JP3386862B2 - Adsorbent composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel adsorptive composition for removing harmful components such as malodorous components. INDUSTRIAL APPLICABILITY The adsorbent composition of the present invention is widely used for deodorizing household odors such as toilets, refrigerators, and household odors, and industrial odors generated in hospitals, hotels, automobiles, livestock farms, sewage treatment plants, and the like. Further, among the adsorptive compositions of the present invention, those having excellent antibacterial properties are also used for antibacterial, insecticidal, acaric and deodorant of fibers and resin molded products.

[0002]

2. Description of the Related Art A foul odor that causes human discomfort is generated in various daily living environments or various facilities such as factories, human waste treatment plants, garbage treatment plants, and livestock farms. The complaints are increasing as well. Examples of substances that cause such a malodor include ammonia, hydrogen sulfide, amines, mercaptans, aldehydes, and lower fatty acids, but the actual malodorous components are more complicated and are not necessarily limited to these substances. Conceivable. In recent years, research on treatment technology against such odors has become popular,
The following various measures have been proposed.

(I) Masking method: A method which utilizes masking with an aromatic substance and offsetting effect by a plant extract component. This method merely masks the malodor with a fragrance and does not essentially remove the malodor. Moreover, the scientific basis for the method of utilizing the offsetting effect is not clear. (Ii) Chemical method: a neutralization method with an acid / alkali or a decomposition method of a substance causing an offensive odor with an oxidizing agent / reducing agent. Of these, the substances that can be treated by the neutralization method are limited. Further, there is a problem in safety including the oxidation / reduction method, and the apparatus becomes complicated. (Iii) Biological deodorization method: Although it is a deodorization method using microorganisms and enzymes, it lacks deodorization speed and persistence, and its use conditions are often limited. (Iv) Adsorption method: A method in which a malodorous component is adsorbed and removed by an adsorbent such as activated carbon. In this method, the conventional adsorbent does not have a sufficient adsorption capacity and cannot cope with a strong malodor. Further, it is difficult to adsorb many kinds of malodorous substances with one adsorbent.

Although some of these conventional deodorizing methods have some deodorizing effects and are put to practical use, further technical improvements are strongly desired to solve the above problems. Conventionally, activated carbon has been widely used as a deodorizing adsorbent. However, activated carbon alone has a small capacity for adsorbing ammonia and hydrogen sulfide, and cannot be said to be an excellent deodorizing adsorbent. Therefore, activated carbon has halides, metal ions, acids,
Although a substance carrying an alkali or the like has been devised, a deodorant having a sufficient ability is not known yet. Further, zeolite, silica gel, activated alumina and the like are also used as deodorants, but they are not necessarily satisfactory in terms of adsorption ability. Further, zinc oxide, magnesium oxide, iron oxide, iron hydroxide and the like are also used as inorganic adsorbents, but although these are suitable for adsorbing hydrogen sulfide, they are not so effective for adsorbing ammonia gas. On the other hand, zirconium oxide, zirconium phosphate, titanium oxide and the like are relatively excellent in adsorbing ammonia gas, but are inferior in hydrogen sulfide adsorbing ability.

As described above, conventional deodorants are effective against either acidic odors or basic odors, but generally not so effective against the other (Japanese Patent Laid-Open No. 64-474).
45, JP-A-55-51421, JP-A-53-1370.
89, JP-A-58-156539, JP-A-59-146.
578, JP-A-63-22074, JP-A-1-1483.
40, JP-A-1-151938, JP-A-1-20304
No. 0 publication). Further, Japanese Patent Laid-Open No. 63-54935 discloses an adsorbent using TiO2, but its adsorption performance is not sufficient. Furthermore, JP-A-63-2
No. 58644 discloses phosphoric acid or a salt thereof, and Fe and C.
Although it is disclosed that a simple mixture of o, Ni, Zr or a compound thereof is supported on a conventional carrier (activated carbon etc.) and used as a deodorant, a sufficient deodorizing effect has not been obtained yet.

On the other hand, in recent years, various products have been proposed in which an antibacterial agent, an antibacterial insecticide or the like is kneaded into a base material such as a fiber or a synthetic resin, and the antibacterial and insect repellent effects are utilized. When applied to such an application, the organic antibacterial agent has a problem in heat resistance such as decomposition and evaporation at a temperature of 150 to 300 ° C. required for kneading into a resin to weaken the effect. Inorganic antibacterial agents include those in which activated carbon is loaded with silver, and those in which zeolite is loaded with antibacterial metals (silver, copper, zinc) (JP-A-60-181002) and the like. ing. However, in the case of activated carbon, silver ions are easily eluted in the solution, and the antibacterial activity of the product is not permanent. In the case of zeolite, there is a problem that it is easily discolored by sunlight or heat, and its own ability to adsorb harmful components is small. Furthermore, research and development of antibacterial fibers using antibacterial materials are also being conducted. However, a satisfactory antibacterial material for fiber processing has not been found from the viewpoints of fiber processability, safety for human body, washing resistance, handling and the like. As an adsorbent that solves the above problems, a mixture of a water-insoluble phosphate such as titanium and a hydroxide such as zinc is proposed in PCT International Publication WO-08049 / 91. However, with this adsorbent, the cost of raw materials is high, the specific surface area is not sufficient, and the adsorption capacity may not be satisfactory.

[0007]

The object of the present invention is to eliminate the disadvantages of these conventional adsorbents and to strongly and efficiently adsorb both acidic components such as hydrogen sulfide and basic components such as ammonia gas. It is to provide an inexpensive novel adsorbent composition that can be obtained.

[0008]

The present inventors have found that a composition containing silicon dioxide, a water-insoluble phosphate of a tetravalent metal and a hydroxide of a divalent metal has excellent adsorptivity. After further studies, the present invention has been completed.
That is, the present invention provides an adsorbent composition containing silicon dioxide, a water-insoluble phosphate of a tetravalent metal and a hydroxide of a divalent metal, and a method for producing the composition.

As the tetravalent metal of the water-insoluble phosphate of the tetravalent metal in the composition of the present invention, any tetravalent metal may be used, but Group 4 elements are preferable. Specific examples include titanium, zirconium, thorium, hafnium, germanium, tin and lead. Among these, Group 4A metals (titanium, zirconium, hafnium) are preferable.
Particularly, titanium and zirconium are preferable. These tetravalent metal phosphates are usually water insoluble. Further, it is preferable that this phosphate forms an amorphous salt. The above-mentioned tetravalent metal phosphates may be used alone or as a mixture of two or more metal phosphates.
The phosphoric acid in this phosphate may be any of orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid and the like. The phosphate also includes hydrogen phosphate.

As the divalent metal of the divalent metal hydroxide in the composition of the present invention, any divalent metal may be used, and specifically, magnesium, calcium, strontium, barium, zinc and cadmium. , Chromium, manganese, iron, cobalt, nickel, copper and the like.
Divalent transition metals such as manganese, iron, cobalt, nickel, copper and zinc are preferred. In particular, copper and zinc are preferably used. These divalent metal hydroxides are usually
It is insoluble in water in the weakly acidic to weakly alkaline region (pH 4 to 10). Further, the hydroxide preferably forms an amorphous salt. The above divalent metal hydroxides may be used alone or as a mixture of two or more kinds of metal hydroxides.

In the composition of the present invention, the content ratio of the tetravalent metal and the divalent metal is preferably 0.1 to 10, particularly preferably 0.2 to 5 in terms of metal atom ratio (divalent metal / tetravalent metal). It is a range. When a plurality of tetravalent metal phosphates and / or divalent metal hydroxides are mixed and used, the metal atomic ratio should be within the above range with respect to the total amount of each metal. Any silicon dioxide may be used in the composition of the present invention. For example, one in which silicon dioxide itself is made into an inorganic polymer, a composite compound of silicon dioxide and a tetravalent metal phosphate, a composite compound of silicon dioxide and a divalent metal hydroxide,
Examples thereof include a composite compound of silicon dioxide and silver. Also,
They may be hydrous silicon dioxide. Of these, the amorphous one is preferable. The content ratio of this silicon dioxide is 0.2 to 10 in terms of metal atom ratio {(silicon atom) / (divalent metal + tetravalent metal)} with respect to the total amount of metals of tetravalent metal and divalent metal. Those in the range are preferred. More preferably, the range of 1-8 is preferable.

The adsorbent composition of the present invention may contain appropriate other components in addition to the above components. A preferable example of such other component is silver. The silver may be metallic silver itself or a silver compound. In order for this silver to be used as a component of the adsorbent composition of the present invention, it is preferably water-insoluble. For example, it may be an inorganic or organic silver compound. Preferred water-insoluble compounds of silver include silver phosphate, silver chloride, silver oxide, a complex compound of tetravalent metal phosphate and silver, a complex compound of divalent metal hydroxide and silver, or silicon dioxide and silver. Is a complex compound. Also,
Two or more of these may be mixed. Further, the water-insoluble compound of silver is preferably amorphous. A preferable content ratio of the water-insoluble compound of silver is such that the metal atom ratio {(silver) / (divalent metal + tetravalent metal)} is 0.01 to the total amount of the metal of the tetravalent metal and the divalent metal. The range is 1.0, particularly preferably 0.02 to 0.5. Among the compositions of the present invention containing the above components, an amorphous composition, particularly a coprecipitation composition obtained by coprecipitation, is suitable.

Such an adsorbent composition of the present invention is usually
It has a BET specific surface area of 100 to 1000 m ² / g. Preferably 150~1000m ² / g, more preferably from sorbent composition having a specific surface area of 200~1000m ² / g. The composition of the present invention can be easily obtained by mixing silicon dioxide, a tetravalent metal phosphate and a divalent metal hydroxide, and optionally a water-insoluble compound of silver in the above proportion. is there. For this mixing, each component may be simply mixed as a powder by pulverization or the like.

In the production of the composition of the present invention, an aqueous solution containing silicate ions or silicon dioxide, divalent metal and tetravalent metal ions is used to obtain a mixed precipitate of these water-insoluble substances. The method is more suitable. The mixed precipitate thus obtained is usually in the form of gel, and when it is dried, it becomes a mixture having an amorphous structure. The silicon dioxide may be hydrogel or hydrosol. Various water-soluble metal compounds are used for the preparation of the aqueous solution. Examples of such water-soluble metal compounds of divalent and tetravalent metals or silver include metal compounds such as various metal salts and metal alkoxides. As the metal salt, in addition to a normal metal salt (normal salt), an acid salt, an oxy salt, and other double salts or complex salts may be used. Further, the compound may be insoluble when the pH of the aqueous solution is near neutral, or may be dissolved in an acidic solution. Specifically, the following are mentioned.

(1) Halides of metal chlorides, fluorides, iodides, bromides, etc .: CoCl ₂ , NiCl ₂ ,
CuCl ₂ , ZnCl ₂ , TiCl ₄ , SnCl ₄ , ZrC
l ₄ , FeCl ₂ , FeF ₂ , FeI ₂ , FeBr ₂ , Na ₂
(SnF ₆ ), K ₂ (SnF ₆ ), K ₂ (SnCl ₆ ), T
hCl ₄ , PbCl ₄ , GeCl ₄ , CaCl ₂ , CrCl
₂ , BaCl ₂ , MgCl ₂ , MnCl _2, etc.

(2) Sulfate, ammonium sulfate, and other sulfates (inorganic acid salts): FeSO ₄ , CoSO ₄ , Zr
(SO ₄ ) ₂ , Sn (SO ₄ ) ₂ , Th (SO ₄ ) ₂ , Pb
(SO ₄ ) ₂ , Ti (SO ₄ ) ₂ , (NH ₄ ) ₂ Fe (S
O ₄ ) ₂ , ZnSO ₄ , CdSO ₄ , Ag ₂ SO ₄ , CrSO
₄ , CuSO ₄ , NiSO ₄ , MgSO ₄ , MnSO ₄ , K ₂
Co (SO ₄ ) ₂ , (NH ₄ ) ₂ Mn (SO ₄ ) _{2 and the} like.

(3) Nitrate (inorganic acid salt): Zn (N
O ₃ ) ₂ , Co (NO ₃ ) ₂ , Cd (NO ₃ ) ₂ , Ca (NO
₃ ) ₂ , AgNO ₃ , Sn (NO ₃ ) ₄ , Fe (NO ₃ ) ₂ ,
Cu (NO ₃ ) ₂ , Th (NO ₃ ) ₄ , Ni (NO ₃ ) ₂ , B
a (NO ₃ ) ₂ , Mn (NO ₂ ) ₂ , Zr (NO ₃ ) ₄ , Ti
(NO ₃ ) ₄ etc.

(4) Other various inorganic acid salts such as chlorate, perchlorate, thiocyanate, diammine silver sulfate, diammine silver nitrate and chromate: Zn (ClO ₃ ) ₂ ,
Ca (ClO ₃ ) ₂ , AgClO ₃ , Ba (ClO ₃ ) ₂ ,
Ca (ClO ₄ ) ₂ , AgClO ₄ , Fe (ClO ₄ ) ₂ ,
Ni (ClO ₄ ) ₂ , Ba (ClO ₄ ) ₂ , Mg (Cl
O ₄ ) ₂ , Co (ClO ₄ ) ₂ , Zn (SCN) ₂ , Ca
(SCN) ₂ , CaCrO ₄ , Ag ₂ CrO ₄ , Ag ₂ CO ₃
Such.

(5) Organic acid salts such as acetate, formate and oxalate: (CH ₃ CO ₂ ) ₂ Zn, (CH ₃ CO ₂ ) ₄ Z
r, C ₂ O ₄ Co, (CH ₃ CO ₂ ) ₂ Co, (CH ₃ C
O ₂ ) ₂ Fe, (CH ₃ CO ₂ ) Cu, (CH ₃ CO ₂ ) ₂ N
_{i, (CH 3 CO 2)} 2 Ba, (CH 3 CO 2) 2 Mg, (C
H ₃ CO ₂₎ Ag, etc. _{(C 2 O 4) 2 Th} .

(6) Oxymetal salt (oxymetal salt in the form of halide, inorganic acid salt, organic acid salt): ZrOC
l ₂ , ZrOSO ₄ , ThOCl ₂ , TiOSO ₄ , ZrO
(NO ₃ ) ₂ , ZrOCO ₃ , (NH ₄ ) ₂ ZrO (CO ₃ )
₂ , ZrO (CH ₃ CO ₂ ) _2, etc.

(7) Metal alkoxides: Zr (OCH
₃ ) ₄ , Ti (OCH ₃ ) _4, etc.

Of the above, salts of inorganic acids are preferred as raw materials. Of these, strong acid salts are preferred. For example, sulfates and nitrates can be mentioned. Specifically, FeSO ₄ , T
i (SO ₄ ) ₂ , ZnSO ₄ , CuSO ₄ , AgNO ₃ , C
u (NO ₃ ) _{2 and the} like. Among the tetravalent metals,
As the compound of titanium or zirconium, an oxy metal salt is preferable, and specifically, ZrOCl ₂ , ZrOSO ₄ , T
iOSO ₄ may be mentioned.

Examples of the water-soluble silicate compound as a source of silicate ions include alkali metal salts of silicic acid such as sodium silicate and potassium silicate, alkaline earth metal salts of silicic acid such as calcium silicate and barium silicate, and ammonium silicate. Can be used. Further, with respect to silicon dioxide, it is also possible to use a silicon dioxide xerogel (silica gel), hydrosol or hydrogel as a raw material for production even if it is not water-soluble. Usually, an alkaline silicate is used. Among them, alkali metal silicates, hydrogels,
Hydrosols are preferable, and sodium silicate is particularly preferable in terms of price and ease of handling.

The mixed precipitate can be obtained by forming a hydroxide of a divalent metal in the presence of a water-insoluble phosphate of a tetravalent metal and silicon dioxide and / or silicate ions. In such a production method, silicate ions become hydrous silicon dioxide at the same time when divalent metal hydroxide is formed. Further, in the case of containing a water-insoluble compound of silver, the water-insoluble compound of silver previously generated may be allowed to coexist with a water-insoluble phosphate of a tetravalent metal, or a water of a divalent metal. It may be carried out at the same time as the oxide formation step. The concentration of the metal salt in the aqueous solution at the time of production described below is not particularly limited, but is 0.01 to 5.0.
It is preferably mol / l. If the manufacturing method is specifically shown, the following methods (i) and (ii) can be mentioned.

(I) Method of Using Alkaline Silicate Solution as Neutralizer (a) Forming a phosphate of a tetravalent metal ion in an aqueous solution in which a divalent metal ion and a tetravalent metal ion coexist, and then,
A method for producing a hydroxide of a divalent metal. When a precipitate is produced using an aqueous solution in which divalent metal ions and tetravalent metal ions coexist, an aqueous solution (pH is usually about 0 to 6) containing a predetermined amount of both divalent and tetravalent metal compounds is stirred. However, if necessary, an acid is added so that the divalent metal does not form an insoluble hydroxide, the pH is lowered to 4 or less, and then phosphoric acid or a phosphate is added to the insoluble phosphate of the tetravalent metal. To produce a gel. At this time, when a composition containing silver is desired, a silver insoluble compound may be formed by allowing silver ions to coexist with divalent metal ions and tetravalent metal ions in advance.

For such pH adjustment, an appropriate alkali or acid is used as a neutralizing agent. In addition to alkaline silicate solutions (sodium silicate, potassium silicate, etc.) as alkali, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide, inorganic alkalis such as ammonia, Organic amines such as triethanolamine are used. As the acid, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, oxalic acid or the like is used. Examples of the phosphoric acid or phosphate used for producing the insoluble phosphate include phosphoric acid, metaphosphoric acid, pyrophosphoric acid, and their alkali metal salts (sodium, potassium, etc.) and ammonium salts. Specifically, sodium phosphate (first, second, third), potassium phosphate (first,
Second, third), ammonium phosphate (first, second, third), sodium metaphosphate, potassium metaphosphate, sodium pyrophosphate, potassium pyrophosphate and the like.

Next, the produced tetravalent metal insoluble phosphate is aged sufficiently. As a method of aging, stirring at room temperature (about 10 to 30 ° C) for a long time (about 1
A method of leaving it for about 48 hours), a method of heating at 100 ° C. or lower for a long time (about 1 to 48 hours) with stirring if necessary, a method of heating under reflux, and the like are adopted. After completion of the aging, an aqueous alkaline silicate solution is added to adjust the pH to 4 to 10. In this pH range, a divalent metal hydroxide is produced. At the same time, silicon dioxide is also produced. At this time, silicon dioxide is generally a hydrate. A mixed precipitate of these and an insoluble phosphate of a tetravalent metal is obtained. In addition, at this time, if silver ions are present in the system, a water-insoluble compound of silver is produced and a silver-containing mixed precipitate is obtained. At this time, you may use together other alkali as needed. Examples of the addition of such an alkali include a method of dropping an alkaline solution into an acidic solution containing a water-insoluble phosphate of a tetravalent metal to adjust the pH of the reaction solution to a predetermined value, and a method in which the reaction solution has a predetermined pH. A method may be mentioned in which a predetermined amount of an acidic solution and an alkaline solution are simultaneously dropped and mixed so as to maintain the temperature.

The reaction temperature of such a reaction is from room temperature to about 1
It is in the range of 00 ° C. If the reaction at room temperature is slow, it may be heated. If necessary, the reaction may be performed under pressure at a temperature of 100 ° C. or higher. Air may be used for stirring. In addition to the above-mentioned phosphates, tetravalent metals may partially form water-insoluble hydroxides, and divalent metals form water-insoluble phosphates other than hydroxides. You may have.

(B) In an aqueous solution containing a tetravalent metal ion, a tetravalent metal water-insoluble phosphate is first formed, and then a divalent metal ion is added to form a divalent metal hydroxide. Method. Phosphoric acid or phosphate is added to an aqueous solution containing tetravalent metal ions to obtain water-insoluble phosphate. After aging this phosphate, the pH is adjusted to 4 or less in some cases, and a metal salt containing silver ions and divalent metal ions or an aqueous solution thereof is added and stirred. At this time, a water-insoluble compound of silver may be formed. Then, the pH of the solution is adjusted to 4 or more by the same method as the method (a) to obtain a mixed precipitate. The silver ions may coexist in an aqueous solution containing tetravalent metal ions.
In such a method, the water-insoluble compound of silver may be formed together with the water-insoluble phosphate of the tetravalent metal or may be formed together with the water-insoluble hydroxide of the divalent metal. This is determined by the raw material used. Also in this reaction, the aging of the tetravalent metal phosphate is sufficient in a relatively short time. In addition to the above-mentioned phosphates, tetravalent metals may partially form water-insoluble hydroxides, and divalent metals form water-insoluble phosphates other than hydroxides. You may have.

(Ii) Method using sol or gel of silicon dioxide This method is substantially the same as the method (i) described above, except that a sol or gel of silicon dioxide prepared in advance is used as a divalent metal. This is a method of mixing before forming hydroxide. At this time, the sol or gel of silicon dioxide used may be one prepared with an alkaline silicate solution and an acid, or commercially available silica gel or colloidal silica (silica hydrosol). (A) Prior to producing the hydroxide of a divalent metal by the production methods (i)-(a) and (b), a sol or gel of silicon dioxide is added to the reaction solution. This addition may be performed before or after the formation of the tetravalent metal water-insoluble phosphate or before the formation of the divalent metal hydroxide. After that, the pH is adjusted by the same method as the above-mentioned respective production methods (i)-(a) and (b) to obtain the desired product. However, in the case of this production method, the pH adjusting solution may be a solution containing no silicate.

(B) Before the production of the divalent metal hydroxide by the above-mentioned production methods (i)-(a) and (b), the pH is adjusted.
Add an aqueous alkaline silicate solution within the range of not more than 4. By performing such addition and mixing, a sol or gel of silicon dioxide is produced in the aqueous solution. Then, the pH is adjusted by the same method as each of the above-mentioned production methods (i)-(a) and (b) to obtain the desired product. In each of the above production methods, the amount of each metal compound used is in the range of the reagent amount corresponding to each of the metal amounts described above.

The mixed precipitate obtained by the production methods (i) and (ii) can be obtained as the composition of the present invention by a method known per se. For example, the mixed precipitate-containing solution is filtered, and anion species mixed in the metal salt are washed and removed using ion-exchanged water. Then, the obtained residue is dried to obtain the desired product. The filtration operation may be performed by using a filter paper at room temperature and atmospheric pressure, using a filter cloth, or by a centrifugal separation method, a pressure filtration method, or a vacuum filtration method. Further, as a cleaning method, an inclined cleaning method or the like may be used. The drying operation is carried out by air drying or under heating at about 400 ° C. or lower, preferably 200 ° C. or lower.

In the presence of such a water-insoluble phosphate of a tetravalent metal, a mixed precipitate produced by forming a hydroxide of a divalent metal and a water-insoluble compound of silver simply produces each component individually. The composition is different from the composition obtained by mixing and forms an amorphous composite. The composition of the present invention is one of the preferred embodiments.

The composition of the present invention may be used as it is as a deodorant or may be crushed and atomized before use. It is also possible to granulate these fine particles and form them into a spherical shape, a pellet shape, a granule or the like. It can also be used after being formed into a shape such as a honeycomb shape, a thin plate shape, or a film shape. Also, it may be in the form of a sheet. For example, the powder of the composition of the present invention is filtered into paper, the paper or plate-like material is coated with this composition,
Examples thereof include a bag-shaped or corrugated material such as a non-woven fabric which holds granules or powder of the present composition. This pulverized product can be supported on another substrate. It can be used by kneading it into a polymer film or the like, or by compounding it with synthetic fibers. For kneading into synthetic fibers, the powder of the composition of the present invention is mixed with the resin at high temperature. For example, in the case of a polyester resin, it needs to be performed at a high temperature of about 300 ° C. The composition of the present invention retains its deodorizing effect even under such high temperature conditions and is stable. In particular, since the composition of the present invention containing a water-insoluble compound of silver also has an antibacterial function, it can suppress the growth of microorganisms, prevent the generation of bad odors, and adsorb and remove the existing odors.

For example, when the composition of the present invention is used, excellent underwear (curtains, carpets, blankets, synthetic cotton, shoe insoles, air conditioner filters, towels, sports equipment (armor, clothing, etc.), underwear such as pantyhose, etc. , Diapers, socks, gloves, sanitary products, etc.) can be obtained. It can also be applied to wallpaper, synthetic resin bath tubs and kitchen utensils. In addition, clothes using the fiber containing the composition of the present invention have a light-scattering effect (especially ultraviolet rays) and are effective in blocking heat and light from the outside. Further, the composition of the present invention is also effective for the purpose of preventing spoilage of cooling water for cooling towers and water used for circulation such as water-soluble cutting oil. Particularly, in the case where the composition of the present invention is used as a honeycomb structure, if the circulating water passes through the honeycomb cell holes of the honeycomb structure, the bactericidal and deodorant of the circulating water can be efficiently achieved. . Further, such a honeycomb structure can be mounted on an air cleaner or an air conditioner for use. Due to its antibacterial effect, the composition of the present invention can be used for ordinary antibacterial applications. Examples of the microorganisms to be subjected to the antibacterial, antifungal, etc. are as follows.

--- Bacteria --- (1) Gram-negative bacteria-Escherichia coli (Escherichia coli, etc.)-Pseudomonas aerugino
sa etc.) Salmonella typhi (Sallmonella typhi)
Murium, etc.)-Klebsiella neumo
niae etc.) etc. (2) Gram-positive bacteria Staphylococcus a
ureus, etc.)-Micrococcus lut
eus, etc.)-Corynebacterium
um xerosis, etc.) Bacillus subtilis, etc.

--- Molds --- (3) Molds and Aspergillus nigar (Aspergillus nigar, As)
pergillusrestrictus, Asper
gillus graucus, etc.-Blue mold (Penicillium citrinum)
・ Cladosporium clas
dosporioides, etc.) ・ Cetomium (Globosu)
m) etc.-Wallemia sebi etc. --- Algae --- (4) Green algae, Chlorella pyrenoides
・ Senedesmus quadr
icauda etc.)-Selenastrum capr
icornutum etc.) etc.

(5) Bacterium, Skeletonema costa
etc.) (6) Blue-green algae (Oscillatoria rose)
a) etc.

The composition of the present invention exhibits a repellent effect against mites and harmful insects in addition to the above-mentioned antibacterial effect against microorganisms. For example, for cotton, wool, and synthetic fibers, Actnomy
ces sp. And Acremonium sp. Breed and contaminate and deteriorate the product. Also, for nylon, Bl
emmoria sp. , Vinylon has Cl. her
barum uses Pe. frequ
Entans breed. In the case of clothes, sweat and urine serve as nutritional sources, and Staphylococcus spp.
The illus genus is easy to reproduce and produces a foul odor. As described above, prevent various malodors and product deterioration caused by bacteria and molds in socks, underwear, clothes, carpets, curtains, etc. manufactured from the fiber using the composition of the present invention. You can

[0040]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. Example 1 Cu (II) -Ti (IV) -SiO ₂ composition 43.9 g of copper sulfate crystals (CuSO ₄ .5H ₂ O, Wako Pure Chemical Industries Reagent Special Grade) were dissolved in 1 liter of distilled water. Next, 60.0 g of titanium sulfate solution (about 30
A weight% concentration, Wako Pure Chemicals Reagent) was added. This aqueous solution contains 0.175 mol of Cu (II) ions and 0.075 mol of Ti (IV) ions. P of this aqueous solution
H was about 1. An aqueous sodium silicate solution (Wako Pure Chemicals Reagent diluted to 30% by weight with distilled water) was added dropwise to this aqueous solution to adjust the pH of the aqueous solution to 1.5. The amount of the aqueous sodium silicate solution added dropwise was 150 g (0.27 mol as SiO ₂ ). A sol of silicon dioxide was formed here.

About 11% of this aqueous solution was stirred at room temperature.
A white precipitate formed when 0 g of phosphoric acid solution (15% by weight) was added dropwise. This was stirred as it was at room temperature overnight.
Next, 321 g of the above-mentioned sodium silicate aqueous solution (0.59 mol as SiO ₂ ) was added dropwise to the aqueous solution containing this white precipitate while stirring at room temperature, and a more bluish white precipitate was formed. Furthermore, aqueous sodium hydroxide solution (15% by weight) was added dropwise until the pH of the solution reached 7.0 (about 30 m
l) Continue stirring at room temperature, and if the pH drops during this time, add sodium hydroxide solution (15% by weight) to adjust the pH.
Was held at 7. When the stirring was continued until no decrease in pH was observed, a pale-white mixed precipitate containing Cu (II) -Ti (IV) -SiO ₂ was formed. Then, the blue-white precipitate is filtered by suction, washed thoroughly with warm deionized water, and then washed with 40
It was dried at ° C. This was pulverized with a mortar to a size of 120 microns or less to obtain a pale white powder containing Cu (II) -Ti (IV) -SiO ₂ .

Example 2 Cu (II) -Ti (IV) -SiO ₂ composition 18.8 g of copper sulfate crystal (CuSO ₄ .5H ₂ O, Wako Pure Chemical Industries, Ltd. special grade reagent) was added to 1 liter of distilled water. Dissolved. Next, 140.0 g of titanium sulfate solution (about 3
0 wt% concentration, Wako Pure Chemical Industries reagent) was added. In this aqueous solution, 0.075 mol of Cu (II) ion, 0.175
It contains moles of Ti (IV) ions. The pH of this aqueous solution was about 1. An aqueous sodium silicate solution (Wako Pure Chemicals Reagent diluted to 30% by weight with distilled water) was added dropwise to this aqueous solution to adjust the pH of the aqueous solution to 1.5. The amount of the aqueous sodium silicate solution added dropwise was 471 g (0.86 mol as SiO2). A sol of silicon dioxide was formed here.

About 25% of this aqueous solution is stirred at room temperature.
A white precipitate formed when 7 g of phosphoric acid solution (15 wt%) was added dropwise. This was stirred as it was at room temperature overnight.
Next, an aqueous sodium hydroxide solution (15% by weight) was added to the aqueous solution containing the white precipitate while stirring to adjust the pH of the solution.
Was dropped to about 7.0 (about 200 ml), and stirring was continued at room temperature. During this period, if the pH was lowered, sodium hydroxide solution (15% by weight) was further added to keep the pH at 7. When the stirring was continued until no decrease in pH was observed, a pale-white mixed precipitate containing Cu (II) -Ti (IV) -SiO ₂ was formed. Next, this pale white precipitate was filtered by suction, thoroughly washed with warm deionized water, and then dried at 40 ° C. This is crushed in a mortar to less than 120 microns and Cu
To give a pale powder containing (II) -Ti (IV) -SiO 2.

Example 3 Cu (II) -Ti (IV) -SiO ₂ Composition 140 g of titanium sulfate solution (about 3 parts) in 1 liter of distilled water.
0 wt% concentration, Wako Pure Chemical Industries reagent) was added. This aqueous solution contains 0.175 mol of Ti (IV) ions.
About 257 g of a phosphoric acid aqueous solution (15% by weight) was added dropwise to this aqueous solution with stirring at room temperature to produce a white precipitate. This was stirred as it was at room temperature for 2 hours. Next, 18.8 g of copper sulfate crystals (CuSO ₄ .5H ₂ O, Wako Pure Chemical Industries, Ltd. special grade reagent) were added to and dissolved in the aqueous solution containing this white precipitate. 0.075 mol of Cu was added to the added copper sulfate.
(II) Ions are included.

To this aqueous solution, an aqueous sodium silicate solution (a reagent manufactured by Wako Pure Chemical Co., Ltd. diluted with distilled water to 30% by weight) was added dropwise at room temperature with continuous stirring until the pH reached 7.0 to lower the pH. Then, an aqueous sodium silicate solution was further added to maintain the pH at 7.0. If stirring is continued until the decrease in pH is not observed, Cu (II) -Ti (IV)
A bluish white mixed precipitate containing —SiO ₂ was formed. The sodium silicate aqueous solution added at this time was 884 g (S
It was 1.6 mol as iO ₂ . Next, this pale white precipitate was filtered by suction, washed thoroughly with warm deionized water, and then
It was dried at 0 ° C. This was pulverized with a mortar to a size of 120 microns or less to obtain a pale white powder containing Cu (II) -Ti (IV) -SiO ₂ .

Example 4 Ag (I) -Cu (II) -Ti (IV) -SiO ₂ composition 18.8 g of copper sulfate crystals (CuSO ₄ .5H ₂ O, Wako Pure Chemicals Reagent Special Grade) were used. It was dissolved in 1 liter of distilled water. Next, 4.26 g of silver nitrate crystal (AgN
O ₃ ; special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added and dissolved. Further, 120 g of titanium sulfate solution (concentration of about 30% by weight, Wako Pure Chemical Industries, Ltd. reagent) was added to the aqueous solution. In this aqueous solution,
0.025 mol Ag (I) ion, 0.075 mol C
It contains u (II) ions and 0.150 mol of Ti (IV) ions. The pH of this aqueous solution was about 1. An aqueous sodium silicate solution (Wako Pure Chemicals Reagent diluted to 30% by weight with distilled water) was added dropwise to this aqueous solution to adjust the pH of the aqueous solution to 1.5. The dropped sodium silicate aqueous solution was 420 g.

About 22% of this aqueous solution was stirred at room temperature.
When 8 g of phosphoric acid solution (15% by weight) was added dropwise, a white precipitate was formed. This was stirred as it was at room temperature overnight.
Next, 51 g of the above-mentioned sodium silicate aqueous solution was added dropwise to the aqueous solution containing this white precipitate while stirring at room temperature, and a more bluish white precipitate was formed. Further, an aqueous solution of sodium hydroxide (15% by weight) was added dropwise until the pH of the solution reached 7.0 (about 270 ml), and stirring was continued at room temperature. During this period, if the pH was lowered, further sodium hydroxide solution (15
Wt%) was added to maintain the pH at 7. Ag (I) -Cu was added when stirring was continued until the decrease in pH was not observed.
(II) -Ti (IV) mixtures precipitate pale containing -SiO ₂ was produced. Next, this pale white precipitate was filtered by suction, thoroughly washed with warm deionized water, and then dried at 40 ° C. This is crushed in a mortar to a size of 120 microns or less, and Ag (I) -C
A pale white powder containing u (II) -Ti (IV) -SiO ₂ was obtained.

Example 5 Ag (I) -Cu (II) -Ti (IV) -SiO ₂ composition 18.8 g of copper sulfate crystals (CuSO ₄ .5H ₂ O, Wako Pure Chemical Industries, Ltd. special grade reagent) were used. It was dissolved in 1 liter of distilled water. Next, 8.5 g of silver nitrate crystals (AgNO ₃ ;
Wako Pure Chemical Industries, Ltd. reagent special grade) was added and dissolved. Further, 100 g of titanium sulfate solution (concentration of about 30% by weight, Wako Pure Chemical Industries, Ltd. reagent) was added to the aqueous solution. In this aqueous solution, 0.05
Mol of Ag (I) ion, 0.075 mol of Cu (II)
Ions, 0.125 mol of Ti (IV) ions are included. The pH of this aqueous solution was about 1.

An aqueous sodium silicate solution (Wako Pure Chemicals Reagent diluted to 30% by weight with distilled water) was added dropwise to this aqueous solution to adjust the pH of the aqueous solution to 1.5. The dropped sodium silicate aqueous solution was 240 g. About 192 g of a phosphoric acid solution (15% by weight) was added dropwise to this aqueous solution with stirring at room temperature to give a white precipitate. This was stirred as it was at room temperature overnight. Next, 231 g of the above-mentioned sodium silicate aqueous solution was added dropwise to the aqueous solution containing the white precipitate while stirring at room temperature, and a more bluish white precipitate was formed. Furthermore, aqueous sodium hydroxide solution (15% by weight) was added dropwise until the pH of the solution reached 7.0 (about 80 m
l) Continue stirring at room temperature, and if the pH drops during this period, add sodium hydroxide solution (15% by weight) to adjust the pH.
Was held at 7.

When the stirring is continued until the decrease in pH is not observed, Ag (I) -Cu (II) -Ti (IV) -Si.
A pale white mixed precipitate containing O ₂ was formed. Next, this pale white precipitate was filtered by suction, thoroughly washed with warm deionized water, and then dried at 40 ° C. This is crushed to less than 120 microns in a mortar, and Ag (I) -Cu (II) -Ti (IV) -S
A pale white powder containing iO ₂ was obtained.

Example 6 Cu (II) -Ti (IV) -SiO ₂ Composition 43.9 g of copper sulfate crystal (CuSO ₄ .5H ₂ O, Wako Pure Chemical Industries, Ltd. special grade reagent) was added to 1 liter of distilled water. Dissolved. Next, 60.0 g of titanium sulfate solution (about 30
A weight% concentration, Wako Pure Chemicals Reagent) was added. This aqueous solution contains 0.175 mol of Cu (II) ions and 0.075 mol of Ti (IV) ions. P of this aqueous solution
H was about 1. Furthermore, while stirring at room temperature, about 11
When 0 g of phosphoric acid solution (15% by weight) was added dropwise, a white precipitate was produced. This was stirred as it was overnight.

A liquid containing this precipitate (liquid A), 471
A solution prepared by previously adding 30 ml of an aqueous sodium hydroxide solution (15% by weight) to an aqueous sodium silicate solution (30% by weight of Wako Pure Chemicals Reagent diluted with distilled water: 0.86 mol as SiO ₂ ) (B (Liquid) and while stirring in separate beakers into a container containing 500 ml of distilled water at the same time, a blue-white mixed precipitate containing Cu (II) -Ti (IV) -SiO ₂ was formed. . The dropping amount was adjusted so that the pH during mixing was always 7.0. Subsequently, stirring was continued for 2 hours while heating to 60 ° C. on a water bath. Next, this pale white precipitate was filtered by suction, thoroughly washed with warm deionized water, and then dried at 40 ° C. This was pulverized with a mortar to a size of 120 microns or less to obtain a pale white powder containing Cu (II) -Ti (IV) -SiO ₂ .

Example 7 Ag (I) -Cu (II) -Ti (IV) -SiO ₂ composition 31.2 g of copper sulfate crystals (CuSO ₄ .5H ₂ O, Wako Pure Chemicals reagent special grade) and 8. 5 g of silver nitrate crystals (AgNO ₃ ,
Wako Pure Chemicals Reagent Special Grade) was dissolved in 1 liter of distilled water.
Further, 60 g of titanium sulfate solution (about 30% by weight, Wako Pure Chemicals Reagent) was added to the aqueous solution. In this aqueous solution, 0.
05 mol Ag (I) ion, 0.125 mol Cu (I)
I) ion and 0.075 mol of Ti (IV) ion. About 123 g of this aqueous solution at room temperature with stirring
When a phosphoric acid solution (15% by weight) was added dropwise, a white precipitate was produced. This was stirred overnight at room temperature (Liquid A).

On the other hand, 471 g of sodium silicate solution (Wako Pure Chemicals Reagent diluted to 30% by weight with distilled water: S
20 ml of a sodium hydroxide aqueous solution (15% by weight) was added to 0.86 mol of iO ₂ (solution B). 500 ml
When the solution A and the solution B were simultaneously dropped into the container containing the distilled water described above so that the pH was always 7.0, a bluish white precipitate was formed. Then, stirring was continued for another 2 hours while heating to 60 ° C. on a water bath. Next, the pale white precipitate was filtered by suction, thoroughly washed with warm deionized water, and then dried at 40 ° C. Grind this to 120 microns or less in a mortar,
was obtained g (I) -Cu (II) -Ti (IV) pale powder containing -SiO _2.

Example 8 Ag (I) -Zn (II) -Ti (IV) -SiO ₂ composition In Example 7, instead of copper sulfate, zinc sulfate (0.1
25 mol: ZnSO ₄ .7H ₂ O, Wako Pure Chemical Reagent Special Grade) was used in exactly the same manner except that Ag (I) -Zn (I
To obtain a white powder comprising _{I) -Ti (IV) -SiO 2} .

Example 9 Cu (II) -Ti (IV) -SiO ₂ Composition 43.9 g of copper sulfate crystals (CuSO ₄ .5H ₂ O, Wako Pure Chemicals reagent special grade) were dissolved in 1 liter of distilled water. did. Further, 60.0 g of titanium sulfate solution (about 30% by weight, Wako Pure Chemicals Reagent) was added to the aqueous solution. In this aqueous solution, 0.
175 mol Cu (II) ion, 0.075 mol Ti
(IV) Contains ions. Meanwhile, 471 g of 471 g of sodium silicate solution (Wako Pure Chemicals Reagent diluted to 30% by weight with distilled water: 0.86 mol as SiO ₂ )
dropwise with stirring to 3.6N-H ₂ SO ₄ solution of l,
A sol of silicon dioxide was produced. At this time, the pH is 1.
It was 5.

A solution containing this silicon dioxide sol was added to the above C
It was added to a solution containing u (II) -Ti (IV) with stirring. Next, 110 g of a phosphoric acid solution (15% by weight) was added to this solution, and stirring was continued all day and night (solution A). This solution A and a 15% by weight sodium hydroxide solution were simultaneously dropped into a container containing 500 ml of distilled water while stirring so that the pH was kept constant at 7.0. Cu (II) -Ti (IV )
Pale precipitate containing -SiO ₂ was produced. Then, stirring was continued for 2 hours, heating at 60 degreeC on a water bath. Thereafter, in the same manner as in Example 7, Cu (II) -Ti (IV) -S
A pale white powder containing iO ₂ was obtained.

{Test Example 1} Adsorption characteristics test The adsorption characteristics of the powders obtained in the examples for malodorous substances were measured for hydrogen sulfide and ammonia by the following methods. 40 mg of dried powder with an internal volume of 3,000 m
It was put in a glass desiccator (with a stirring device) of 1 and capped with a rubber stopper. Then, the malodorous component gas is injected into the desiccator using a syringe so that the initial concentration (Co) becomes 100 ppm. 30 minutes after injecting the gas, the air in the desiccator was taken out with a microsyringe and subjected to gas chromatography {manufactured by Shimadzu Corporation, Shimadzu GC-14.
The gas concentration (C30) was measured by A type} and the removal rate was obtained.
The results are shown in {Table 1}. {Test Example 2} Measurement of specific surface area The BET specific surface area of the powder obtained in the example was measured with ASAP-2400 manufactured by Shimadzu Corporation. The results are shown in {Table 1}
Shown in.

[0059]

[Table 1]

{Test Example 3} Antibacterial test As a test bacterium, Bacillus subtilis
IFO-13719 and Escherichia col
i IFO-3301 was used. These platinum strains were pre-cultured in PY medium at 37 ° C. for 24 hours, and a fresh culture of one platinum loop was uniformly suspended in 5 ml of sterilized water. 0.2
5 ml of this bacterial solution was dispensed in 10 ml of a TBS medium (manufactured by BBL) containing 0.1% (W / V) sample (100 m).
1 volume Erlenmeyer flask was inoculated, and the rotary shaker (200
The culture was performed at 28 ° C. for 24 hours. This culture solution was diluted 10-fold with water, and then the turbidity (C ₁ ) at 600 nm was measured by a spectrophotometer (U-1080 Au manufactured by Hitachi, Ltd.).
to Sipper Photometer). The turbidity (C ₂ ) of this culture solution before culturing was also determined by the following formula to determine the antibacterial activity (%). As a control, the turbidity (C ₃ ) when the bacteria were cultured in TSB medium containing no sample and the turbidity (C ₄ ) before the culture were measured. The obtained results are shown in {Table 2}. The PY medium is 10 g
/ L (manufactured by Nippon Pharmaceutical) of polypeptone, 2 g / L of yeast extract (Difco Co.), magnesium sulfate _{1g / L (MgSO 4 · 7H} 2 O) and 20 g / L
Was dissolved in water to that concentration and the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, which was used as a slant medium.

[0061]

[Equation 1]

[0062]

[Table 2]

{Test Example-4} Heat resistance test (discoloration) The powder obtained in Example 8 was dried in an electric dryer in air at 115 ° C, 200 ° C and 300 ° C for 2 hours, respectively. Further, it was heated in air in an electric furnace at 500 ° C. for 2 hours. As a control, the same test was carried out on a zeolite on which silver was supported by the following method. The discolored state of the powder at each temperature was observed. The results are shown in [Table 3].

(Manufacturing method of silver-zeolite) 200 ml of pure water was put into a 300 ml beaker, and 3.39 g of silver nitrate crystal (manufactured by Wako Pure Chemical Industries, special grade) was dissolved therein. 20 g of Na-4A type zeolite (Silton T
M: manufactured by Mizusawa Chemical Co., Ltd., containing about 13% by weight of water) was added, and the mixture was stirred at room temperature for 2 hours. Thereafter, filtration washing, drying and pulverization were carried out in the same manner as in Example-1 to obtain silver-zeolite powder. This powder contained 10% by weight of silver as measured by an atomic absorption spectrometer.

[0065]

[Table 3]

[0066]

As described above, the composition of the present invention has the following advantages. (1) Since it has a large specific surface area, it has a high adsorption capacity. (2) High adsorption performance for both acidic malodorous gases such as hydrogen sulfide and alkaline malodorous gases such as ammonia. (3) It is effective in removing lower fatty acid salts such as valeric acid, which were difficult with conventional products. (4) The adsorption rate is large and the deodorizing effect is promptly exhibited. (5) The deodorizing effect lasts for a long time. (6) It also has a broad antibacterial spectrum. (7) Strong against heat. (8) It is hard to discolor by sunlight or heat. (9) It is harmless to the human body. (10) It is inexpensive. (11) It can be manufactured by a relatively simple process.

Therefore, the adsorptive composition of the present invention can be effectively used for the purpose of removing the malodor which is currently a problem in daily living environment and the malodor generated from various treatment facilities, industrial facilities and the like. Further, it can be widely used for the purpose of imparting deodorant properties and antibacterial properties to resins and fibers, and has excellent heat resistance.

Front Page Continuation (72) Inventor Harumi Obayashi 13-14 Ezance Takezono, 2-14 Takezono, Tsukuba, Ibaraki Prefecture (72) Inventor Masanori Tanaka 7-7-17, Daieicho, Shibata, Niigata (56) Reference Literature JP-A-53-116288 (JP, A) JP-A-6-154592 (JP, A) International publication 91/8049 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) B01J 20/00-20/34

Claims (10)

(57) [Claims] 1. An adsorptive composition containing silicon dioxide, a water-insoluble phosphate of a tetravalent metal, and a hydroxide of a divalent metal. 2. The adsorptive composition according to claim 1, wherein the tetravalent metal is a Group 4 element. 3. The adsorptive composition according to claim 1, wherein the tetravalent metal is titanium. 4. The adsorptive composition according to claim 1, wherein the divalent metal is a divalent transition metal. 5. The adsorptive composition according to claim 4, wherein the divalent transition metal is copper or zinc. 6. The content ratio of the tetravalent metal and the divalent metal is 0.1 to 10 in terms of metal atomic ratio (divalent metal / tetravalent metal),
The content ratio of silicon dioxide is 0.2 to 10 in terms of metal atom ratio {(silicon atom) / (divalent metal + tetravalent metal)} with respect to the total amount of tetravalent metal and divalent metal. The adsorptive composition according to claim 1. 7. A water-insoluble compound of silver is contained.
7. The adsorptive composition according to any one of to 6. 8. The content ratio of the water-insoluble compound of silver is a metal atom ratio {(silver) / (divalent metal + tetravalent metal)} with respect to the total amount of the metal of the tetravalent metal and the divalent metal. 0.01-1.0
The adsorbent composition according to claim 7, which is 9. The composition of claim 1, wherein the composition components are amorphous.
9. The adsorptive composition according to any of 8. 10. A divalent metal hydroxide is produced in the presence of a tetravalent metal water-insoluble phosphate and silicon dioxide and / or silicate ions.
10. The method for producing the adsorptive composition according to any of 9.