JP2011104274A - Sulfur-based gas deodorant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material which has a large effect of deodorizing the malodor components of various kinds of sulfur-based gas, in particular, the components such as hydrogen sulfide by solving the problem of a conventional deodorant. <P>SOLUTION: This deodorant is achieved by finding that amorphous metal silicate having specific physical property has excellent deodorization performance to the malodor component of sulfur-based gas. That is, a sulfur-based gas deodorant is constituted of amorphous metal silicate salt where an elemental composition (mole) ratio between silicon and at least one kind of metal selected among copper, zinc, manganese, cobalt and nickel is within the range of 0.60-0.80, and also crush strength is within the range of 1-3N. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a deodorant having excellent deodorizing performance with respect to various bad odors, particularly so-called sulfur-based gas, which contains a compound containing sulfur element as a main component.

  In recent years, the demand for a comfortable life has increased rapidly, and attention has been focused on deodorizing products that can remove malodors that occur around us. In particular, sulfur-based gases composed mainly of compounds containing sulfur elements such as hydrogen sulfide and methyl mercaptan are disliked as those that give strong discomfort, and there are deodorizers that are effective for the malodor of these sulfur-based gases. It is desired. 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 the polymer compound having a sulfone group have low deodorizing ability for sulfurous 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).
Moreover, it is shown that a specific fine particle zinc oxide has high deodorizing performance with respect to hydrogen sulfide (for example, refer 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.

  Further, as a sulfur-based gas deodorant that is a silicate, a malodorous gas deodorant that includes a metal salt such as copper or zinc inside a silicate gel structure has been proposed (see, for example, Patent Document 4). . This deodorant is designed to deodorize both the sulfur gas hydrogen sulfide and methyl mercaptan and the basic gases ammonia and amine so as not to increase the metal salt content. By suppressing it, it is set so that the specific surface area of the deodorant can be maintained high. For this reason, it is possible to deodorize two types of gas, but the deodorizing amount of sulfur-based gas is not sufficient.

  Patent Document 5 discloses that an amorphous complex of a metal salt such as copper, zinc, manganese, cobalt, and nickel and a silicate exhibits high deodorizing performance with respect to methyl mercaptan. This amorphous composite has a relatively small amount of metal relative to silicic acid, and the disclosed production method has room for improvement in productivity such as filtration, drying, and pulverization.

JP-A-1-223968 Japanese Patent Laid-Open No. 10-155883 JP 2003-52800 A JP-A-4-290546 JP 2005-87630 A

  The problem of the present invention is to solve the problems of conventional metal silicate deodorants, have a large deodorizing effect on sulfur-based gas, and easily pulverize and easily control the particle size. It is to provide a gas deodorant.

  As a result of intensive studies, the present inventors have found that amorphous metal silicates having specific physical properties have excellent deodorizing performance against sulfur-based gases, particularly hydrogen sulfide, and have high filterability and friability. The inventors have found that productivity is good and have completed the present invention. That is, the present invention is a sulfur comprising an amorphous metal silicate having a metal / silicon elemental composition (molar) ratio in the range of 0.60 to 0.80 and a crushing strength in the range of 1 to 3N. It is a system gas deodorant.

  Since the sulfur-based gas deodorant of the present invention has a high deodorizing effect on sulfur-based gases such as methyl mercaptan and hydrogen sulfide, it excludes various odors generated in the living environment such as excrement odor, living odor, and garbage odor. In addition, since the productivity is high, it can be produced industrially at low cost and put into practical use.

  The sulfur-based gas deodorant of the present invention has an elemental composition (molar) ratio of at least one metal selected from copper, zinc, manganese, cobalt, and nickel to metal / silicon = 0.60 to 0.80. It is made of an amorphous metal silicate with a crushing strength of 1 to 3 N.

  The sulfur-based gas deodorant of the present invention has an amorphous metal silicate elemental composition (molar) ratio of 0.60 to 0.80 and an amorphous metal silicate crushing strength of 1 to 3N. It can be produced by a production method that may include a step of making the above-mentioned amorphous metal silicate into a fine powder by a method such as pulverization and classification, with the step of producing a porous metal silicate as an essential step. Amorphous metal silicate can be produced by blending a metal salt and an alkali silicate salt. The deodorizing performance and productivity of the deodorant are affected by the blending ratio of both raw material components to be blended and the blending conditions.

The metal salt used in the production of the sulfur-based gas deodorant of the present invention is an inorganic salt such as sulfuric acid, hydrochloric acid, nitric acid and / or formic acid of at least one metal selected from copper, zinc, manganese, cobalt, and nickel. Organic salts such as acetic acid and oxalic acid can be used. Among these, copper (I), copper (II), and zinc (I) are preferable as metals, and copper (II) that is easy to obtain a stable and soluble salt is more preferable. It is an inorganic salt obtained and chemically stable. Specifically, copper (II) sulfate and hydrated salts thereof are preferably used.
When these metal salts are used in the reaction, it is preferable to dissolve them in a polar solvent such as water in advance, and the concentration at that time is such that the salt does not precipitate and the higher concentration can increase the slurry concentration, It is preferable because production efficiency can be increased.

The alkali silicate salt used for manufacture of the deodorizer of this invention is represented by Formula (1).

M ₂ O. nSiO ₂ . xH ₂ O (1)

(In the formula (1), M represents a monovalent alkali metal, n is a positive number, x is 0 or a positive number.) The alkali silicate salt in the present invention is any one represented by the formula (1). But it can also be used. Specific examples of M include sodium, potassium, rubidium, lithium, cesium, and the like. Sodium and potassium are preferable because they can be obtained industrially at low cost, and sodium is more preferable because high deodorizing capacity can be obtained. It is. Further, n is preferably 1 to 4, more preferably n is 1.3 to 3, and more preferably 2 to 2.5. Further, an aqueous solution of alkali silicate is preferably for use in reaction, the concentration in terms of SiO _2, SiO ₂ concentration is preferably from 20 to 40 wt% in aqueous solution, even at 39% by weight to 33.

  An amorphous metal silicate can be obtained by mixing and reacting these metal salt and alkali silicate salt under certain conditions. The elemental composition ratio (molar ratio) of the metal and silicon contained in the amorphous metal silicate is defined by the number of moles of the metal element to 1 mole of the Si element, and the molar ratio is generally between 0 and 0.80. The larger the molar ratio, the greater the deodorizing ability of the sulfur-based gas as the deodorant tends to be. However, when the molar ratio exceeds 0.80, the deodorizing ability tends to decrease. It is 0.60-0.80, More preferably, it is 0.61-0.75, More preferably, it is 0.62-0.70.

  In the method for producing an amorphous metal silicate, it is essential that the pH when the metal salt and the alkali silicate salt are mixed in the reaction solution does not exceed the range of 6.0 to 9.0. The more preferable pH range is 6.5 to 8.5, and even more preferably 7.0 to 8.0. For example, in Patent Document 4, a silicate and a zinc compound are dissolved in an alkaline aqueous solution to adjust the pH to 9 to 11, and the solution is kept at 50 to 70 ° C. There is a description of a method for producing a malodorous gas adsorbent in which a polysilicate molecular sol is formed by polymerization, and then the silicate sol undergoes phase transition to the gel and precipitates when the liquid is neutralized. The acid salt is produced by a completely different method from the conventional method for aging a silicate sol under high temperature alkaline conditions.

  In the method for producing an amorphous metal silicate, the pH condition when the metal salt and the alkali silicate salt are added to the reaction solution and mixed (this step is called preparation) is the metal salt and the alkali silicate. It is not the final pH after completion of the preparation determined by the composition of the salt, but the actual pH of the reaction mixture during preparation from the start of preparation to the end of preparation. Since precipitation of metal silicate occurs immediately after compounding, pH during compounding means pH at the time of metal silicate production. In order to maintain pH 6.0 to 9.0 during the preparation of the metal salt that is an acidic solution and the alkali silicate that is an alkaline solution, it is preferable to add both raw materials simultaneously from the beginning of the preparation, It is preferable to appropriately measure the pH and adjust the dropping rate of the metal salt and the alkali silicate salt. However, if the pH is maintained at 6.0 to 9.0, it is possible to supply only one raw material or to supply it alternately as part of the preparation process. The process until the process is completed is called a blending process.

  Moreover, since it is easier to cope with a sudden change in pH when the initial dropping rate is kept small, preparation should be performed at a dropping rate of 30 minutes or more, preferably 1 hour or more until the dropping of all raw materials is completed. Is preferred. Amorphous metal silicate of the present invention having a crushing strength of 1 to 3N, which is easy to filter and dry, has good productivity and has a crushing strength of 1 to 3N when the pH at the time of preparation is in the range of 6.0 to 9.0. Produces. The pH of the liquid can be measured with a normal pH meter or the like using a glass electrode, and automatic control of the dropping rate of the raw material based on the measured pH value is also carried out by applying known techniques. Can do.

  Since the temperature at which the amorphous metal silicate is prepared affects the performance of the deodorant, it is preferably in the range of 5 to 40 ° C, more preferably 10 to 40 ° C. Since the reaction is not completely completed immediately after the raw material preparation, it is preferable to continue aging for 10 minutes to 24 hours, more preferably about 1 to 12 hours immediately after the raw material preparation. The temperature can be measured by immersing a normal thermometer in the reaction solution.

  Since the amorphous metal silicate precipitates, it can be obtained by solid-liquid separation by a known method such as centrifugal sedimentation, filtration or decantation, and can also be washed. It can be known that the cleaning has sufficiently progressed by measuring the electrical conductivity of the cleaning liquid. Preferably, cleaning is performed until the electric conductivity of the cleaning liquid is 500 μS / cm or less, more preferably 200 μS / cm or less, and more preferably 50 μS / cm or less. In addition, S means a Siemens unit.

  The higher the crushing strength of the amorphous metal silicate, the more fine powder is suppressed and the filtration becomes easier, and the lower the crushing strength, when pulverized into a powder deodorant product Is preferable. In the present invention, the crushing strength is 1 to 3N, preferably 1.3 to 2.6N.

Method of measuring the crushing strength granulate ^{JIS-Z8841 -1993} - can be measured according to the strength test method. For example, an amorphous metal silicate dried for 24 hours at 150 ° C. is ASTM standard no. No. 4 after sieving with standard sieve. A particle having a size of about 3 mm on a sieve of 10 is randomly selected and subjected to a crushing strength tester to record the maximum indicated value until the particle breaks. Preferably, a plurality of average values, for example, The average value of 20 pieces can be used as the crushing strength (unit N: Newton).

  The particle size of the amorphous metal silicate can be controlled, for example, by grinding and classification. However, it is preferable that a special classification step is not required because productivity varies greatly depending on whether or not a classification operation is performed. In particular, when applied to various deodorized processed products, it is preferable that the particles having a large particle size be less because they may deteriorate the appearance or cause clogging or scratches in the processing step. In the deodorizer of the present invention, for example, in a volume-based particle size distribution generally referred to as “d90”, the particle size value of 90% of the particles is cumulative, and “d50” is 50 It is preferable to reduce each of the values that mean the particle diameter of%, that is, the median diameter. The particle size distribution varies slightly depending on the measurement method, but in the present invention, the measurement value by a laser diffraction particle size distribution meter is used as a reference, and when measuring by a method of another measurement principle, the measurement of a standard substance, etc. The measured value can be applied by a method such as obtaining a correction coefficient by the method.

  In the deodorizer of the present invention, preferable d90 is 50 μm or less, and d50 is 10 μm or less. This value means that the large particle size is small and the fiber or film can be easily processed. When the crushing strength of the amorphous metal silicate is 1 to 3 N, it can be easily pulverized and can be obtained without classification with a particle size of d50 of 10 μm or less and d90 of 50 μm or less. It is. For the pulverization, a pin mill, atomizer, ball mill, which is a fine pulverizer, a jet mill, which is an ultrafine pulverizer, or the like can be used.

  In the present invention, the deodorant has a d50 particle size that is easier to handle because it is less likely to cause agglomeration, but the smaller one is easier to apply to thinner or thinner products, so 0.5 to 10.0 μm. Is more preferable, it is 1.0-8.0 micrometers, More preferably, it is 2.0-5.0 micrometers. The d90 particle size is preferably 1 to 50 μm, more preferably 2 to 30 μm, for the same reason. The closer the d50 and d90 values are, the closer the particle size of the deodorant is, and the better the processability, etc., so the d90 value is preferably between 2 and 15 times d50, more preferably It is between 3 times and 12 times.

The specific surface area of the deodorant of the present invention is preferably larger because it tends to have higher deodorizing ability, but it is difficult to obtain a larger surface area, so it is preferably 200 to 400 m ² / g, more preferably. 250-350 m ² / g. In the first place, in the neutralization reaction of sodium silicate, it is known that the specific surface area of silica gel obtained depends on the conditions of neutralization and aging, but in the present invention, the elemental composition (mole) ratio of metal / silicon is 0. .60-0.80, which is a composition with more metal than silicon, and the tendency is different from the mere neutralization reaction of sodium silicate. Moreover, even if it manufactures on the same conditions, a specific surface area changes with metal element types. Copper or zinc is preferable as the metal capable of obtaining a relatively large specific surface area, and copper is more preferable.

  The deodorizing ability of the deodorant of the present invention preferably exhibits 40 ml or more of methyl mercaptan per 1 g of the deodorant at 25 ° C. This is expressed as a deodorizing ability of 40 ml / g or more. Similarly, a high deodorizing performance of preferably 60 ml / g or more with respect to hydrogen sulfide is exhibited.

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

  Among these, zinc oxide and zirconium phosphate are preferable, and layered zirconium phosphate is preferable, and the deodorizing performance of the basic gas is also greatly improved without impeding the deodorizing performance of the sulfur-based gas. . The preferred proportion of the sulfur-based gas deodorant of the present invention in the deodorant composition varies depending on the composition of the target malodorous gas, but is usually preferably 3% by mass to 90% by mass, and more preferably 10%. It is not less than 70% by mass.

○ 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, paint, sheet, or molded product 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 in an amount of 5% by mass or less based on the total slurry mass. 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.

The powder physical properties and deodorizing performance of the deodorant of the present invention were measured by the following methods.
(1) d50 and d90 particle diameters Measured with a laser diffraction particle size distribution meter, and the results were analyzed on a volume basis. The particle diameters d50 and d90 of the deodorant were measured by first using an “ultracentrifugal mill ZM200” manufactured by Lecce and using amorphous metal silicate particles ground under conditions of 80 μm mesh and 10,000 rpm in deionized water. After being dispersed and treated with ultrasonic waves of 70 W for 2 minutes or longer, measurement was performed with a laser diffraction particle size distribution analyzer, and the results were analyzed on a volume basis. The content percentage of the particle size distribution is the volume% in all particles from this analysis method, but has the same meaning as the mass% because the density of the amorphous metal silicate is constant. Specifically, it was measured by a laser diffraction particle size distribution measuring device “MS2000” manufactured by Malvern.

(2) specific surface area JIS Z8830 ^-2001, the "specific surface area measurement method of the powder (solid) by gas adsorption", was measured using "SA-6200" manufactured by Horiba continuous flow type surface area analyzer.

(3) Composition (metal / silicon ratio)
Measurement was made by fluorescent X-ray analysis using a Rigaku ZSX100e type fluorescent X-ray analyzer, and the result was analyzed on the basis of the amount of substance to calculate the elemental composition (mole) ratio of metal / silicon.

(4) Crushing strength Amorphous metal silicate particles dried at 150 ° C. for 24 hours were measured according to ASTM standard no. No. 4 after sieving with standard sieve. 10 particles having a size of about 3 mm, which was sieved with 10 sieves, were randomly selected, and the results measured by a crushing strength meter were averaged to obtain crushing strength. For the measurement of crushing strength, Pacific Transducer Corp. “Model 306L Type A Classic Style Durometer” manufactured by KK was used.

(5) Deodorizing performance 0.01 g of dried deodorant powder was placed in a bag (hereinafter referred to as a Tedlar bag) made using a polyvinyl fluoride film, and methyl mercaptan (initial concentration 600 ppm) or hydrogen sulfide (initial) 1 L) was injected, and the residual gas concentration in the Tedlar bag after 30 minutes was measured with a gas detector tube. The detector tube is manufactured by Gastec Co., Ltd. Series 4 (for hydrogen sulfide) or No. 71 (for methyl mercaptan) was used. No. No. 4 system is No. 4LL, 4LT, 4H, etc. were properly used. The lower limit of detection is approximately 0.2 ppm.

<Example 1>
While stirring 75 ml of deionized water in a 300 ml beaker, 37.5 g of No. ₂ sodium silicate (Na ₂ O.2.5SiO ₂ .xH ₂ O, SiO ₂ concentration 35 mass%) and copper sulfate pentahydrate Two types of solutions in which 17.75 g was added and dissolved in 100 ml of deionized water were dropped simultaneously over 1 hour. The dropping speed was adjusted so that the liquid temperature during dropping was within the range of 23 to 27 ° C. and the pH was maintained within the range of 6 to 7.
Note that the No. 2 sodium silicate, which means that is intended to conform to the standards of the sodium silicate No. 2 based on JIS K1408 ^{-1 966.}

  After completion of the dropwise addition, the mixture was further stirred for 1 hour to obtain a slurry having a pH of 6.8 containing a blue precipitated product. The slurry was filtered under reduced pressure with a glass filter with a microfilter having a mesh opening of 0.5 μm, and the precipitate was washed by flowing deionized water that did not overflow from the suction filter. Finally, the precipitate was obtained by suction filtration. . At this time, the electrical conductivity of the filtrate flowing out was measured, and washing was performed until the electrical conductivity reached 50 μS / cm or less.

  The time from the start of suction filtration of the slurry until the electric conductivity reached 50 μS / cm or less was measured and used as an index of filtration / cleanability. Evaluation is based on the criteria of ○ when the suction filtration and cleaning until the electric conductivity is 50 μS / cm or less are completed within 1 hour, × when it is not completed over 6 hours, and Δ when it is completed in the middle. However, in Example 1, since filtration and washing were completed within 1 hour, the evaluation was good. After the washing, the precipitated product was dried at 150 ° C. for 24 hours, and the crushing strength of this dried product was measured. Furthermore, the sulfur-type gas deodorizer was obtained by grind | pulverizing a dried product. The particle size d50 and d90 of the obtained deodorant powder was measured. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Example 2>
The same raw material as in Example 1 was dropped over 40 minutes so that the pH at the time of dropping the raw material was within the range of 7 to 8, but at the end of dropping of the raw material sodium silicate aqueous solution, Since there was a surplus, the entire amount was dropped over a period of 20 minutes within the range of pH 6-9. Other than that performed the same operation as Example 1, and obtained the sulfur type gas deodorizer. In addition, the pH of the slurry stirred for 1 hour after completion of preparation was 6.9, and filtration and washing were completed within 1 hour. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Example 3>
Two types of solutions prepared by adding 41.0 g of No. 2 sodium silicate and 17.75 g of copper sulfate pentahydrate to 100 ml of deionized water were adjusted to a pH within the range of 8 to 9 when the raw material was dropped. However, since the undropped copper sulfate aqueous solution remained at the end of dropping of the raw material sodium silicate aqueous solution, the entire amount was dropped over 20 minutes within the range of pH 6-9. Other than that performed the same operation as Example 1, and obtained the sulfur type gas deodorizer. In addition, the pH of the slurry stirred for 1 hour after the completion of preparation was 8.2, and filtration and washing were completed within 1 hour. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Example 4>
The same procedure as in Example 1 was performed except that 37.5 g of sodium silicate 2 and 19.5 g of copper sulfate pentahydrate were used, and the mixture was prepared so as to maintain the pH in the range of 6 to 7, and sulfur. A system gas deodorant was obtained. In addition, pH of the slurry stirred for 1 hour after completion of preparation was 6.0, and filtration and washing were completed within 1 hour. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Example 5>
The same operation as in Example 1 was performed except that 65.6 g of No. 2 equivalent potassium silicate (K ₂ O.3.5SiO ₂ .xH ₂ O, SiO ₂ concentration 20 mass%) was used instead of sodium silicate. The mixture was prepared so as to maintain the pH in the range of 6 to 7, and a sulfur-based gas deodorant was obtained. In addition, pH of the slurry stirred for 1 hour after completion of preparation was 8.8, and filtration and washing were completed within 1 hour. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Example 6>
The same operation as in Example 2 was performed except that 65.6 g of No. 2 equivalent potassium silicate (K ₂ O.3.5SiO ₂ .xH ₂ O, SiO ₂ concentration 20 mass%) was used instead of sodium silicate. A sulfur-based gas deodorant was obtained. In addition, the pH of the slurry stirred for 1 hour after completion of preparation was 8.0, and filtration and washing were completed within 1 hour. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Example 7>
The same procedure as in Example 1 was performed except that 20.45 g of zinc sulfate heptahydrate was used instead of 17.75 g of copper sulfate pentahydrate, and the formulation was adjusted so as to maintain the pH in the range of 6-7. The sulfur-based gas deodorant was obtained. The pH of the slurry stirred for 1 hour after the completion of the preparation was 7.2, and filtration and washing were completed within 1 hour. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Comparative Example 1>
The amount of raw materials charged was the same as in Example 1, but by adding a larger amount of the copper sulfate aqueous solution, the pH was adjusted to a range of 5 or more and less than 6, and the mixture was prepared for 40 minutes. The aqueous sodium silicate solution remaining at the end of the dropping of the aqueous copper sulfate solution was then added dropwise over 20 minutes. Otherwise, the same operation as in Example 1 was performed to obtain a sulfur-based gas deodorant. The slurry stirred for 1 hour after completion of the preparation had a pH of 6.7, and filtration and washing took 6 hours or more. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Comparative example 2>
The raw materials were charged in the same amount as in Example 1, but the amount of sodium silicate aqueous solution was increased so that the pH during the preparation was within the range of 10 to 11, and the preparation was carried out over 40 minutes. The copper sulfate aqueous solution remaining at the end of dropping of the raw material sodium silicate aqueous solution was dropped over 20 minutes thereafter. Otherwise, the same operation as in Example 1 was performed to obtain a sulfur-based gas deodorant.
The slurry stirred for 1 hour after completion of the preparation had a pH of 7.4, and filtration and washing took 6 hours or more. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Comparative Example 3>
A solution (pH 3.6) prepared by adding 17.75 g of copper sulfate pentahydrate to 175 ml of deionized water was placed in a 300 ml beaker and stirred. A solution (pH 13.2) prepared by adding 37.5 g of No. 2 sodium silicate to 100 ml of deionized water was added dropwise to the aqueous copper sulfate solution over 1 hour while maintaining the water temperature at about 25 ° C. After completion of the dropwise addition, the mixture was further stirred for 1 hour to obtain a blue precipitated product. At this time, the pH of the slurry was 6.7. The slurry was filtered, and the precipitated product was washed until the electrical conductivity of the filtrate was 50 μS / cm or less, but filtration and washing took 6 hours or more. After washing, the precipitated product was dried at 150 ° C. and then pulverized to obtain a sulfur-based gas deodorant. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Comparative example 4>
The preparation was carried out in the same manner as in Example 1 except that 23.0 g of copper sulfate pentahydrate was used and the pH was between 6 and 7 over 40 minutes. When the copper sulfate aqueous solution remaining at the end of dropping of the sodium silicate aqueous solution as the raw material was further dropped over 20, the pH of the reaction solution dropped to 4.9 on the way. The slurry stirred for 1 hour after completion of the dropping had a pH of 5.5, and filtration and washing took 6 hours or more. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Comparative Example 5>
The raw material was prepared in the same manner as in Example 1 except that 44.00 g of No. 2 sodium silicate and 17.75 g of copper sulfate pentahydrate were used and the pH was adjusted between 6 and 7 over 40 minutes. The dropping of the aqueous sodium silicate solution remaining at the end of dropping of the certain aqueous copper sulfate solution was dropped over the course of 20 minutes, but the pH rose to 10.3 on the way. The slurry having a pH of 10.0 after the completion of dropping was adjusted to pH 7.0 with a 10 wt% sulfuric acid aqueous solution and stirred for 1 hour to obtain a sulfur-based gas deodorant. The filtration and washing took 6 hours or more. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Comparative Example 6>
No. 2 sodium silicate 32.75 g and copper sulfate pentahydrate 21.50. In the same manner as in Example 1 except that g was used, the pH was dropped between 6 and 7 over 40 minutes. When the copper sulfate aqueous solution remaining at the end of dropping of the sodium silicate aqueous solution as a raw material was further dropped over 20, the pH dropped to 4.9 on the way, and the pH after the dropping was 5.1. The slurry after completion of the preparation was adjusted to pH 7.0 with a 10 wt% aqueous sodium hydroxide solution and stirred for 1 hour to obtain a sulfur-based gas deodorant. The filtration and washing took 6 hours or more. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Comparative Example 7>
A solution (pH 11.6) prepared by adding 37.5 g of No. 2 sodium silicate to 175 ml of deionized water was placed in a 300 ml beaker and stirred. A solution (pH 3.2) in which 17.75 g of copper sulfate pentahydrate was added and dissolved in 100 ml of deionized water was added dropwise to the aqueous copper sulfate solution over 1 hour while maintaining the water temperature at about 25 ° C. After completion of the dropwise addition, the mixture was further stirred for 1 hour to obtain a blue precipitated product. At this time, the pH of the slurry was 6.7. The slurry was filtered, and the precipitated product was washed until the electrical conductivity of the filtrate was 50 μS / cm or less, but filtration and washing took 6 hours or more. After washing, the precipitated product was dried at 150 ° C. and then pulverized to obtain a sulfur-based gas deodorant. Table 1 shows the properties of the sulfur-based gas deodorant, and Table 2 shows the results of the deodorization test.

<Comparative Example 8>
1 liter of deionized water, 270 g of No. 2 sodium silicate, 25 g of zinc sulfate heptahydrate and 507 g of aluminum sulfate hexahydrate were added to a 2 liter beaker, and the pH was adjusted to 10 with a sodium hydroxide solution. Further, it was aged at 50 ° C. for 20 minutes. Next, 40% sulfuric acid was added with stirring to obtain a deodorant. The pH of the slurry after aging was 7.1, and filtration and washing were completed within 1 hour. Table 1 shows the properties of this deodorant and Table 2 shows the results of the deodorization test.

<Properties of sulfur gas deodorant>

<Deodorization test results>

<Examples 8 and 9>
Deodorant test for deodorized fiber 3 parts by mass of the deodorant of Example 1 or 3 parts by mass of the deodorant of Example 1 and 2 parts by mass of layered zirconium phosphate with respect to 100 parts by mass of pure water Were added to 3 parts by mass of an acrylic binder (KB-1300, manufactured by Toagosei Co., Ltd.) to prepare suspensions A and B.
50 parts by weight of each of these suspensions A and B and acrylic binder were applied to 100 parts by weight of polyester fiber, dried at 150 ° C., and then fiber A (Example 8) and fiber B (Example 9). And fiber C (deodorant content was 1.5 parts by mass with respect to 100 parts by mass of polyester fiber).
5 g of these fibers are put into a Tedlar bag, and 1 L of methyl mercaptan (initial concentration 15 ppm), hydrogen sulfide (initial concentration 20 ppm), and ammonia (initial concentration 100 ppm) are injected therein, and the residual gas concentration in the Tedlar bag after 30 minutes is measured. did. The results are shown in Table 3 (unit: ppm. ND indicates that it could not be detected).

As shown in the above examples, the sulfur-based gas deodorant of the present invention is excellent in productivity such as filter detergency and easy pulverization, and deodorant using the deodorant or deodorant. Compositions and deodorant products are excellent in deodorizing performance against sulfur-based malodors.

  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 (5)

The elemental composition (mole) ratio of at least one metal selected from copper, zinc, manganese, cobalt, and nickel is in the range of metal / silicon = 0.60-0.80, and the crushing strength is 1-3N. A sulfur-based gas deodorant comprising an amorphous metal silicate in the range of
A sulfur-based gas deodorant comprising the amorphous metal silicate according to claim 1, wherein the particle size distribution on a volume basis is 10 μm or less in terms of median diameter (d50 value) and 50 μm or less in terms of d90 value.
The method for producing a sulfur-based gas deodorant according to claim 1 or 2, wherein an aqueous solution containing a metal salt and an aqueous solution of an alkali silicate salt are prepared within a pH range of 6 to 9.
A deodorant composition comprising the sulfur-based gas deodorant according to claim 1 or 2.
  A deodorized product containing the sulfur-based gas deodorant or deodorant composition according to claim 1.