JPH0422583B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention is a ceramic material that has a deodorizing effect, more specifically, it has a deodorizing effect itself, and by supporting various deodorants or deodorizing ingredients, it can be used as a deodorizer. This invention relates to ceramic materials that further enhance odor effects. BACKGROUND TECHNOLOGY In general, deodorants are broadly classified into sensory deodorization, chemical deodorization, physical deodorization, and biological deodorization based on their mechanism of action, and commercially available deodorant preparations are effective because they have one of these mechanisms of action. It has been devised to demonstrate. As a result of extensive research into deodorizing carriers that can further enhance the deodorizing effects of the various deodorizing agents mentioned above, the present inventors have discovered that generally known unglazed materials such as earthenware, pottery, porcelain, etc. It was recognized that the balance between retention and volatility of the deodorant and the adsorption and decomposition of malodorous components were still insufficient, and it was difficult to maintain the desired deodorizing or deodorizing effect over a long period of time. In other words, in the above-mentioned unglazed materials, it was generally thought that the greater the pore density, the better the deodorizing effect.However, in reality, if the material is too porous, it tends to become severely clogged and the efficiency decreases. It was observed. In addition, unglazed materials usually have pore diameters that are too large, making it difficult to adjust the pores to the angstrom level, and some malodorous particles may pass through the material, making it impossible to remove odors. In subsequent research, the present inventor found that a ceramic material prepared and sintered using porous coral fossils and/or shellfish fossils has excellent adsorption properties for malodorous component particles and has a deodorizing effect due to its own catalytic action. We have discovered a new fact that this deodorant has an excellent balance of retention and volatility for various deodorants, and that when used as a deodorant carrier, an excellent deodorizing effect can be sustained, and we have hereby developed the present invention. I was able to complete it. Structure of the Invention That is, the present invention relates to a ceramic material having a deodorizing effect, which is made by adjusting porous coral fossils and/or shell fossils with a binder and sintering them. The porous coral fossils and shell fossils used in the present invention are commonly known coral fossils (scientific name:
It may be either Ryukyu coral limestone) or fossil shellfish. Their typical compositions and specific gravity are shown in Table 1 below.

[Table] The ceramic material of the present invention has the above-mentioned coral fossils and/or shellfish fossils as essential components, and is manufactured by mixing this with a suitable binder to prepare a base soil, and then sintering it. Here, as the binder, various conventionally known mineral substances such as Amakusa pottery stone, frog's eye clay, silicate colloid liquid, etc. can be used. There are no particular restrictions on the blending ratio of coral fossils and/or shellfish fossils to the binder, but usually coral fossils and/or shellfish fossils are at least 20% by weight, usually 20 to 90% by weight, based on the weight of the mixture. Preferably, the amount is about 40-70% by weight. Further, the above-mentioned base soil is prepared by simply mixing the raw materials or by adding water and kneading according to a conventional method.
In this case, depending on the form of use of the ceramic material of the present invention, the prepared product is prepared in advance in a suitable shape, such as a container shape for accommodating the deodorant component, or a powder, granule, or gravel capable of impregnating and retaining the deodorant component. It can be made into a shape such as a shape or a plate shape, and furthermore, it can be made into an arbitrary shape such as a flower vase or a doll in consideration of decorativeness. In addition, in order to adjust the pore size of the ceramic material obtained as required, the above preparation may contain organic substances such as a super absorbent resin made by crosslinking an alkali metal salt of isobutene-maleic anhydride copolymer with polyethyleneimine. Water retention agents and the like may also be added and blended. Sintering of the preparation thus obtained is generally carried out under sintering temperature conditions of about 800 to 1000 DEG C., thereby making it possible to obtain the desired ceramic material. By allowing a deodorizing agent to coexist with the ceramic material of the present invention, the deodorizing effect of the deodorant can be further enhanced. There are no restrictions on the deodorant that can be present, and it may be liquid or solid at room temperature, and may have any of the mechanisms of action described above. Therefore, the above-mentioned deodorants should be interpreted in the broadest sense, and are not limited to deodorants that utilize the inclusion, neutralization, and decomposition reactions of malodorous components, but also deodorants that utilize masking effects, etc. It also includes fragrances, fragrances, and the like. The coexistence form of the ceramic material of the present invention and the above deodorant is also arbitrary; for example, a liquid deodorant or a preparation containing the same may be used as it is, or dissolved or suspended in water or other solvent. The deodorant may be impregnated with the material of the present invention in the shape of a container, or a liquid or solid deodorant or a preparation containing the same may be housed in the material of the present invention in the shape of a container. The amount of the above-mentioned deodorizing agent impregnated is determined as appropriate, but it is usually appropriate to range from about 1 to 30% by weight based on the weight of the ceramic material. Thus, the ceramic material of the present invention containing a deodorant can exhibit an excellent deodorizing effect as a deodorant product, and in particular, the deodorizing effect is sufficiently exhibited even in a high temperature range (about 80° C.). In addition, the deodorant product is selected depending on the deodorant that should coexist with it and the shape of the product.
The desired deodorizing effect can be achieved regardless of the type or form of malodorous components. In other words, the above-mentioned product absorbs and absorbs all kinds of bad odors, such as bad odors generated from water or humid places, dried bad-smelling particles floating in the air, and bad odors attached to some kind of carrier material.
Can be deodorized. Therefore, the deodorizing product using the ceramic material of the present invention can be installed in, for example, refrigerators, toilets, cars, rooms, sewage treatment plants, livestock sheds, and other various factories to achieve the desired deodorizing effect. be. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. The coral fossils and shell fossils used in each example are:
Those shown in Table 1 above were used. Example 1 Coral fossil 40.0 parts by weight Amakusa clay 50.0 Frog-eye clay 20.0 Silicate colloid liquid (SiO ₂ content 40%, manufactured by Asahi Denka Kogyo Co., Ltd., trade name "Adelite AT40") 5.0 The above composition was obtained. The components were mixed, molded into a box-shaped container, and then sintered at 800 to 1000°C to obtain a ceramic material of the present invention. This material had a specific gravity of 2.6, a pore volume of 0.57 cc/g, and a water absorption rate of 31%. 120 parts by weight of the obtained ceramic material was added with a deodorant ("Viara 10", manufactured by Koryu Industries Co., Ltd., tea extract,
Ceramic samples impregnated with deodorizer were impregnated with 30 parts by weight of water content (75%) and left to dry naturally for 3 days.
130 parts by weight were obtained. For comparison, a comparative sample was prepared by using activated carbon (granular) instead of the ceramic material of the present invention and impregnating it with a deodorant in the same manner. A 4000 cm ³ airtight container containing certain weights of the ceramic material of the present invention, deodorant-impregnated ceramic sample, activated carbon, and deodorant-impregnated activated carbon sample, and predetermined amounts of ammonia, trimethylamine, acetic acid, and hydrogen sulfide as malodorous substances. The concentration of malodor remaining in the container (mg) after 3 hours and 20 hours was determined by titration method, and the malodor removal rate (%) was determined. The results are shown in Table 2 below. The upper row in the table shows the residual concentration (mg), and the lower row (in parentheses) shows the removal rate (%).

[Table] From Table 2 above, it can be seen that by using the ceramic material of the present invention, the deodorizing effect is further enhanced compared to activated carbon. Example 2 Coral fossil 30.0 parts by weight Shellfish fossil 20.0 〃 Amakusa clay 45.0 〃 Frog-eye clay 5.0 〃 Silicate colloid liquid (same as in Example 1) 4.0 〃 Water retention agent (“KI Gel-20” manufactured by Clarei Soprene Chemical Co., Ltd., Ultrafine particles) 1.0 After mixing predetermined amounts of each of the above components, the mixture was sintered at 800 to 1000°C to obtain a granular ceramic material of the present invention. This material had a specific gravity of 2.1, a pore volume of 0.4 cc/g, and a water absorption rate of about 28%. 200 parts by weight of the obtained ceramic material was impregnated with 50 parts by weight of a deodorizer ("Viala 10E", manufactured by Koryu Kogyo Co., Ltd., carbonized nettle product, water content 73%), and left to air dry for 3 days. A deodorant-impregnated ceramic sample was obtained. The following tests were conducted using the above samples. First, the malodor source gas is adjusted as follows. In other words, take 20g of cormorant feces in a washing bottle, add 50ml of purified water, and heat at 50℃.
The bottle is left in a constant temperature room for 24 hours, and then the generated gas in the air washing bottle is expelled with 50% pure air and collected in a bag, which is used as the odor source gas. On the other hand, a test sample is filled in a glass tubular container, and the entire amount of the malodor source gas 5 adjusted above is passed through the container at a flow rate of 1/min, and the passing gas is collected in a bag. Using this as a sample gas, the concentration of each gas component is measured by the following method. Hydrogen sulfide and methyl mercaptan; by gas chromatography method. Ammonia; by indophenol blue spectrophotometry. Further, as a blank, the malodor source gas 5 was passed through a glass tubular container not filled with a test sample, and the component concentration of the passing gas was measured in the same manner. Table 3 below shows the results of using the ceramic material of the present invention and a sample impregnated with a deodorant as test samples, in comparison with a blank.

[Table] It is clear from Table 3 above that the ceramic material of the present invention exhibits an excellent deodorizing effect. Example 3 Fossil shells 64.0 parts by weight Amakusa china clay 40.0 〃 Silicic colloid liquid (same as in Example 1) 2.0 〃 Water retention agent (same as in Example 2) 2.5 〃 Using each of the above components, mix in the same manner as in Example 2, A granular ceramic material of the present invention was obtained by sintering. This material has a specific gravity of 1.4 and a pore volume of 0.4cc/g
It was hot. Place 4.0g of the above ceramic material on a watch glass, and add 0.38g of the blended fragrance material with the composition shown in Table 4 below.
A perfume-impregnated sample was prepared by impregnating the sample with For comparison, 30% of the preservative diethyl phthalate was added to the same fragrance material.
% by weight and 0.5g of it was added to scented paper (7.5×11.5cm ³ ,
A comparative sample was prepared by uniformly coating 2.6 g of the sample.

【table】

[Table] Each sample above was tested at constant temperature and humidity (temperature 30℃, humidity 50%,
Leave it open in a wind speed of 0.05 m/sec or less for 0 minutes,
After being left for 150 minutes, 270 minutes, and 450 minutes, five panelists evaluated the fragrance retention effect. The results are shown in Table 5 below according to the following criteria. <Judgment Criteria> ○: The fragrance is well-balanced and judged as good by 4 or more panelists △: The fragrance is slightly unbalanced ×: The fragrance is greatly unbalanced

[Table] The blended fragrance materials used in the above test (listed in Table 4) emit a fresh citrus aroma, but when diethyl phthalate, which is commonly used as a preservative, is used, As shown in the table, the balance of fragrance is lost over time and the freshness is greatly impaired. On the other hand, when the ceramic material of the present invention is used, there is very little deterioration of the fragrance.
It can be seen that after 450 minutes, it was significantly superior to the case using the above-mentioned retention agent. Example 4 Coral fossil 43.7 parts by weight Amakusa pottery stone 50.2 Frog-eye clay 5.0 Silicate colloid liquid (same as Example 1) 3.0 Water retention agent (same as Example 2) 1.0 The above ingredients were the same as in Example 1 A plate-shaped ceramic material of the present invention was obtained by mixing and sintering in the same manner. For comparison, instead of using coral fossils in the above, Motoyama Kibushi clay, Kirishima clay, Tokoname clay, Harajime clay, Izumiyama stone, and Amakusa pottery stone were used in the same manner to produce earthenware, pottery, pottery, etc. We created an unglazed material that mimics the typical composition of porcelain. The composition of each plate-shaped product obtained above is shown in Table 6 below.

[Table] Either 100 parts by weight of each of the obtained ceramic material and unglazed ceramic material are used alone, or a deodorizer (
The following deodorizing effect test was conducted using a deodorizing agent-impregnated sample piece prepared by impregnating 5 parts by weight of ``100'' (manufactured by Koryu Kogyo Co., Ltd., vegetable essential oil) in a vacuum container. That is, a fixed amount of ammonia or acetic acid as a source of bad odor was placed in a 3000 cm ³ airtight container, each sample piece was placed in the container, and after being left at 80 ± 2°C for 3 hours,
The odor inside the container was determined by a human panel. The judgment criteria are as follows. <Judgment Criteria> 5: No odor 4: Slight odor but not bothersome 3: Slight odor but acceptable 2: Odor is strong but tolerable 1: Strong irritating odor and cannot be tolerated The results are shown in Table 7 below. Shown below.

[Table] From Table 7 above, the superiority of the ceramic material of the present invention is clear. It can be seen that it can exhibit an excellent deodorizing effect enhancement effect not found in other bisque fired materials. Example 5 Coral fossil 40.0 parts by weight Amakusa china clay 20.0 parts by weight Frog's eye clay 30.0 〃 Silicate colloid liquid (same as Example 1) 15.0 〃 Water retention agent (same as Example 2) 1.5 〃 The above ingredients were used as in Example 1. A plate-shaped ceramic material of the present invention was obtained by mixing and sintering in the same manner. As a result of the same deodorizing test as in Example 4, this product exhibited approximately the same excellent deodorizing effect enhancement effect.

Claims (1)

[Claims] 1. A ceramic material having a deodorizing effect, which is made by adjusting porous coral fossils and/or shellfish fossils with a binder and sintering them.