JP2005087630A - Deodorant suitable for deodorization of sulfur-based malodor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide material which has a large effect of deodorizing various kinds of malodor components, in particular, malodor components of sulfur-based gas such as hydrogen sulfide, methyl mercaptan by solving the problem of a conventional deodorant. <P>SOLUTION: This deodorant is completed by finding that amorphous metal silicate having specific physical property has excellent deodorization performance to the malodor component of sulfur-based gas. That is, this deodorant is a sulfur-based deodorant which is an amorphous compound of at least one kind of metal salt selected from copper, zinc, manganese, cobalt and nickel, and silicate, and which has a pore volume of 0.3 to 0.5 ml/g. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a deodorant having excellent deodorizing performance against various malodors, particularly so-called sulfur-based malodors composed mainly of a compound containing sulfur element, and a composite malodor composed of sulfur-based malodors and other malodors. The present invention relates to a deodorant composition having excellent deodorant performance.

  In recent years, the demand for a comfortable life has increased rapidly, and one of them is deodorizing products that can remove bad odors that occur around us. In particular, sulfur-based gases mainly composed of compounds containing sulfur elements such as hydrogen sulfide and methyl mercaptan are disliked because they give particularly strong discomfort, and a deodorant effective for these sulfur-based gas malodors is desired. It is rare. However, conventionally known deodorants such as activated carbon, activated carbon impregnated with aromatic primary amine, activated carbon adjusted pH, combination of iron compound and ascorbic acid, amino group And polymer compounds having a sulfone group have low deodorizing ability for sulfur-based malodors. In addition, these deodorizers are originally colored, or cause coloring or discoloration by adsorbing or chemically reacting malodorous components, so that there is a problem that they cannot be used depending on applications.

On the other hand, as a deodorant having a deodorizing function against a sulfurous malodor, a deodorant containing zirconium or a lanthanoid element hydroxide or a hydrous oxide as an active ingredient has been reported (for example, see Patent Document 1). In addition, a deodorant composed of a tetravalent metal phosphate containing a specific metal ion has been proposed (see, for example, Patent Document 2). Furthermore, specific fine zinc oxide is shown as having high deodorizing performance against hydrogen sulfide (see, for example, Patent Document 3). Although these deodorizers have the feature that there is no coloring or discoloration of the deodorants themselves, their deodorizing performance against sulfur-based malodorous gases, particularly methyl mercaptan, is not sufficient.
Amorphous copper silicate having a BET specific surface area of 300 m ² / g or less, an oil absorption of 130 ml / 100 g or less, and an elution amount of copper ions with 1 N ammonia water of 1.5% or less per total copper is It has shown that it is excellent in antibacterial performance (for example, refer patent document 4). However, this product does not have sufficient methyl mercaptan deodorization performance.
Furthermore, a malodorous gas deodorant that includes a metal salt such as copper or zinc inside the silicic acid gel structure has been proposed (see, for example, Patent Document 5).

JP-A-1-223968 (Claims) JP-A-10-155883 (Claims) JP 2003-52800 A (Claims) Japanese Patent Laid-Open No. 8-283013 (Claims) JP-A-4-290546 (Claims)

  An object of the present invention is to solve the problems of conventional deodorants and to provide a material having a large deodorizing effect on various malodorous components, in particular, malodorous components of sulfur-based gases such as hydrogen sulfide and methyl mercaptan. It is.

  As a result of intensive studies, the present inventor has found that an amorphous silicate metal having specific physical properties has an excellent deodorizing performance with respect to a malodorous component of a sulfur-based gas, and has completed the present invention. That is, the deodorizer of the present invention is an amorphous complex of at least one metal salt selected from copper, zinc, manganese, cobalt, and nickel and silicate, and has a pore volume of 0.3 to 0.5 ml. Relates to a sulfur-based gas deodorant which is / g.

  Since the deodorizer of the present invention has a high deodorizing effect on bad odors of sulfur-based gases such as methyl mercaptan and hydrogen sulfide, it excludes various odors generated in the living environment such as excretion odor, living odor, and garbage odor. Useful for.

The deodorant of the present invention is an amorphous complex of at least one metal salt selected from copper, zinc, manganese, cobalt, and nickel and a silicate, and has a pore volume of 0.3 ml / g or more and 0 .5 ml / g or less. The metal salt is preferably copper, zinc, or manganese, more preferably copper or zinc, and particularly preferably copper because of its excellent deodorizing performance against sulfur-based gas. As metal salts such as copper and zinc used in the production of the deodorant of the present invention, salts such as sulfuric acid, hydrochloric acid and nitric acid can be used. The silicate is preferably an alkali metal silicate, more preferably sodium silicate or potassium silicate, and particularly preferably sodium silicate.
If the pore volume of the deodorizer of the present invention is less than 0.3 ml / g, the deodorization performance against sulfurous malodor such as methyl mercaptan and hydrogen sulfide may not be sufficient. Specifically, the deodorization rate may be slow. If the pore volume is larger than 0.5 ml / g, the deodorizing performance may be inferior. In particular, the deodorizing performance of methyl mercaptan may not be sufficient. Moreover, since particles tend to aggregate, it becomes difficult to handle as powder, which is not preferable. The pore volume can be easily measured by a mercury intrusion method using a porosimeter.
The molar ratio of the metal salt to the silicate when producing the deodorant of the present invention is 0.29 or more and less than 0.5, preferably 0.3 to 0.45, more preferably 0.00. 3 to 0.4. That is, the deodorizer of the present invention is obtained from a metal salt to silicate molar ratio of 0.29 or more and less than 0.5.

  In order to efficiently remove a composite malodor containing several types of malodorous sources including sulfur-based malodorous gases, the deodorizer of the present invention is mixed with or combined with a known deodorant. It can also be used as a composition. Known deodorants include activated carbon, zeolite, silica gel, aluminum silicate, hydrous zirconium oxide, zirconium phosphate, zinc oxide, and sepiolite.

○ Use The deodorant or deodorant composition of the present invention can be used as a final deodorant product in powder or granule as it is in a container such as a cartridge, and can be left in the vicinity of a bad odor source indoors or outdoors. The effect can be demonstrated by placing. Further, the deodorant or deodorant composition of the present invention can be used for producing a deodorant product by blending it into a fiber, a paint, a sheet, a molded product or the like as described in detail below.

One useful deodorant product using the deodorant or deodorant composition of the present invention is a deodorant fiber. The raw fiber in this case may be any of natural fibers and synthetic fibers, and may be any of short fibers, long fibers, and composite fibers having a core-sheath structure.
There is no particular limitation on the method for imparting deodorant performance to the fiber using the deodorant or deodorant composition of the present invention. For example, the fiber is post-processed with the deodorant or deodorant composition of the present invention. In the case of coating with a water-based or organic solvent-based suspension containing a deodorant or deodorant composition, it is applied to the fiber surface by a method such as coating or dipping, and the solvent is removed to remove the solvent. Can be coated. Further, a binder for increasing the adhesion to the fiber surface may be added and mixed. The pH of the aqueous suspension containing the deodorant is not particularly limited, but the pH is preferably in the vicinity of 6 to 8 in order to sufficiently exhibit the performance of the deodorant.

  In addition, the deodorant or deodorant composition of the present invention is kneaded into the melted liquid fiber resin or the dissolved fiber resin solution, and fiber is obtained to obtain a fiber having deodorizing performance. it can. As the fiber resin that can be used in this method, any known chemical fiber can be used. Specific examples of such preferable examples include polyester, nylon, acrylic, polyethylene, polyvinyl, polyvinylidene, polyurethane, and polystyrene. These resins may be homopolymers or copolymers. In the case of a copolymer, there is no particular limitation on the polymerization ratio of each copolymer component.

The ratio of the deodorant or deodorant composition of the present invention contained in the fiber resin is not particularly limited. In general, if the content is increased, the deodorizing ability can be exerted strongly and can be sustained for a long time, but even if it is added to a certain extent, there is no significant difference in the deodorizing effect, or the strength of the fiber is reduced. Therefore, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass per 100 parts by mass of the resin for fibers.
The deodorizing fiber using the deodorant or deodorant composition of the present invention can be used in various fields that require deodorizing properties, such as underwear, stockings, socks, duvets, duvet covers, cushions, and blankets. Can be used for many textile products such as carpets, curtains, sofas, car seats, air filters, nursing clothes.

The second main application using the deodorant or deodorant composition of the present invention is a deodorant paint. When producing a deodorant paint, there is no particular limitation on the oil or resin as the main component of the paint vehicle used, and any of natural vegetable oils, natural resins, semi-synthetic resins and synthetic resins may be used, and thermoplasticity. Either a resin or a thermosetting resin may be used.
Examples of the oils and resins that can be used include dry oil or semi-dry oil such as linseed oil, linden oil, soybean oil, rosin, nitrocellulose, ethylcellulose, cellulose acetate butyrate, benzylcellulose, novolac type or resol type phenol. Resins, alkyd resins, amino alkyd resins, acrylic resins, vinyl chloride, silicone resins, fluororesins, epoxy resins, urethane resins, saturated polyester resins, melamine resins, and polyvinylidene chloride resins.

The deodorant or deodorant composition of the present invention can be used for both liquid paints and powder paints. In addition, the deodorant coating composition using the deodorant or deodorant composition of the present invention may be of a type that cures by any mechanism, specifically, an oxidation polymerization type, a moisture polymerization type, a heat curing type, a catalyst curing type. Type, ultraviolet curable type, and polyol curable type. There are no particular restrictions on the pigments, dispersants and other additives used in the coating composition, except for those that may cause a chemical reaction with fine zinc oxide and deodorant substances used in combination therewith. .
The coating composition using the deodorant or deodorant composition of the present invention can be easily prepared. Specifically, the deodorant or deodorant composition and the paint component are mixed into a ball mill, roll mill, disperser, mixer, etc. It is sufficient to sufficiently disperse and mix using a general mixing apparatus.

The ratio of the deodorant or deodorant composition of the present invention contained in the deodorant paint is not particularly limited. In general, if the content is increased, the deodorizing ability can be exerted strongly and can be sustained for a long period of time, but even if it is added to a certain extent, there will be no significant difference in the deodorizing effect or the gloss of the painted surface will be lost Since cracking occurs, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass per 100 parts by mass of the coating composition.
The deodorant paint containing the deodorant or deodorant composition of the present invention can be used in various fields that require deodorization, for example, inner walls / outer walls of buildings, vehicles, railways, etc. Can be used in incineration facilities, garbage containers, etc.

Another important use of the deodorant or deodorant composition of the present invention is a deodorant sheet. The sheet material used as a raw material is not limited in its material, microstructure and the like. A preferred material is resin, paper, or the like, or a composite thereof, and a porous material is preferred. Preferable specific examples of the sheet material include Japanese paper, synthetic paper, non-woven fabric, resin film and the like, and particularly preferable sheet material is paper made of natural pulp and / or synthetic pulp.
When natural pulp is used, the powder of deodorant particles is sandwiched between finely branched fibers, and there is an advantage that a practical carrier can be obtained without using a binder. It has the advantage of excellent chemical properties. When using synthetic pulp, it may be difficult to support deodorant particles by sandwiching the powder between the fibers. It is also possible to increase the adhesion between the fiber and the fiber, or to mix another thermosetting resin fiber in a part of the fiber. When natural pulp and synthetic pulp are mixed at an appropriate ratio, paper with various characteristics can be obtained. Generally, increasing the ratio of synthetic pulp increases strength, water resistance, and chemical resistance. In addition, a paper excellent in oil resistance and the like can be obtained. On the other hand, when the proportion of natural pulp is increased, a paper excellent in water absorption, gas permeability, hydrophilicity, molding processability and texture can be obtained.

There is no particular limitation on the method for supporting the deodorant or deodorant composition of the present invention on the sheet material. The deodorant or deodorant composition of the present invention may be supported either during the production of the sheet or after the production of the sheet. For example, in the case of carrying on a paper, the deodorant is introduced in any step of the paper making process. Or a liquid in which a deodorant is dispersed together with a binder is applied, dipped or sprayed onto a previously manufactured paper.
Hereinafter, as an example, a method for introducing the deodorant of the present invention during the paper making process will be described. The paper making process itself may be carried out according to a known method. For example, first, a cationic and anionic flocculant is added to each slurry containing deodorant and pulp at a predetermined ratio of 5% by weight or less of the total slurry weight. To produce aggregates. Next, the aggregate is subjected to paper making by a known method, and dried at a temperature of 100 to 190 ° C., whereby a paper carrying a deodorant can be obtained.

The amount of the deodorant or deodorant composition according to the present invention supported on the sheet material is generally enhanced by increasing the amount supported, and can be sustained for a long period of time. However, since a large difference does not occur in the deodorizing effect, the preferred loading amount of the deodorant or deodorant composition is when the deodorant or deodorant composition is supported on the entire surface and inside of the sheet during the paper making process. The amount is 0.1 to 10 parts by mass per 100 parts by mass of the sheet, and 0.05 to 10 g / m ² when the deodorant or deodorant composition is supported only on the surface of the sheet by post-processing such as coating.
The deodorant sheet using the deodorant or deodorant composition of the present invention can be used in various fields that require deodorizing properties, such as medical wrapping paper, food wrapping paper, and electrical equipment. Packaging paper, nursing care paper products, freshness preservation paper, paper clothing, air cleaning filters, wallpaper, tissue paper, toilet paper, etc.

-Resin molded product Application to a resin molded product is mentioned as a use of the deodorizer or deodorant composition of this invention. When the deodorant of the present invention is added to the resin, the resin and the deodorant can be mixed as they are, and then put into a molding machine for molding. Alternatively, a pellet-like resin containing a high concentration of the deodorant can be prepared in advance. It is also possible to mold this after mixing with the main resin. In order to improve the physical properties of the resin, various pigments, dyes, antioxidants, light stabilizers, antistatic agents, foaming agents, impact resistance enhancers, glass fibers, moisture proofing agents, bulking agents, etc. Other additives can also be blended. As a molding method for producing a deodorant resin molded product using the deodorant of the present invention, general resin molding methods such as injection molding, extrusion molding, inflation molding, and vacuum molding can be used.
The deodorant resin molded article using the deodorant or deodorant composition of the present invention can be used in various fields that require deodorization, for example, home appliances such as air purifiers and refrigerators, There are general household items such as trash cans and drainers, various nursing items such as portable toilets, and daily items.

<Example>
The pore volume was easily measured by mercury porosimetry using a porosimeter.

  20 g of sodium silicate No. 2 (Hokuetsu Chemical Co., Ltd.) and 100 ml of ion-exchanged water were placed in a plastic container to obtain a uniform solution. The solution was kept at 30 ° C. while stirring, and a solution prepared by adding 10 g of copper sulfate pentahydrate to 100 ml of ion-exchanged water was added dropwise to the aqueous sodium silicate solution over 1 hour, and further to 30 ° C. The agitation was continued for 4 hours with aging, and a blue product was obtained. At this time, the pH of the slurry was 6.9. This slurry was filtered, and further washed until the electrical conductivity of the washing liquid from the cake was 50 μS / cm or less. The cake after washing was dried at 110 ° C. and then pulverized to obtain Sample A having a median diameter of 3.0 μm and a pore volume of 0.35 ml / g.

  A sample B having a median diameter of 3.0 μm and a pore volume of 0.35 ml / g was obtained in the same manner as in Example 1 except that the sodium silicate aqueous solution was dropped into the copper sulfate aqueous solution. The pH of the slurry after aging was 7.1.

  13 g of sodium silicate No. 3 (Hokuetsu Chemical Co., Ltd.) and 200 ml of ion-exchanged water were placed in a plastic container to obtain a uniform solution. This solution was kept at 30 ° C. while stirring, and a solution prepared by adding 4.8 g of copper sulfate pentahydrate to 50 ml of ion-exchanged water was dropped into the aqueous sodium silicate solution over 1 hour, and further 30 Stirring was continued for 4 hours while maintaining the temperature, and a blue product was obtained. At this time, the pH of the slurry was 7.3. This slurry was filtered, and further washed until the electrical conductivity of the washing liquid from the cake was 50 μS / cm or less. The washed cake was dried at 110 ° C. and then pulverized to obtain Sample C having a median diameter of 3.0 μm and a pore volume of 0.40 ml / g.

  A white sample D was obtained in the same manner as in Example 1 except that 11.5 g of zinc sulfate heptahydrate was added to 100 ml of ion exchange water instead of copper sulfate pentahydrate and dissolved. At this time, the pH of the slurry of the reaction solution was 7.0, the median diameter after pulverization was 3.0 μm, and the pore volume was 0.35 ml / g.

  A white sample E was obtained in the same manner as in Example 3 except that 5.5 g of zinc sulfate heptahydrate was added to 100 ml of ion-exchanged water instead of copper sulfate pentahydrate and dissolved. At this time, the pH of the slurry of the reaction solution was 7.0, the median diameter after pulverization was 3.0 μm, and the pore volume was 0.35 ml / g.

<Comparative Example 1>
20 g of sodium silicate No. 3 (Hokuetsu Chemical Co., Ltd.), 6 g of sodium hydroxide and 300 ml of ion-exchanged water were weighed and dissolved in a 2 L beaker. The solution was kept at 30 ° C. while stirring, and a solution prepared by adding 26 g of copper sulfate pentahydrate to 200 ml of ion-exchanged water was dropped into the aqueous sodium silicate solution over 2 hours, and kept at 30 ° C. Stirring was continued for an additional 4 hours while aging to obtain a blue product. At this time, the pH of the slurry was 7.5. The obtained slurry was filtered, and further washed until the electrical conductivity of the washing liquid from the cake was 50 μS / cm or less. The cake after washing was dried at 110 ° C. and then pulverized to obtain a sample a having a median diameter of 3.0 μm and a pore volume of 0.22 ml / g.

<Comparative example 2>
20 g of sodium silicate No. 2 (Hokuetsu Chemical Co., Ltd.) and 100 ml of ion-exchanged water were placed in a plastic container to obtain a uniform solution. The solution was kept at 30 ° C. while stirring, and a solution prepared by adding 8 g of copper sulfate pentahydrate to 100 ml of ion-exchanged water was added dropwise to the aqueous sodium silicate solution over 1 hour, and further to 30 ° C. The mixture was aged by continuing the stirring for 4 hours while keeping it. The pH was then adjusted to 7.1 with 10% sulfuric acid with stirring to give a blue product. The obtained slurry was filtered, and further washed until the electrical conductivity of the washing liquid from the cake was 50 μS / cm or less. The cake after washing was dried at 110 ° C. and then pulverized to obtain a sample b having a median diameter of 3.0 μm and a pore volume of 0.55 ml / g.

<Comparative Example 3>
A white sample c was obtained in the same manner as in Comparative Example 1 except that 30 g of zinc sulfate heptahydrate was added to 200 ml of ion-exchanged water instead of copper sulfate pentahydrate and dissolved. At this time, the pH of the slurry of the reaction solution was 7.2, the median diameter after pulverization was 3.0 μm, and the pore volume was 0.20 ml / g.

<Comparative example 4>
A white sample d was obtained in the same manner as in Comparative Example 2 except that 9.2 g of zinc sulfate heptahydrate was added to 100 ml of ion-exchanged water instead of copper sulfate pentahydrate and dissolved. At this time, the pH of the slurry of the reaction solution was 7.0, the median diameter after pulverization was 3.0 μm, and the pore volume was 0.56 ml / g.

○ Deodorization test of samples 0.01 g of each of samples A to E prepared in Examples 1 to 5 and samples a to d prepared in Comparative Examples 1 to 4 were used as separate polyvinyl fluoride films. Into a bag (hereinafter referred to as a Tedlar bag) prepared using a gas, methyl mercaptan (initial concentration 500 ppm) or hydrogen sulfide (initial concentration 800 ppm) is injected every 1 L, and the residual gas concentration in the Tedlar bag after 30 minutes Was measured with a gas detector tube (manufactured by Gastec Co., Ltd.). The results are shown in Table 1.

O Deodorizing test for deodorizing fiber 3 parts by mass of sample A prepared in Example 1 with respect to 100 parts by mass of pure water and 3 parts by mass of an acrylic binder (KB-1300, manufactured by Toagosei Co., Ltd.) Suspension A was prepared by adding and stirring. Similarly, the suspensions C to E and the suspensions a to A using the samples B to E prepared in Examples 2 to 5 and the samples a to d prepared in Comparative Examples 1 to 4 were used. d was produced. In addition, the suspension e was prepared in the same manner without using a sample.
50 parts by mass of each of these suspensions A to E and suspensions a to e were applied to 100 parts by weight of polyester fiber, dried at 150 ° C., and then fibers A to E and fibers a to e (deodorant). The content of the agent was 1.5 parts by mass with respect to 100 parts by mass of the polyester fiber.
5 g of these fibers were put into a Tedlar bag, and 1 L of methyl mercaptan (initial concentration 15 ppm) or hydrogen sulfide (initial concentration 20 ppm) was injected therein, and the residual gas concentration in the Tedlar bag after 30 minutes was measured in the same manner as in Example 6. did. The results are shown in Table 2 (unit: ppm, indicating that ND could not be detected).

O Deodorizing test for coated steel plate 70 parts by mass of acrylic resin (product name J-500 manufactured by SC Johnson Polymer Co., Ltd.) and 100% by weight of xylene solvent, and product name BYK- manufactured by BYK Chemie Co., Ltd. 110 parts), 3 parts by weight of a thickener (trade name Benton SD2 manufactured by Wilber Els Co., Ltd.), 200 parts by weight of sample A prepared in Example 1, and then a three-roll mixer. A paste-like composition A that was well kneaded and dispersed was obtained. Similarly, the paste compositions B to E and a to d were prepared using the samples B to E prepared in Examples 2 to 5 and the samples a to d prepared in Comparative Examples 1 to 4. Obtained. Moreover, the paste-like composition e was obtained in the same manner without adding a sample. These were diluted 10 times with xylene, and coated steel plates B to E and a to e coated on both surfaces of a 70 mm × 150 mm galvanized steel sheet to a film thickness of 100 μm were prepared.
One of these coated steel sheets is placed in a Tedlar bag, and 1 L of methyl mercaptan (initial concentration 15 ppm) or hydrogen sulfide (initial concentration 20 ppm) is injected therein, and the residual gas concentration in the Tedlar bag after 30 minutes is set in the same manner as in Example 6. It was measured. The results are shown in Table 3 (unit: ppm, indicating that ND could not be detected).
Moreover, the unevenness | corrugation of the coating surface was observed visually and the result was also shown in Table 3.

  As is clear from the evaluation of deodorizing performance against various malodors in Examples and Comparative Examples, the deodorant or deodorizing composition of the present invention is excellent in deodorizing performance against sulfurous malodors such as methyl mercaptan and hydrogen sulfide. Thus, by using the deodorant or deodorant composition of the present invention, excellent deodorant properties can be imparted to fibers, paints, sheets, molded articles, etc., and it can be used as a deodorant product.

Claims (3)

  Sulfur-based gas deodorant, which is an amorphous composite of at least one metal salt selected from copper, zinc, manganese, cobalt and nickel and silicate, and has a pore volume of 0.3 to 0.5 ml / g Agent.   A deodorant composition comprising the sulfur-based gas deodorant according to claim 1.   A deodorant product comprising the sulfur-based gas deodorant or deodorant composition according to claim 1.