be used as is, to deodorize large spaces, the odor gas is collected in one place and forced into contact with porous materials using methods such as forced ventilation to obtain an effective deodorizing effect. . However, since the gas is passed through a solid packed bed, there is a drawback that the gas resistance is large and the power consumption for ventilation is large. [Objective of the Invention] The object of the present invention is to eliminate the drawbacks of currently used deodorants, to provide a deodorizing agent that can be used both locally and in large spaces, and whose deodorizing effect can last for a long time. The object of the present invention is to provide a deodorizing material that has good deodorizing efficiency, is easy to use, and is economical, as well as a manufacturing method. [Summary of the Invention] The deodorizing material of the present invention for achieving this purpose has the following features:
By selecting an appropriate carrier, deodorants that have been difficult to use can be easily loaded onto the carrier, and, like the above-mentioned glyoxysal, the remarkable properties obtained by drying can be easily activated. It was obtained by focusing on the above, and has super absorbent resin fibers on the surface of a fibrous base material that retains its shape even when it comes in contact with water. It is characterized by having a sheet-like shape as a whole, in which deodorizing ingredients with poor evaporability are absorbed. In addition, in the method of the present invention, a material having a super absorbent resin on the surface of a fibrous thread, and a deodorizing component that is water-soluble and has a lower evaporability than water, are dissolved in water, and the pH is 4 or more.
The water absorbed by the superabsorbent resin is removed by contacting it with a deodorizing aqueous solution containing a strong electrolyte of 1% by weight or less and an organic solvent concentration of less than 50% by weight, and then drying at a temperature below the volatilization temperature of the deodorizing component. It is characterized by removing. As a result of intensive research to improve the above-mentioned drawbacks of currently used deodorants, the present inventors found that
By absorbing an aqueous solution containing a water-soluble deodorizing ingredient extracted from plants into a resin with a highly water-absorbing function or fibers having the resin on its surface, and drying this, or by repeating this operation, a highly water-absorbing It has been found that a deodorizing component can be concentrated in a resin having a sexual function or in a resin on the surface of fibers. Furthermore, it has been found that the more deodorizing components are attached to this resin or the resin on the fiber surface, the more the odor removal rate is improved and the effective time of deodorization becomes longer. The present invention was arrived at based on this knowledge. [Specific Examples of the Invention] According to the present invention, a resin having a highly water-absorbing function or a fiber resin having the same resin on the surface (either the outer surface or the inner surface) contains a water-soluble deodorizing component extracted from a plant. A deodorizing material is obtained by absorbing an aqueous solution and drying it. A resin having a highly water-absorbing function or a resin on the surface of a fiber has the ability to absorb water up to 30 to 1000 times its own weight in pure form. This type of material is known for its use as an absorbent material for sanitary napkins. The resin having a highly water-absorbing function used in the present invention is a resin (available in powder or granule form) obtained by crosslinking an electrolyte polymer having an ionic group. For example, saponified or partially saponified products of acrylate polymers, crosslinked products of water-soluble polymers having anionic groups such as sodium polyacrylate, products obtained by graft polymerizing and saponifying acrylate monomers onto starch, amylose, polyvinyl alcohol, etc., or partially saponified products. You can give things that have been saponified. However, resins with highly water-absorbent functions are not limited to these; water-soluble polymers and highly hydrophilic polymers whose water content has been increased by crosslinking or other means than ordinary resins and fibers are also available. All of them can be used as resins or fibers with high water absorption function for use in the present invention. The amount of deodorizing aqueous solution absorbed by the highly absorbent resin is about 30 times its own weight, which is a fraction of the amount of pure water. This is thought to be due to various substances contained in the deodorizing aqueous solution inhibiting the water absorption function. The deodorizing aqueous solution to be absorbed into a super absorbent resin requires the following conditions due to the water absorption mechanism of the resin. First, the pH of the liquid must be 4 or higher. When the pH is less than 4, the water absorption ability of the resin decreases rapidly. Furthermore, if the strong electrolyte is dissolved in an amount exceeding 1% by weight, the water absorption capacity will decrease rapidly. Furthermore, if an organic solvent is dissolved, the water absorption capacity decreases, but especially if the concentration of organic solvent is 50% by weight or more, especially 40% by weight.
Above that, the water absorption capacity decreases rapidly. Generally, the methods for removing odorous gases include bringing the odorous gas into contact with a deodorant and removing the odorous gas through a reaction or other action, or bringing the odorous gas into contact with a porous material such as activated carbon to adsorb the odorous gas. There is a way to remove it. As mentioned above, the adsorption removal method using a porous material is conveniently used for local deodorization, for example, deodorization in a refrigerator. In addition, treatment of large amounts of odor gas is used industrially, but it is also used for medium-sized industrial purposes, such as fish, meat, and bread processing factories and sales floors, as well as apartments, offices, etc. rooms, vehicles, and aircraft interiors. It is rarely used for deodorization because it is not convenient and consumes a lot of power. Spraying a deodorizing aqueous solution is convenient, but as mentioned above, it poses safety issues for people and food, and there is a possibility of contamination due to adhesion to equipment, so it is not recommended for hotels, offices, etc. It cannot be used in places where the aesthetics may be damaged, such as in apartments, cars, and aircraft. Furthermore, in food processing plants and the like, deodorizing liquid comes into direct contact with the liquid, so even if it is harmless, it is difficult for the senses to accept it. To compensate for these drawbacks, if the deodorizing liquid is absorbed or adsorbed onto a solid, and the odor gas and deodorizing component are brought into contact and reacted on the solid surface to remove the odor gas, the deodorizing liquid will prevent contamination due to adhesion, etc. It is possible to eliminate sensory difficulties in use. In view of these points, in the present invention, a resin with a high absorption mechanism is used as a binder for the deodorizing component, and the deodorizing component is absorbed into the resin as an aqueous solution.
Drying removes only the moisture and fixes the non-volatile deodorizing ingredients inside and on the surface of the resin. When superabsorbent resin absorbs water, it becomes gel-like and difficult to handle, so it is necessary to remove water to make it easier to handle. Absorbed moisture cannot be removed sufficiently by applying pressure, so it is best to dry it by applying heat. The drying temperature may be 100°C or lower, but is preferably 80°C or lower in view of the heat resistance of the resin or fiber. Once dried to remove water, if the non-volatile deodorizing active ingredient is still attached and the aqueous solution containing the deodorizing ingredient is brought into sufficient contact with the superabsorbent resin again, the amount of deodorizing will be approximately the same as the amount absorbed the first time. Absorbs odor aqueous solutions. When this resin is dried again, only the water is removed and the effective deodorizing ingredient remains. In other words, when the deodorizing active ingredient is absorbed into the resin mat in the form of an aqueous solution, most of it is absorbed by crosslinking the interfiber voids, but by drying, the crosslinked water surface Since the tension is eliminated, it is extremely unlikely to adhere to each of the resins themselves and form a film surface in the gaps between the resins.
Even in repeated adhesion and drying processes, stable overlapping adhesion on the initial adhesion surface is possible.
In this way, the deodorizing active ingredient is sufficiently fixed on the surface and inside of the super absorbent resin, and this resin or fibers having the same resin on the surface are used to create filter-shaped, spherical, cubic, or rectangular deodorizing materials. Once manufactured, local deodorization can be achieved through natural ventilation contact with odorous gases.
It can be easily used in the same way as activated carbon and liquid deodorants that have been conventionally used as deodorants. Furthermore, for the removal of medium to large volumes of odorous gases, a filter-like process is used to provide effective contact with the odorous gases through forced ventilation, resulting in efficient deodorization. Therefore, the use of the deodorizing material according to the present invention has the advantage that deodorization can be performed in a harmless, safe, clean, and simple manner from small to large scales. An example of the structure of the deodorizing material according to the present invention will be explained with reference to FIGS. 1 to 3. The illustrated example is in the form of a nonwoven fabric, and the details of the sheet 1 are as shown in FIG. 2, in which filamentous bodies 2 are intertwined. The filament 2 is the third
As shown in the figure, the outer peripheral surface of the main body 3 which does not substantially deform even when it comes into contact with water is coated with a super absorbent resin 4. Such deodorizing materials are used for deodorizing or deodorizing the air filters of building air conditioners and family heating and cooling equipment, the air purifying filters in automobiles, the soles of shoes, and the like. Moreover, products having such a structure can be obtained as commercially available products, except that they contain a deodorizing component. For example, "Lanseal F" manufactured by Nippon Extran Kogyo Co., Ltd. is a typical example. The filament has a length of 7 denier and 51 mm. This nonwoven fabric is the same as that defined in the claims of Japanese Patent Publication No. 58-10508. When used in filters, etc., the main body thread must not be substantially deformed even when it comes in contact with water, that is, it does not dissolve or swell in water, and has shape retention properties when it comes into contact with an aqueous solution of deodorizing ingredients. , which is desirable in order to avoid compromising breathability when subsequently dried. In addition to acrylic, the material of the main thread includes polyethylene, polypropylene, rayon,
Synthetic fiber yarns such as polyester, nylon, and vinylon, semi-synthetic fibers such as rayon and acetate, natural fibers such as hemp, cotton, wool, and silk, as well as glass fibers and carbon fibers can also be used. If desired, it may be a metal thread. The main yarn can be coated with the superabsorbent resin by any suitable method in addition to the method described in Japanese Patent Publication No. 58-10508. In addition, the deodorizing component needs to be an aqueous solution because it is absorbed by the target superabsorbent resin. In this case, suitable deodorizing ingredients include those extracted from the components mainly present in the leaves of Camellia plants described in JP-A No. 58-61751, and Shiraimatsu Shinyaku Co., Ltd. It is commercially available as "Fretsuyu Shiraimatsu". However, it can be used as long as it is soluble in water and has worse evaporability than water. The absorption method of deodorizing ingredients into polymeric substances is as follows:
The sheet is brought into contact with the aqueous solution of the deodorizing component by immersing the sheet or by applying the aqueous solution by spraying or the like. Due to this contact, the polymer material absorbs water and the deodorizing component and swells, as shown in FIG.
After this absorption, it is dried at room temperature or under heating. However, as mentioned above, the heat resistance temperature of the main body yarn and the volatilization temperature of the deodorizing component should be lower than that. The absorption and drying operations may be carried out only once, but if the operations are carried out multiple times as in the examples described later, more deodorizing ingredients can be absorbed. However, if the number of times is 4 or more, the rate of increase in the amount of absorption will be low considering the number of operations, so it is preferable to do it 3 times or less. In addition to using the obtained deodorizing material as a single sheet, it can also be used by stacking multiple sheets, forming them into an appropriate shape, or holding them with other breathable materials such as wire mesh. do it. On the other hand, many commercially available superabsorbent resins are in the form of powder. In this case, as shown in Figure 5,
The superabsorbent resin powder 6 may be held in the form of a sandwich sandwich between breathable (water-permeable) sheets 5, 5, such as non-woven fabrics. Further, it is also possible to use the super absorbent resin powder by molding it into an appropriate shape using an appropriate binder. However, these embodiments do not have a sufficient deodorizing effect compared to the deodorant material according to the present invention. [Examples of the Invention] The present invention will be explained in more detail below with reference to Examples. <Examples 1 to 3, Comparative Examples 1 to 2> Extracts mainly from the leaves of plants of the Camellia family were used as a deodorizing ingredient (see JP-A No. 58-61751), and 5% by weight of this and 0.5% by weight of polypropylene glycol. %,
Deodorizing aqueous solution with a composition of 94.5% water (PH5.7)
(Frescar 800M, manufactured by Shiraimatsu Shinyaku Co., Ltd.) and various super absorbent resins or fibers (3 cm x 3 cm non-woven fabric)
The sample was immersed for a minute and the amount of liquid absorbed per gram of resin or fiber was measured. The results are shown in Table 1.

[Table] The amount of liquid absorbed is determined by removing the soaked resin or fiber from the liquid and dehydrating it for about 3 minutes using a centrifugal force of about 300 g.
This is the value obtained by measuring the weight and subtracting the weight before immersion. The samples used in the comparative examples and examples are as follows. Comparative Example 1 “FS 6200” manufactured by Nippon Vilene Co., Ltd. Comparative Example 2 “FR 285” manufactured by Nippon Vilene Co., Ltd. Example 1 “Aqua Keep” manufactured by Seitetsu Kagaku Co., Ltd. Example 2 “Arasorp” manufactured by Arakawa Chemical Co., Ltd. ” Example 3 “Lanseal-F” manufactured by Nippon Exlan Kogyo Co., Ltd. Examples 1 and 2 are super absorbent resins, and 3 is a fiber with a super absorbent resin. Comparative Examples 1 and 2 are air conditioning filters that are made of polyester fiber and are commonly used. As a result, it can be seen how well the superabsorbent resin or fiber absorbs the deodorizing aqueous solution. <Examples 4 and 5> The above-mentioned "Frescar 800M" (Example 5),
A deodorizing liquid with a pH of 2.1 containing 5% by weight of divalent iron ions and a small amount of L-ascorbic acid (Anico).
Super absorbent fiber "Lanseal-F" (3 cm x 3 cm non-woven fabric) manufactured by "Anico" (Example 4) manufactured by Co., Ltd.
was absorbed into. The results are shown in Table 2.

[Table] When observed under a microscope after drying at 60°C for 2 hours after absorbing the liquid, it was found that very little of the deodorizing liquid ``Anico'' was absorbed into the fibers, and crystals were deposited on the surface of the fibers. On the other hand, in "Flescar 800M", the deodorizing component is absorbed throughout the fibers, and it is clear that a deodorant liquid with a low pH and containing a strong electrolyte cannot be used in the present invention. <Examples 6 to 11> Super absorbent resin or fibers were immersed in the above-mentioned deodorizing liquid "Frescar 800M" for 5 minutes, and dried at 80°C for 1.5 hours. After each drying, the deodorizing material (resin or The amount of deodorizing active ingredient absorbed into the nonwoven fabric + deodorizing liquid) was measured, and its ratio and increase rate were measured. The results are shown in Tables 3 and 4.

[Table] The proportion of active ingredients consumed is defined as follows. Proportion of consumed active ingredient = amount of absorbed deodorant active ingredient (gr) x 100 / weight of deodorizing material after drying (gr) The concentration of deodorizing active ingredient in the deodorizing aqueous solution used for absorption is 5wt %, it clearly shows that the deodorizing active ingredient is efficiently concentrated within the superabsorbent resin or fiber.

[Table] The increase rate is defined as follows. Increase rate = increase amount of absorbed deodorizing active ingredient (gr)
×100/Amount of deodorizing component before absorption (gr) The superabsorbent resins or fibers used in the examples shown in Tables 3 and 4 are as follows. Examples 6, 9 “Aqua Keep” super absorbent resin manufactured by Tetsutsu Kagaku Co., Ltd. Examples 7, 10 Examples 8, 11 of “Arasoap” super absorbent resin manufactured by Arakawa Chemical Co., Ltd. 8, 11 “ Lanseer-F" Super Water Absorbent Fiber From the results shown, the amount of deodorizing ingredients absorbed increases as the number of times of soaking and drying increases, but the rate of increase decreases considerably after 4 times. From an economic standpoint, it is found that it is preferable to repeat the process about 2 to 3 times. <Examples 12 to 23> When 2 gr of super absorbent resin powder or fiber (nonwoven fabric) is immersed in the above-mentioned deodorizing liquid "Flescar 800M" for 5 minutes, dried at 80°C for 1.5 hours, and this operation is performed once. The process was repeated twice to create a deodorizing material and investigate its odor gas removal performance. The dried superabsorbent resin was wrapped in a sandwich shape with 200 mesh polypropylene cloth to a size of 10 cm x 15 cm. The dried superabsorbent fibers were cut into pieces of 10 cm x 15 cm. These deodorizing materials have an inlet odor concentration of 2-8 ppm of ammonia, 0.2-1.3 ppm of trimethylamine, and 0.01-~ of hydrogen sulfide.
0.15 ppm and methyl mercaptan in the range of 0.05 to 1.05 ppm were mixed with air and brought into contact with the deodorizing material for about 0.5 seconds. Table 5 shows the odor gas removal rate at this time.

[Table] Removal rate was defined as follows. Removal rate = (inlet odor concentration - outlet odor concentration) ×
100/Inlet odor concentration The super absorbent resins or fibers used in the examples shown in Table 5 are as follows. Examples 12, 15, 18, 21: Example 13, 16, 19, 22 of "Aqua Keep" super absorbent resin manufactured by Tetsuto Kagaku Co., Ltd. Example 14 of "Arasoap" super absorbent resin manufactured by Arakawa Chemical Co., Ltd. , 17, 20, 23: "Lanseal-F" manufactured by Nippon Exlan Kogyo Co., Ltd. Super water-absorbent fiber From the results in Table 5, it was found that the deodorizer made by absorbing a deodorizing aqueous solution into a super absorbent resin or fiber and drying it. It has become clear that the odor material has a sufficient deodorizing function. Furthermore, it has become clear that the odor gas removal rate is better when the deodorizing material is soaked and dried twice than when it is soaked and dried once. In addition, as shown in Table 3, the amount of deodorizing active ingredients absorbed into resins and fibers is determined by the number of times the dipping and drying operations are repeated.
In the case of 1 time, it is about twice as much as 1 time, so
It is estimated that if the operation is repeated twice, the effective period of deodorizing the deodorizing material will be approximately doubled. The reason why the odor gas removal rate shown in Table 5 is better for the fibrous material than for the resinous material is presumed to be due to the difference in the contact area between the deodorizing material and the gas.
For the same weight of resin and fiber, the fibrous material has a larger surface area. <Examples 24 to 26> In order to increase the deodorizing effect of the deodorant material according to the present invention,
This is applied to the process of processing the deodorant material into a plate shape and bringing the odor gas into contact with it through forced ventilation. The pressure loss during ventilation of the deodorizing material was measured. The air velocity passing through the deodorizing material was 0.3 m/sec.
The results are shown in Table 6.

[Table] The superabsorbent resins or fibers used in the examples shown in Table 6 are as follows. Example 24: “Aqua Keep” manufactured by Seitetsu Kagaku Co., Ltd. Example 25 of super-absorbent resin: “Arasoap” manufactured by Arakawa Chemical Co., Ltd. Example 26 of super-absorbent resin: “Lanseal-F” manufactured by Nippon Exlan Kogyo Co., Ltd. ” Super water-absorbing resin If you try to increase the deodorizing efficiency by forcing the indoor odor gas into contact with the deodorizing material through strong ventilation,
From the results shown in Tables 5 and 6, it can be seen that the fibrous deodorizing material (nonwoven fabric) is the most effective. [Effects of the Invention] As described above, according to the deodorizing material of the present invention, the deodorizing material is in the form of a fibrous sheet, and it is possible to deodorize while being used in the form of a filter, etc. Since the deodorizing component is absorbed into the super absorbent resin fiber, the contact area with the gas is larger than that of powdered resin, etc., and the deodorizing effect is improved, as explained quantitatively in the example above. becomes higher. In addition, according to the method for producing a deodorizing material of the present invention, the deodorizing component can be reliably absorbed into the super absorbent resin, and water is removed, so that the deodorizing component can be absorbed into or on the surface of the super absorbent resin. It comes to exist in a concentrated form and exhibits a sufficient deodorizing effect.

[Brief explanation of drawings]

Fig. 1 is a perspective view showing one form of the deodorizing material according to the present invention, Fig. 2 is an enlarged view of part A thereof, Fig. 3 is a longitudinal cross-sectional view of the filament, and Fig. 4 is a cross-sectional view of the deodorizing component aqueous solution. FIG. 5 is a longitudinal cross-sectional view showing the swollen state of the filamentous body due to contact, and FIG. 5 is a cross-sectional view showing another example of the deodorizing material. DESCRIPTION OF SYMBOLS 1... Sheet, 2... Thread-like body, 3... Main body thread, 4... Super water absorbent resin, 6... Super water absorbent resin powder.

Claims (1)

[Claims] 1. A fibrous base material that retains its shape even when in contact with water has super-absorbent resin fibers on its surface, and the super-absorbent resin fibers have a higher evaporability than water. A deodorizing material that absorbs bad deodorizing ingredients and is in the form of a sheet as a whole. 2 A material having a super absorbent resin on the surface of the fibrous filament and a deodorizing component that is water-soluble and has lower evaporability than water are dissolved in water, the pH is 4 or more, and the content of strong electrolyte is 1 weight % or less and an organic solvent concentration of less than 50% by weight, and then drying at a temperature below the volatilization temperature of the deodorizing component to remove moisture absorbed by the super absorbent resin. A method of manufacturing deodorant.