JP2866212B2 - Cellulose-based deodorant material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant material for removing malodorous components present in a room, a refrigerator, or various environments, and more particularly to a cellulosic deodorant material. is there.

[0002]

2. Description of the Related Art Conventionally, Japanese Unexamined Patent Publication (Kokai) No. 2-107264 has been used for removing malodorous components such as ammonia, methyl mercaptan, methyl sulfide, methyl disulfide, hydrogen sulfide, trimethylamine, and acetaldehyde in a room or a refrigerator.
Various deodorant materials are proposed in Japanese Patent Application Publication No. JP-A-2005-163873. In the old days, there is a deodorant material containing activated carbon as a main component, but activated carbon is granular and black, so it is necessary to store it in a container with a good appearance and use it. There were restrictions. Therefore, a deodorant material that can be formed into a free shape is desired, and a cellulosic deodorant material based on a cellulosic material such as a cellulosic fiber or an oxidized cellulosic fiber that can be easily treated after use is used. Is particularly desired.

[0003]

However, the cellulosic deodorizing materials proposed so far have a satisfactory deodorizing performance in a low moisture state, that is, a deodorizing performance in a low moisture environment in a refrigerator or the like. Was not.

[0004]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that alginic acid, chitosan and a specific metal element are immobilized in order on a cellulosic material such as cellulosic fiber or oxidized cellulosic fiber. It has been found that such a cellulosic deodorant material effectively acts on a wide range of malodorous components even in a low moisture state, and has completed the present invention. That is, the present invention provides a cellulose-based deodorizing material characterized by sequentially fixing alginate and chitosan and one or more metal elements selected from the group consisting of specific metal elements to a cellulose-based substance. It is the gist. The cellulose-based material used in the present invention includes bleached sulphite pulp (NBSP, LBSP)
P, NDSP and LDSP, etc.) and pulp fibers such as bleached kraft pulp (NBKP, LBKP, etc.), hemp such as Manila hemp and jute, cotton such as absorbent cotton, cotton linter, kuzo and mitsumata, etc. Examples include cellulosic fibers such as rayon and oxidized cellulose fibers obtained by oxidizing them. Further, other cellulosic fiber-containing materials such as rice hulls, buckwheat husks and sawdust, and those obtained by oxidizing them can also be used. Two or more of these cellulosic materials may be used in combination. As a method for oxidizing the oxidized cellulose fiber used in the present invention, a conventionally known method may be applied, and examples thereof include an oxidizing method using nitrogen dioxide and an oxidizing method using hypochlorite. When oxidation proceeds due to the oxidation treatment, the number of functional groups chemically bonded to the specific metal element increases and tends to become brittle. Therefore, the degree of the oxidation treatment is appropriately determined depending on the deodorant performance and processing form of the intended deodorant material. select. For example, in the case of molding into granules, it is easier to mold when the oxidation is advanced. Specific metal elements used in the present invention have atomic numbers of 12 to 13, 20 to 30, and 3
Among these are metal elements of 8 to 51, 57 to 83 and 88 to 89, of which Cu and Zn are more preferable because of their excellent fixability and deodorizing performance as a cellulosic deodorant material.
In the present invention, alginic acid and chitosan, and at least one or more metal elements from the group consisting of the above metal elements are immobilized on the cellulosic substance by chemical bonding or adhesion in order to obtain a cellulosic deodorant material. Is obtained by dissolving (a) alginic acid dissolved in water and chitosan dissolved in water as needed with an acid such as acetic acid, and (b) a water-soluble compound among the compounds of the specific metal element as described above, using a cellulosic substance. And immobilized by adding them in an aqueous system in the order of (a) and (b). The alginic acid used in the present invention is not particularly limited as long as it is water-soluble, and examples thereof include alkali metal salts such as sodium alginate. The water-soluble compound of the specific metal element used in the present invention is not particularly limited, for example, calcium chloride, calcium nitrate, copper sulfate, copper chloride, copper nitrate, copper acetate, zinc sulfate, zinc chloride, zinc nitrate , Zinc acetate, iron (III) sulfate nonahydrate,
Potassium molybdate, sodium tungstate and the like can be mentioned. These metals may be used in combination of two or more. (A) After the addition in the order of (b), the pH of the reaction system was adjusted to sodium hydroxide, potassium hydroxide, sodium carbonate,
The use of an alkaline substance such as sodium bicarbonate and the like depends on the water-soluble compound of the metal element to be used, etc., but cannot be said in general, but is generally about 3.0 to 10.0, more preferably about 5.0.
Adjustment to the range of 8.0 is more preferable because the fixability of alginic acid and chitosan to the above-mentioned metal element is improved. For example, in the case of Cu, the pH is preferably about 5.0 to 7.0, and in the case of Zn, the pH is preferably about 5.0 to 8.0. The cellulosic deodorant material obtained as described above may be used directly as a deodorant material, or may be further processed into a sheet-like or three-dimensional molded article by a known papermaking method or the like to form a deodorant material, or It may be processed into a thread-like molded body by a known spinning method to obtain a deodorant material. In addition, a cellulose-based material or the like in which alginic acid and chitosan and the above-mentioned metal element are not fixed may be mixed within a range that satisfies the required deodorizing performance and processability. In the case of processing into a molded article, a paper-making aid such as a wet paper strength enhancer or a polymer flocculant usually used for fibers or the like is used as long as the deodorizing performance and processing suitability of the molded article are not impaired. An agent or a spinning aid may be added. Further, the molded body obtained as described above may be subjected to secondary processing into a honeycomb shape or the like to be used as a deodorant material.

[0005]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the measured value of an Example was measured by the following method. (1) Cu and Zn concentrations Measured by atomic absorption spectroscopy. (2) Moisture (%) of measurement sample According to JIS P8203. (3) Relative viscosity According to JIS P8101.

Example 1 A 3% by weight aqueous solution of sodium alginate was dissolved in a 1% by weight acetic acid solution in 3 kg of a 3% by weight aqueous solution using a Werner-type pulverizer.
After adding 3 kg of an aqueous solution of chitosan by weight and stirring for 30 minutes, 900 g of NDSP powdery fiber is further added with stirring and mixed for 30 minutes to disintegrate into a slurry, and then an aqueous solution of 21% by weight copper sulfate (CuSO ₄ ) is converted to Cu. And N
3.7% by weight based on DSP powdery fiber and 30
After stirring for 10 minutes, the pH of the reaction system was further adjusted to 6.0 with a 10% by weight aqueous solution of sodium hydroxide, followed by stirring for 30 minutes.
A dispersion of NDSP deodorant fibers in which alginic acid, chitosan, and Cu were immobilized sequentially on NDSP powder was obtained. Next, the NDSP deodorant fiber was separated by filtration from the dispersion, washed once with water, separated by filtration, and dried with a hot air drier to obtain a powdery NDSP deodorant fiber. The amount of alginic acid fixed in the deodorant fiber obtained as described above was 8% by weight based on NDSP fiber in terms of sodium alginate.
The amount of chitosan is 8% by weight based on the NDSP fiber,
The u content was 2.8% by weight based on the NDSP fiber.
Further, the deodorizing fibers were subjected to a deodorizing performance test for H ₂ S gas and NH ₃ gas by the following method. Deodorizing performance test method Put 1 g of a measurement sample in a 1.5-liter plastic bag, and supply 1.5 l of a predetermined concentration of odorous gas (100 ppm in each case).
After sealing, the concentration of the offensive odor gas remaining in the sealed bag after a predetermined time was measured by a gas detector tube to obtain a residual ratio (%). Tables 1 and 2 show the obtained results.

Example 2 1.9 kg of a 3% by weight aqueous solution of chitosan dissolved in a 1% by weight acetic acid solution was added to 1.9 kg of a 3% by weight aqueous solution of sodium alginate in a Werner grinder, and the mixture was stirred for 30 minutes. 990 g of NDSP powder fiber was added with stirring and mixed for 30 minutes to disintegrate into a slurry,
Next, 3.5% by weight of a 21% by weight aqueous solution of copper sulfate (CuSO ₄ ) was added to the NDSP powdery fiber in terms of Cu, and the mixture was stirred for 30 minutes. Then, the pH of the reaction system was further adjusted with a 10% by weight aqueous solution of sodium hydroxide. Adjust to 6.0 and stir for 30 minutes, then add alginic acid and chitosan and C to NDSP powder.
Thus, a dispersion liquid of NDSP deodorant fibers having u immobilized sequentially was obtained. Next, the NDSP deodorant fiber was separated by filtration from the dispersion, washed once with water, separated by filtration, and dried with a hot air drier to obtain a powdery NDSP deodorant fiber. The amount of alginic acid immobilized in the deodorizing fiber obtained as described above was 4.9% by weight based on NDSP fiber in terms of sodium alginate, and the amount of chitosan was 4.9 based on NDSP fiber.
%, And the Cu content was 3.0% by weight with respect to the NDSP fiber. Further, the deodorizing fiber was subjected to a deodorizing performance test for H ₂ S gas and NH ₃ gas in the same manner as in Example 1. Tables 1 and 2 show the obtained results.

Example 3 A 3% by weight aqueous solution of sodium alginate was dissolved in a 1% by weight acetic acid solution in 3 kg of an aqueous solution of 3% by a Werner type pulverizer.
After adding 3 kg of an aqueous solution of chitosan by weight and stirring for 30 minutes, 900 g of NDSP powdery fiber is further added with stirring and mixed for 30 minutes to disintegrate into a slurry, and then the aqueous solution of 20% by weight zinc sulfate (ZnSO ₄ ) is converted to Zn. 3. Add 3.7% by weight to NDSP powdery fiber
After stirring for 0 minutes, the pH of the reaction system was further adjusted to 7.0 with a 10% by weight aqueous sodium hydroxide solution, and the mixture was stirred for 30 minutes. Alginic acid, chitosan and Zn were added to NDSP powder.
Were sequentially immobilized to obtain a dispersion of NDSP deodorant fibers. Next, the NDSP deodorant fiber was separated by filtration from the dispersion, washed once with water, separated by filtration, and dried with a hot air drier to obtain a powdery NDSP deodorant fiber. The amount of alginic acid immobilized in the deodorant fiber obtained as described above was 8% with respect to the NDSP fiber in terms of sodium alginate.
The amount of chitosan was 8% by weight with respect to the NDSP fiber, and the amount of Zn was 2.9% by weight with respect to the NDSP fiber. Further, the deodorizing fiber was subjected to a deodorizing performance test for H ₂ S gas and NH ₃ gas in the same manner as in Example 1. The obtained results are shown in Tables 1 and 2.

Example 4 1.9 kg of a 3% by weight aqueous solution of chitosan dissolved in a 1% by weight acetic acid solution was added to 1.9 kg of a 3% by weight aqueous solution of sodium alginate in a Werner grinder, and the mixture was stirred for 30 minutes. 990 g of NDSP powder fiber was added with stirring and mixed for 30 minutes to disintegrate into a slurry,
Then, a 20% by weight aqueous solution of zinc sulfate (ZnSO ₄ ) was
After adding 3.5% by weight to the NDSP powdery fiber in conversion and stirring for 30 minutes, the pH of the reaction system was further adjusted to 7.0 with a 10% by weight aqueous sodium hydroxide solution, and the mixture was stirred for 30 minutes. A dispersion of NDSP deodorant fiber in which alginic acid, chitosan, and Zn were sequentially immobilized on a powder was obtained. Next, the NDSP deodorant fiber was separated by filtration from the dispersion, washed once with water, separated by filtration, and dried with a hot air drier to obtain a powdery NDSP deodorant fiber. The amount of alginic acid immobilized in the deodorant fiber obtained as described above was 4.9% by weight based on NDSP fiber in terms of sodium alginate, and the amount of chitosan was 4.9% based on NDSP fiber.
%, And the Zn content was 3.0% by weight with respect to the NDSP fiber. Further, the deodorizing fiber was subjected to a deodorizing performance test for H ₂ S gas and NH ₃ gas in the same manner as in Example 1. The obtained results are shown in Tables 1 and 2.

Comparative Example 1 1 kg of NDSP powdery fiber was added to 20 l of water, and the mixture was disintegrated into a slurry using a disintegrator to obtain a 5% by weight NDSP disintegration liquid. Sodium hypochlorite is added to the NDSP 5 wt% disintegration solution in an amount of 10% of NDSP in terms of available chlorine, and NDSP is added.
After adjusting the solution to 4% by weight, the solution was heated to a temperature of 58 ° C.
An oxidation treatment was carried out from the initial relative viscosity of 4.5 ° C. to a relative viscosity of 1.8 while stirring, followed by dehydration and washing to obtain powdered oxidized NDSP fiber as oxidized cellulose fiber. The COOH group in 100 g of the oxidized NDSP was 11.0 meq / 100 g. Put 3% strength by weight aqueous solution of sodium alginate 18kg to Werner pulverizer, added copper sulfate solution 600ml obtained by dissolving copper sulfate _{(CuSO 4 · 5H 2 O)} 133g, after stirring for 30 minutes, filtered, washed with water and dried As a result, 573 g of an alginic acid-copper complex was obtained. The Cu content in the obtained alginic acid-copper complex was 5.8% by weight. 573 g of the alginic acid-copper complex prepared in the same manner and 17 kg of water were put into a Werner type pulverizer, and 540 g of the powdered fiber of the oxidized NDSP was added.
Was added with stirring and mixed for 30 minutes to disintegrate into a slurry to immobilize the copper alginate complex on oxidized NDSP powder to obtain a dispersion of oxidized NDSP deodorant fibers. Next, the oxidized NDSP deodorant fiber was separated by filtration from the dispersion, washed once with water, separated by filtration, and dried with a hot air drier to obtain a powdery oxidized NDSP deodorant fiber. The alginic acid-copper complex immobilized in the deodorant fiber obtained as described above was 3.0% by weight in terms of Cu relative to the oxidized NDSP fiber. Further, a deodorizing performance test for NH ₃ gas was performed on the deodorizing fibers in the same manner as in Example 1. Table 2 shows the obtained results.

Comparative Example 2 Oxidized NDSP powdery fiber 1080 prepared in the same manner as in Comparative Example 1 in 17 kg of water using a Werner type pulverizer.
g was added with stirring and mixed for 30 minutes to disintegrate into a slurry. Then, a 21% by weight aqueous solution of copper sulfate was added in an amount of 3.1% by weight to the oxidized NDSP powder-like fiber in terms of Cu.
The mixture was stirred for 0 minutes, the pH of the reaction system was further adjusted to 7.0 with a 10% by weight aqueous sodium hydroxide solution, and the mixture was stirred for 30 minutes, to thereby fix Cu on the oxidized NDSP powder.
A dispersion of the deodorant fiber was obtained. Then, the oxidized NDSP deodorant fiber was separated from the dispersion by filtration, washed once with water, separated by filtration, and dried with a hot air drier to obtain a powdered oxidized NDSP.
A deodorant fiber was obtained. The amount of Cu immobilized in the deodorant fiber obtained as described above was 3.0% by weight based on the oxidized NDSP fiber. Further, a deodorizing performance test for NH ₃ gas was performed on the deodorizing fibers in the same manner as in Example 1. Table 2 shows the obtained results.

Comparative Example 3 In a Werner type pulverizer, 18 kg of a 3% by weight aqueous solution of chitosan dissolved in a 1% by weight acetic acid solution was used.
Powdered fiber 5 of oxidized NDSP prepared in the same manner as above.
40 g was added with stirring and mixed for 30 minutes to disintegrate into a slurry. Then, 6.2% by weight of a 21% by weight aqueous solution of copper sulfate was added to the oxidized NDSP powder-like fiber in terms of Cu, and the mixture was stirred for 30 minutes. The pH of the reaction system was adjusted to 7.0 with a 10% by weight aqueous solution of sodium hydroxide, and the mixture was stirred for 30 minutes to obtain a dispersion of oxidized NDSP deodorant fiber in which chitosan and Cu were immobilized sequentially on oxidized NDSP powder. Was. Next, the oxidized NDSP deodorant fiber is separated from the dispersion by filtration.
After washing once with water and filtering off, the powder was dried with a hot air drier to obtain a powdery oxidized NDSP deodorant fiber. The amount of chitosan immobilized in the deodorant fiber obtained as described above was 49% by weight based on the oxidized NDSP fiber, and the amount of Cu was 3.0% by weight based on the oxidized NDSP fiber. . Further, a deodorizing performance test for NH ₃ gas was performed on the deodorizing fibers in the same manner as in Example 1. Table 2 shows the obtained results. From the results in Table 2, it is clear that the deodorant fiber of the present invention exhibits excellent deodorant performance against NH ₃ gas even in a low moisture state.

[0013]

[Table 1] Deodorizing performance test for H ₂ S

[0014]

[Table 2] Deodorizing performance test for NH ₃

[0015]

According to the present invention, alginic acid and chitosan are added to a cellulosic material, and a specific metal element, more preferably, Cu or Zn is used.
The cellulose-based deodorant material of the present invention, which is immobilized in order, has a low moisture state, that is, even in a low humidity environment such as a refrigerator, ammonia, methyl mercaptan, methyl sulfide,
Sufficient deodorant performance against malodorous gas components such as methyl disulfide, hydrogen sulfide, trimethylamine and acetaldehyde, or ammonia and hydrogen sulfide in aqueous solution. . Furthermore,
The cellulosic deodorant material of the present invention is an excellent deodorant material as a single substance, but among them, fibrous ones are excellent in moldability, and are practically usable sheets, honeycombs, granules,
It can be processed into a molded article of an arbitrary shape such as a thread to obtain a deodorant material, and can be applied to a wide range of deodorant fields.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) A61L 9/01

Claims (2)

(57) [Claims] 1. A cellulosic substance selected from the group consisting of alginic acid and chitosan and a specific metal element.
A cellulosic deodorant material comprising at least one kind of metal element fixed in order. 2. The cellulosic deodorant material according to claim 1, wherein the selected metal element is Cu or Zn.