JPS60259267A - Deodorizing material and its production - 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] [Technical field of invention] The present invention relates to a deodorizing material and a method for producing the same.

More specifically, we use a deodorizing aqueous solution containing water-soluble deodorizing ingredients extracted from plants, and #! The present invention relates to a deodorizing material that is brought into contact with a resin of a base material such as a cone and absorbs a deodorizing component into the resin, and a method for producing the same.

[Technical background of the invention and its period] The shapes of deodorants currently used are mainly water-based and alcohol-based aerosol types, plastic-like, gel-like, sublimation-type, pomander-type cylinders, -Can be divided into droplet type, liquid injection type, and powder type for biological agents. Since aerosol deodorizers are used by spraying, they are suitable for deodorizing both localized areas and large spaces, but they are harmless when used in areas where they will come into contact with people or food. This is an absolutely necessary condition. However, if you use it for a long time, the non-volatile deodorizing ingredients will stick to your 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 known that it is difficult to powderize it alone, and that special technology is required to powder it (Japanese Patent Laid-Open No. 49-35542).
Gin). 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 waste 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, and to provide a deodorizing agent that can be used both locally and in large spaces.
To provide a deodorizing material that can maintain a deodorizing effect for a long time, has good deodorizing efficiency, is easy to use and is economical, and a manufacturing method.

[Summary of the Invention] To achieve this object, the deodorant material of the present invention is such that if a suitable carrier is selected, a deodorant that has been difficult to use can be easily loaded onto the carrier, and the deodorant can be easily loaded with the glyoxal. It was obtained by focusing on the fact that the remarkable properties obtained by drying can be easily activated. It is characterized by absorbing deodorizing ingredients.

Furthermore, in the method of the present invention, at least the surface has a super-absorbent function! This method is characterized in that a base material made of 61 fat is brought into contact with a water-soluble deodorizing component liquid extracted from plants, and then dried to fix the deodorizing component in the resin.

In order to improve the drawbacks of currently used deodorants as described above, the present inventors have conducted extensive research and have developed a resin with a highly water-absorbing function or fibers having the resin on the surface extracted from plants. Absorbs an aqueous solution containing water-soluble deodorizing ingredients,
It has been found that by drying this and by repeating this operation, it is possible to concentrate the deodorizing component in the resin having a highly water-absorbing function or the resin on the surface of the fiber. Furthermore, it has been found that the greater the amount of deodorizing components attached to this resin or the resin on the fiber surface, the better the odor removal rate will be, and at the same time, the effective deodorizing time will be longer. The present invention was arrived at based on this knowledge.

Example of combination of L total 1!1] According to the present invention, HN Mt having a resin having a highly water-absorbing function or having the same resin on the surface (either the outer surface or the inner surface)
A deodorizing material is obtained by absorbing an aqueous solution containing a water-soluble deodorant component extracted from a plant into the vA fat and drying it.

ri:+Water Absorption+11 A resin having the function Ij 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 kind of material is known for its use as absorbent material 1 of sanitary napkins.

The resin with super absorbent function used in the present invention includes:
Water-soluble polymers with anionic properties, such as saponified or partially saponified acrylate polymers, sodium polyacrylate, etc., which are crosslinked electrolyte polymers with ionic groups (available in powder or granule form) Examples include crosslinked products of starch, amylose, polyvinyl alcohol, etc., obtained by graft polymerization of acrylate monomers and saponification, or partially saponified products.

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.

JL is a deodorizing aqueous solution that is absorbed by resin with high water absorption function.
i is about 30 times its own weight, which is a fraction of that 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 solution needs to 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, and particularly when the concentration of the organic solvent becomes 50% by weight or more, particularly 40% by weight or more, the water absorption capacity decreases rapidly.

Generally, the methods for removing odor residue include contacting the odor gas with a deodorant and removing the odor gas through a reaction or other action, or contacting it with a porous material such as activated carbon to adsorb the odor 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 volumes of odor gas is used industrially, but it is also used in medium-sized industries, such as fish, meat, and bread processing factories and sales floors, as well as apartments, offices, and other rooms, vehicles, and aircraft interiors. It is rarely used for deodorization because it is not convenient and consumes a lot of power.

The method of spraying a deodorizing aqueous solution is simple, but
As mentioned above, there are safety issues for people and food, and there is a possibility of contamination due to adhesion to equipment, so it cannot be used in places where there is a risk of damaging the aesthetics, such as hotels, offices, condominiums, cars, and aircraft. In addition, in food processing plants, etc., the deodorizing liquid comes into direct contact with the liquid, so even if it is harmless, it is difficult to accept the sense of smell. If gas and deodorizing ingredients are brought into contact and reacted to remove odor gas,
It is possible to eliminate contamination due to adhesion of the deodorizing liquid and sensual difficulty in use.

In response to these points, Kanmi 5 In the present invention, the deodorizing component is absorbed into the resin as an aqueous solution by using a resin with a highly absorbent function, and then dried to remove only the moisture, thereby creating a non-volatile deodorizing component. is fixed 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. Since absorbed moisture cannot be removed even by applying pressure, it is best to dry it by applying heat. The drying temperature may be below too'a, but is preferably below 80°C in view of the heat resistance of the resin or fiber.

Once dried to remove moisture, and with the non-volatile deodorizing active ingredient still attached, the superabsorbent resin is brought into sufficient contact with the aqueous solution containing II) deodorizing λ component. Absorbs deodorizing aqueous solution. When this resin is dried again, only the water is removed and the deodorizing active ingredient remains. In this way, the deodorizing active ingredient is sufficiently fixed on the surface and inside of the super absorbent resin, and using this resin or fibers having the same resin on the surface, a filter-like deodorizing material in the shape of a sphere, a cube, or a rectangular parallelepiped is made. Once produced, it can be easily used for localized deodorization by contact with odor gas through natural ventilation, similar to activated carbon and liquid deodorants that have been conventionally used as deodorizing materials. Furthermore, filter-like processing is used to remove medium to large volumes of odor gas.
Forced ventilation provides effective contact with odorous gases and provides 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 example shown is in the form of a non-woven fabric.
As shown in the second rgJ, the filament bodies 2 are intertwined. As shown in FIG. 3, the thread-like body 2 has a shape in which the outer peripheral surface of a main body 3 that 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 to deodorize or deodorize air filters for building air conditioners and household heating and cooling equipment, air purifying filters for automobile interiors, and the soles of shoes.

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 Nihon Exlan Kogyo Co., Ltd.
is a typical example. The filament is 7 denier x 5
It is 1mm long. This non-woven fabric is
This is the same as defined in the claims of Publication No. 0508.

When used in filters, etc., the main body system must not be substantially deformed when it comes in contact with water, that is, it will not dissolve or swell in water, and it will retain its shape when it comes in contact with an aqueous solution of deodorizing ingredients. This is desirable in order to prevent the air permeability from being impaired when the material is dried and then dried. Materials for the main body include acrylic, synthetic fibers such as polyethylene, polypropylene, rayon, polyester, nylon, and vinylon, semi-synthetic fibers such as rayon and acetate, and linen,
Natural fibers such as cotton, wool, and silk, as well as glass fibers and carbon fibers, can also be used. If necessary, it may be a thread-like metal.

The main body system can be coated with the superabsorbent resin by any suitable method in addition to the method described in Japanese Patent Publication No. 5B-10508.

In addition, the deodorizing component needs to be water-soluble since it is absorbed by the target superabsorbent resin. In this case, the deodorizing component is, for example, JP-A-58-1. Preferably, the extract of components mainly present in the leaves of the Camellia family plant described in Publication No. 61751, manufactured by Shiraimatsu Shinyaku Co., Ltd.
It is commercially available as ``Fresh Shiraimatsu''.

However, it can be used as long as it is soluble in water and has worse evaporability than water.

As a method for absorbing the deodorizing component into the polymeric substance, the sheet is immersed in an aqueous solution of the deodorizing component, or the sheet is brought into contact with the aqueous solution by spraying or the like. As a result of 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 temperature should be lower than the heat resistance temperature of the main body and the volatilization temperature of the deodorizing component. 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 it is repeated more than 4 times, the rate of increase in the amount of absorption will be low considering the number of operations, so it is preferable to repeat it 3 times or less.

In addition to using the 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. good.

On the other hand, many commercially available superabsorbent resins are in the form of powder. In this case, as in No. 51M, the super absorbent resin powder 6 may be held in a sandwich-like manner between breathable (water permeable) sheets 5.5 such as nonwoven fabrics.

Further, it is also possible to use super absorbent resin powder by molding it into a suitable shape using a suitable binder.

[Embodiments of the invention] The present invention will now be described in more detail with reference to Examples.

<Examples 1 to 3, Comparative Examples 1 to 2> Extracts of plants of the Camellia family, mainly from Kabu, were used as a deodorizing ingredient (
(see Japanese Patent Application Laid-open No. 58-61751) and 5% by weight of this
, polypropylene glycol 0.5% by weight, water 94.5%
Various super absorbent resins or fibers (30@x3cm non-woven fabric) are immersed in a deodorizing aqueous solution (pH 5, 7) (Fresca-800M, manufactured by Shiraimatsu Shinyaku Co., Ltd.) having a composition of % by weight for 5 minutes. The amount of liquid absorbed per gram of fiber was measured.

The results are shown in Table 1.

The amount of liquid absorbed by the super absorbent resin or fiber (gr/resin, fiber M1gr) The amount of liquid absorbed is approximately 3.
After dehydration for about 3 minutes with a centrifugal force of 00 g, the tonne 771 was measured, and the value was obtained by subtracting the value of the east bank before immersion. The samples used in the comparative examples and examples are as follows.

Comparative Example 1.11 rFS 6200J manufactured by Vilene Co., Ltd. Comparative Example 2. Same as above rFR285J °J,! Example 1. "Aqua Keep" manufactured by Seitetsu Kagaku Co., Ltd. 'Example 2. “Ara Soap” manufactured by Arayo Kagaku Co., Ltd. Example 3. "Lanseal-F" manufactured by Nihon Exshin Kogyo Co., Ltd. Examples 1 and 2 are super absorbent resins, and 3 is a fiber with super absorbent resin. In Comparative Examples 1 and 2, the material is polyester #! This is an air conditioning filter commonly used in textiles.

As a result, it can be seen how well the superabsorbent resin or fiber absorbs the deodorizing aqueous solution.

<Example 4.5> The above-mentioned Fresca-800MJ (Example 5) and a deodorizing liquid with a pH of 2.1 containing a small amount of L-ascorbic acid and a small amount of iron divalent ion 7s deodorizing ingredients ( Manufactured by Anico Co., Ltd.
Aniko' (Example 4) was absorbed into the superabsorbent fiber R Lanseal-FJ (3 cm x 3 cm non-woven I5). The results are shown in Table 2.

Table 2: Absorption amount of deodorant liquid to super absorbent m fibers (gr/
#jitagr) After drying at 60°C for 2 hours after absorbing the liquid, it was observed under a microscope that almost no deodorant liquid "Anico" was absorbed into the fibers, and crystals were precipitated on the surface of the fibers. On the other hand, "Fresca"
At 800 MJ, the deodorizing component is absorbed into the entire fiber, and it is clear that deodorant liquids with low pH and containing strong electrolytes cannot be used in the present invention.

<Examples 6 to 11> A super absorbent resin or fiber was immersed in the above-mentioned deodorizing liquid "Fresca-800MJ" for 5 minutes, and dried at 80"0 for 1.5 hours, and the deodorizing material was dried each time. The amount of consumed active ingredient absorbed into (resin or nonwoven fabric + deodorizing liquid) was measured, and its ratio and increase rate were measured by t-measurement. The results are shown in Tables 3 and 4.

p! Table S3: Percentage of active ingredients in deodorizing material (%) The ratio of consumed active ingredients is defined as follows.

Percentage of active ingredient consumed - amount of deodorizing active ingredient absorbed (gr
) X l 00 / Weight of deodorant material after drying gr) Concentration of deodorizing active ingredient in deodorizing aqueous solution used for absorption is 5% by weight
This clearly shows that the deodorizing active ingredient is efficiently concentrated within the superabsorbent resin or fiber.

Table 4: Increase rate (%) of deodorizing active ingredients in deodorant material The increase rate is defined as follows.

Increase rate = increase amount of absorbed deodorizing active ingredient (gr) x 10
0/Amount of deodorizing ingredient before absorption (g'') The super absorbent resins or fibers used in the examples shown in Table 3.4 are as follows.

Examples 6 and 9. Examples 7 and 10 of “Aqua Keep” super absorbent resin manufactured by Seitetsu Kagaku Co., Ltd. Manufactured by Arakawa Chemical Co., Ltd. - "Arasoap" super absorbent resin Examples s, ii, 1 "Lanseal-F" made by Mokkou Kuslan Kogyo Co., Ltd. Super water absorbent fiber From the results shown, the number of times of dipping and drying is repeated. Although the amount of the deodorizing component absorbed increases due to the increase in the amount of deodorizing ingredients, the rate of increase becomes considerably small after 4 times, so from an economic standpoint, it is found that it is preferable to repeat the process about 2 to 3 times.

<Examples 12 to 23> The above-mentioned deodorizing liquid [2 gr of super absorbent resin powder or fiber (non-woven fabric) was immersed in Fresca-800MJ for 5 minutes,
When drying at ℃ for 1.5 hours and performing this operation once,
The process was repeated twice to create a deodorizing material, and its performance in removing odor gas was investigated. The dried super absorbent resin is wrapped in a sandwich shape with 200 mesh polypropylene cloth.
The size was 0 cm intestine x 15 cm. The dried super absorbent fibers were cut into pieces of 10 cm x 15 cm. These deodorizing materials have an inlet odor concentration of 2% ammonia.
~8 ppm, trimethylamine 0.2-1.3 ppm
, mixed with air in the range of 0.01 to 0.15 ppm hydrogen sulfide and 0.05 to 1.05 PPm of methyl mercaptan,
It was brought into contact with the deodorizing material for about 0.5 seconds. Table 5 shows the odor gas removal rate at this time.

The removal rate was defined as follows.

Removal rate = (person 1j odor concentration - output [1 odor source degree) x 10
0/person [1 Odor source degree Super water absorbent resin used in the examples shown in Table 5 or t
The IA fibers are as follows.

Examples 12, 15, 18, 21 + "Aqua Keep" manufactured by Tetsutsu Kagaku Co., Ltd. Super water absorbent resin Examples 13, 16, 19, 22: "Arasorb j" manufactured by Arakawa Chemical Co., Ltd. Super water absorbent resin Example 14 , 17, 20, 23: 11 "Lanseal-F" manufactured by Exlan Kogyo Co., Ltd. High "Ill Aqueous m1Illk" From the results in Table 5, it was found that a super absorbent resin or fiber was made to absorb a deodorizing aqueous solution and dried. It was revealed that the deodorizing material had sufficient deodorizing function.In addition, the removal rate of odor gas was better when soaked and dried twice than when the deodorizing material was soaked and dried once. It was also found that the amount of deodorizing active ingredients absorbed into resins and fibers was
As shown in the table, the number of times the dipping and drying operations are repeated twice is about twice as long as the number of times repeated, so the effective period of deodorizing material is longer when the immersion and drying operations are repeated twice. It is estimated that the number will approximately double.

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 improve the deodorizing effect of the deodorizing material according to the present invention, the deodorizing material is processed into a plate shape and the odor gas is forced into contact with the plate. The pressure loss when the deodorant was ventilated was measured before absorbing the liquid, after absorbing the liquid, and after drying. The air velocity passing through the deodorant is 0.3
1/see. The results are shown in Table 6.

Table 6: Ventilation pressure loss (nmAq) of deodorizing material The super absorbent resins or mwi used in the examples shown in Table 6 are as follows.

Example 24: "Aqua Keep" super absorbent resin manufactured by Seitetsu Kagaku Co., Ltd. Example 25: "7 Lamp" super absorbent resin manufactured by Arayo Kagaku Co., Ltd. Example 26: "Lan Seal" manufactured by Nippon Exlan Kogyo Co., Ltd. -F” Super water-absorbent resin When trying to increase the deodorizing efficiency by forcing indoor odor gas into contact with the deodorizing material using strong ventilation, the results shown in Tables 5 and 6 show that fibrous It can be seen that deodorizing material (non-woven fabric) is the most effective.

[Effects of the Invention] As described above, the present invention is based on a completely new method of making a super absorbent resin absorb a water-soluble deodorizing component,
Provides advantages such as excellent handling.

In particular, in the method of the present invention, since drying is performed after contact with the deodorizing component liquid, the deodorizing component is suitably fixed in the superabsorbent resin, resulting in the advantage that the deodorizing effect can be maintained for a long time.

[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. A vertical cross-sectional view of the filament in the *m state due to contact, and FIG. 5 is a cross-sectional view showing another example of the deodorizing material. l@・Sheet 2e・Filiform body 3・・Body system 4・・Super absorbent resin 6・・Super absorbent resin powder Patent applicant Tsukishima Kikai Co., Ltd. Representative patent attorney Yoshihisa Nagai Figure 1 Figure 2 Figure 3-f Iko correction form (spontaneous) 3e1 August a=) day 1, 1985! Display of 44 cases 1982 Patent Application No. 115789 2 Name of the invention Deodorizing material and its manufacturing method 3 Relationship with the case of the person making the amendment Patent applicant address Name Tsukishima Kikai Co., Ltd. 4 Agent 101 5 Order for amendment Date Spontaneous amendment 6 Description subject to amendment, Detailed explanation of the invention column 7 Contents of the amendment As shown in the attached sheet (1) Description, Detailed explanation of the invention column, page 9, 1 line 1''
"Using resin" is revised to "Using resin as a binder for deodorizing ingredients." (2) Enclosed, page 9, line 15: ``Insert the following sentence between ``remain.j'' and ``in this way.'' ``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 bridging the interfiber voids, but by drying,
Since the surface tension of the crosslinked water is eliminated, it is extremely unlikely that the resin will adhere to each other and form a film surface in the resin voids, making it stable even during repeated adhesion and drying processes. This allows for superimposed adhesion on the initial adhesion surface. ”

Claims (4)

[Claims] (1) A deodorizing material characterized in that a water-soluble deodorizing component extracted from plants is absorbed into a base material whose at least the surface is a resin having a highly water-absorbing function. (2) A base material whose surface is made of a resin having a highly water-absorbing function is brought into contact with a water-soluble deodorizing component liquid extracted from plants, and then dried to fix the deodorizing component in the resin. A method for producing a deodorizing material characterized by the following. (3) The deodorizing component liquid has a p)I of 4 or more, a strong electrolyte content of 1% by weight or less, and an organic solvent content of 50% by weight or less. A method of manufacturing deodorant. (4) The method for producing a deodorant material according to claim 1, wherein the content of the deodorizing component in the resin is increased by repeating contact and drying.