JP3300085B2 - Adsorbent composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel adsorptive composition which absorbs malodorous components and has antibacterial properties. The adsorptive composition of the present invention is widely used for deodorizing household odors generated from household toilets, refrigerators, garbage, and industrial odors generated in hospitals, hotels, automobiles, livestock breeding farms, sewage treatment plants, and the like.

[0002] Furthermore, antibacterial and insect repellent properties of fibers and resin moldings,
It is also used for mites and odor control.

[0003]

2. Description of the Related Art An offensive odor that causes human discomfort is generated from various facilities such as daily living environment, factories, human waste processing plants, garbage processing plants, and livestock raising facilities. In recent years, complaints of odors have been increasing as "odor odor pollution".

[0004] Examples of substances causing such malodor include ammonia, hydrogen sulfide, amines, mercaptans, aldehydes, lower fatty acids and the like. However, the actual malodorous components are more complicated and are not necessarily limited to these substances.

[0005] In recent years, research on such an odor treatment technique has become active, and the following various measures have been proposed.

(I) Masking method: a masking method using an aromatic substance or a method utilizing a counteracting effect of a plant extract component. This method is merely a hiding of the malodor by the fragrance and does not essentially eliminate the malodor. Also,
The scientific basis for the use of offsetting is not clear.

(Ii) Chemical method: a method of neutralizing a substance causing malodor with an acid or alkali, or a method of decomposing a substance causing malodor with an oxidizing agent or a reducing agent. Among them, substances that can be treated by the neutralization method are limited. In addition, this chemical method, including the decomposition method by oxidation and reduction, has a problem in terms of safety, and its apparatus becomes complicated.

(Iii) Biological deodorizing method: Deodorizing method using microorganisms or enzymes, but lacks deodorizing speed and sustainability, and there are many restrictions on use conditions.

(Iv) Adsorption method: using an adsorbent such as activated carbon
This is a method of removing and removing odorous components. In this method, the adsorption capacity of the conventional adsorbent was not sufficient, and it was not possible to cope with a strong odor. Also, it was difficult to adsorb many kinds of odorous substances by one adsorbent.

Some of these conventional deodorizing methods exhibit a deodorizing effect to some extent and have been put to practical use. However, technical improvements for the above-mentioned problems are strongly desired.

Conventionally, activated carbon is widely used as a deodorizing adsorbent. However, activated carbon alone has a small adsorption capacity for ammonia and hydrogen sulfide, and cannot be said to be an excellent deodorizing adsorbent. So activated carbon has halides and metal ions,
Although those carrying acid, alkali, etc. have been devised,
Deodorizers having sufficient capacity have not yet been obtained.

Zeolite, silica gel, activated alumina and the like are also used as deodorants, but they are not always satisfactory in terms of adsorption capacity.

Further, zinc oxide, magnesium oxide, iron oxide, iron hydroxide and the like are also used as inorganic adsorbents. However, although they are suitable for the adsorption of hydrogen sulfide,
It has little effect on ammonia gas adsorption. On the other hand, zirconium oxide, zirconium phosphate, titanium oxide and the like are relatively excellent in adsorbing ammonia gas, but inferior in hydrogen sulfide adsorbing ability.

As described above, the conventional deodorant is effective for either the acidic odor or the basic odor, but generally has little effect on the other (Japanese Patent Application Laid-Open No. 64-474).
45, JP-A-55-51421, JP-A-53-1370
89, JP-A-58-156439, JP-A-59-146
578, JP-A-63-220074, JP-A-1-1483
40, JP-A-1-151938, JP-A-1-202004
No. 0).

Japanese Patent Application Laid-Open No. 63-54935 discloses an adsorbent using TiO ₂ , but its adsorbing performance is not sufficient. Further, JP-A-63-258
No. 644 discloses phosphoric acid or a salt thereof, Fe, Co,
It is disclosed that Ni, Zr or a simple mixture thereof or a compound thereof is supported on a conventional carrier (such as activated carbon) and used as a deodorant, but a sufficient deodorizing effect has not yet been obtained. JP-A-63-246167 and JP-A-63-220874 disclose adsorbents containing silicon dioxide, zinc oxide and the like, but these adsorbents have poor antibacterial properties. Further, the adsorption capacity of methyl sulfide is small.

In particular, an adsorbent capable of sufficiently adsorbing and removing methyl sulfide as a malodorous or harmful substance has not yet been developed. This methyl sulfide adsorption / removal agent has been taken up as one of the exhaust gas treatment problems in industry.

On the other hand, in recent years, various products have been proposed in which an antibacterial agent, a bactericidal insecticide and the like are kneaded into a base material such as fiber or synthetic resin. When such a product is manufactured, the organic antibacterial agent is used at a temperature of 150 to 300 ° C. when kneading the resin.
There is a problem in heat resistance, such as decomposition and evaporation depending on the temperature, weakening the effect.

Examples of the inorganic antibacterial agent include those in which silver is supported on activated carbon and those in which zeolite has an antibacterial metal (silver,
What carried copper, zinc) (Japanese Patent Application Laid-Open No. 60-18100)
No. 2) is known. However, in the case of activated carbon, silver ions are easily eluted into the solution, and the antibacterial activity of the product is not permanent. In the case of zeolite, there is a problem that the color is easily discolored by sunlight or heat. Furthermore, there is a problem that the adsorption performance of harmful components of zeolite itself is small.

Further, research and development of antibacterial fibers using antibacterial materials have been conducted. However, no satisfactory antibacterial material for fiber processing has yet been found in terms of fiber processing properties, human body safety, washing resistance, handling, and the like.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the drawbacks of these conventional inorganic adsorbents and inorganic antibacterial agents, and to use a single adsorptive composition to produce acidic substances such as methyl sulfide and hydrogen sulfide. An object of the present invention is to provide an excellent adsorptive composition capable of adsorbing and removing both basic substances such as ammonia gas and having antibacterial and insect repellent properties.

[0021]

Means for Solving the Problems The present inventor has created a novel adsorptive composition containing silver, a water-insoluble phosphate of a tetravalent metal and a hydroxide of a divalent metal. The inventors have found that they have an antibacterial effect and a deodorant effect, and have further studied, and completed the present invention.

That is, the present invention relates to an adsorptive composition containing silver, a water-insoluble phosphate of a tetravalent metal and a hydroxide of a divalent metal, and a method for producing the composition.

The silver in the present invention may be metallic silver or a water-insoluble silver compound. Examples of the water-insoluble silver compound include silver phosphate, silver chloride, a composite compound of silver oxide and a tetravalent metal phosphate and silver, or a composite compound of a divalent metal hydroxide and silver. . Among them, silver phosphate is preferred. In addition, those in which two or more kinds are mixed may be used.

The preferable content ratio of silver is such that the metal atomic ratio [(silver)] is based on the total amount of metal of tetravalent metal and divalent metal.
/ (Divalent metal + tetravalent metal)] is in the range of 0.01 to 1.0, particularly preferably in the range of 0.02 to 0.5.

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 a Group 4 element is preferred. Specific examples include titanium, zirconium, thorium, hafnium, germanium, tin, and lead. Among these, a Group 4A metal (titanium, zirconium, hafnium) is preferable.
In particular, titanium and zirconium are preferred. These tetravalent metal phosphates are usually water-insoluble. The phosphate is preferably amorphous. The above tetravalent metal phosphates may be used alone or as a mixture of two or more metal phosphates.

The phosphoric acid of the phosphate in the composition of the present invention may be any of orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid and polyphosphoric acid.

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

In the composition of the present invention, the content ratio of the tetravalent metal to the divalent metal is preferably from 0.1 to 10, particularly preferably from 0.2 to 5, in terms of the metal atomic ratio (divalent metal / tetravalent metal). Range. When a plurality of tetravalent metal phosphates and / or divalent metal hydroxides are mixed and used, the metal atomic ratio in the total amount of each metal may be within the above range.

Further, the composition of the present invention may contain components other than those described above. As such a component, for example, silicon dioxide is suitably used.

This silicon dioxide may be any.
For example, 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, a composite compound of silicon dioxide and silver, and the like. No. Further, those hydrous silicon dioxides may be used. Of these, amorphous ones are preferred.

The content ratio of silicon dioxide is 0.2 in terms of the metal atomic ratio [(silicon atom) / (divalent metal + tetravalent metal)] with respect to the total amount of the metal of the tetravalent metal and the divalent metal. A range of from 10 to 10 is preferred. More preferably, the range of 1 to 8 is preferable.

The adsorptive composition of the present invention containing such silicon dioxide usually has a BET of 100 to 1000 m ² / g.
It has a specific surface area. Preferably 150 to 1000 m
² / g, more preferably having a specific surface area of 200~1000m ² / g.

Among the compositions of the present invention containing the above components, an amorphous composition, particularly a coprecipitated composition obtained by coprecipitation, is preferred.

The composition of the present invention can be easily obtained by mixing silver, a tetravalent metal phosphate and a divalent metal hydroxide in the above proportions. For this mixing, the respective components may be simply mixed as powder by grinding or the like.

For the production of the composition of the present invention, a method of using an aqueous solution containing silver, divalent metal and tetravalent metal ions to obtain a mixed precipitate of these water-insoluble substances is more suitable. It is a thing. The mixed precipitate thus obtained is usually in the form of a gel, and when dried, it becomes a mixture having an amorphous structure.

For preparing the aqueous solution, various water-soluble metal compounds are used. Examples of such a water-soluble metal compound include metal compounds such as various metal salts and metal alkoxides. As the metal salt, a normal metal salt (normal salt)
In addition, metal salts in the form of acid salts, oxy salts, and other double salts and complex salts may be used. Further, the compound may be insoluble when the pH of the aqueous solution is around neutral, or may be a compound that is soluble in an acidic solution. Specifically, the following are mentioned.

(1) metal chlorides, fluorides, iodides,
Halides such as bromide: CoCl ₂ , NiCl ₂ , Cu
Cl ₂ , ZnCl ₂ , TiCl ₄ , SnCl ₄ , ZrC
l ₄ , FeCl ₂ , FeF ₂ , FeI ₂ , FeBr ₂ , Na ₂
[SnFe], K ₂ [SnF ₆ ], K ₂ [SnCl ₆ ], ThCl
₄ , PbCl ₄ , GeCl ₄ , CaCl ₂ , CrCl ₂ , B
aCl ₂ , MgCl ₂ , MnCl _{2 and the} like.

(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 (S
O ₄ ) ₂ , Ti (SO ₄ ) ₂ , (NH ₄ ) ₂ Fe (SO ₄ ) ₂ , ZnS
O 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 (NO 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 , Ba (NO ₃ ) ₂ , Mn (N
O ₂ ) ₂ , Zr (NO ₃ ) ₄ , Ti (NO ₃ ) _{4 and the} like.

(4) Other various inorganic acid salts such as chlorate, perchlorate, thiocyanate, diamine silver sulfate, diamine 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 (Cl
O ₄ ) ₂ , Ba (ClO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , Co (Ci
O ₄ ) ₂ , Zn (SCN) ₂ , Ca (SCN) ₂ , CaCrO ₄ ,
Ag ₂ CrO ₄ , Ag ₂ CO _{3 and the} like.

(5) Organic acid salts such as acetate, formate and oxalate: (CH ₃ CO ₂ ) ₂ Zn, (CH ₃ CO ₂ ) ₄ Zr, C ₂
O ₄ Co, (CH ₃ CO ₂ ) ₂ Co, (CH ₃ CO ₂ ) ₂ Fe, (C
H ₃ CO ₂ ) Cu, (CH ₃ CO ₂ ) ₂ Ni, (CH ₃ CO ₂ ) ₂ B
a, (CH ₃ CO ₂ ) ₂ Mg, (CH ₃ CO ₂ ) Ag, (C ₂ O ₄ ) ₂
Th etc.

(6) Oxymetal salt (oxymetal salt in the form of halide, inorganic acid salt, organic acid salt): ZrOCl ₂ ,
ZrOSO, ThOCl ₂ , TiOSO ₄ , ZrO (N
O ₃ ) ₂ , ZrOCO ₃ , (NH ₄ ) ₂ ZrO (CO ₃ ) ₂ , ZrO
(CH ₃ CO ₂ ) _{2 and the} like.

(7) Metal alkoxides: Zr (OC
H ₃ ) ₄ , Ti (OCH ₃ ) _{4 and the} like.

Of the above, salts of inorganic acids are preferred as raw materials. Among them, 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 , Cu
(NO ₃ ) _{2 and the} like.

The mixed precipitate can be obtained by forming a water-insoluble compound of silver and a hydroxide of a divalent metal in the presence of a water-insoluble phosphate of a tetravalent metal. The concentration of the metal salt in the aqueous solution during the production is not particularly limited, but is preferably 0.01 to 5.0 mol / l. Specifically, the following methods (i) to (iv) are mentioned.

(I) Phosphate of tetravalent metal ion is formed in an aqueous solution in which silver ion, divalent metal ion and tetravalent metal ion coexist, and then, hydroxide of divalent metal and water insoluble of silver A method for producing a compound.

A) An aqueous solution in which silver ions, divalent metal ions and tetravalent metal ions coexist is prepared.

B) When the pH of the aqueous solution is 4 or more, an acid is added to the aqueous solution while stirring to lower the pH to 4 or less. C) adding phosphoric acid or phosphate to the aqueous solution to form a gel-like precipitate of insoluble phosphate of the tetravalent metal. D) aging the formed precipitate sufficiently. E) adjusting the pH of the aqueous solution to 4 or more with an alkali,
The desired mixed precipitate is obtained.

The pH of the aqueous solution prepared in the step a) is usually about pH 0-6.

The step b) is performed so as not to produce a water-insoluble hydroxide of a divalent metal before the water-insoluble phosphate of a tetravalent metal is produced.

For adjusting the pH in the steps b) and e), an appropriate alkali or acid is used as a neutralizing agent. As the alkali, sodium hydroxide, potassium hydroxide,
Hydroxides of alkali metals and alkaline earth metals such as calcium hydroxide, inorganic alkalis such as ammonia, and organic amines such as triethanolamine are used. Further, as the acid, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, oxalic acid and the like are used. Such a neutralizing agent is preferably a water-soluble substance, and is usually used in the form of an aqueous solution.

Phosphoric acid or phosphate used for producing the insoluble phosphate in step c) includes phosphoric acid, metaphosphoric acid, pyrophosphoric acid, and alkali metal salts (such as sodium and potassium) and ammonium salts thereof. It is. 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.

In step c), silver ions may form a water-insoluble silver compound.

The ripening method in the above step d) may be, for example, a method in which the solution is left at room temperature (about 10 to 30 ° C.) for a long time (about 1 to 48 hours) while stirring, or the solution is heated to 100 ° C. or less. If necessary, a method in which the solution is left for a long time (about 1 to 48 hours) with stirring or a method in which the solution is heated to reflux is employed.

In step e), the divalent metal forms a hydroxide. The preferred pH range to adjust is 4-12.
It is. More preferably, it is 5.5 to 11. If silver ions are present in the solution, silver insoluble compounds are produced, and a mixed precipitate of these with the tetravalent metal insoluble phosphate is obtained.

The solution temperature in the above a) to e) is in a range from room temperature to about 100 ° C. If the precipitation at normal temperature is slow, heating may be performed. 100 ° C under pressure if necessary
It may be performed at the above temperature. Further, air may be used for stirring.

After step e), if necessary, the mixed precipitate may be aged by the same method as in step d).

In addition to the above-mentioned phosphate, the tetravalent metal is
Some of them may form a water-insoluble hydroxide,
The divalent metal may form a water-insoluble phosphate in addition to the hydroxide.

(Ii) A water-insoluble phosphate of a tetravalent metal is first formed in an aqueous solution in which a tetravalent metal ion is present, and then a silver ion and a divalent metal ion are added thereto to form a silver insoluble compound or a divalent metal. A method for producing a metal hydroxide.

A) An aqueous solution containing ions of a tetravalent metal is prepared. B) if the pH of the aqueous solution is 4 or higher, add acid to the aqueous solution while stirring to lower the pH to 4 or lower; C) adding phosphoric acid or phosphate to the aqueous solution to form a gel-like precipitate of insoluble phosphate of the tetravalent metal. D) if necessary, allow the formed precipitate to age sufficiently. E) adding silver ions and divalent metal ions to the aqueous solution; F) adjusting the pH of the aqueous solution to 4 or more with an alkali,
The desired mixed precipitate is obtained.

This method is also performed under the same conditions as in the above-mentioned production method (i),
Similar steps may be performed.

The ripening of the phosphate of the tetravalent metal in d) above may be for a relatively short time.

In addition to the above phosphates, tetravalent metals are
Some of them may form a water-insoluble hydroxide,
The divalent metal may form a water-insoluble phosphate in addition to the hydroxide.

The source of the silver ion and the divalent metal ion in the step e) may be the above-mentioned water-soluble salt containing these ions or an aqueous solution in which such a water-soluble salt is dissolved. The salt itself may be added to the reaction solution, or the aqueous solution may be added to the reaction solution.

The pH adjustment of f) may be performed in the same manner as in the above (i) -e).

After step f), if necessary, the mixed precipitate may be aged by the same method as in step d).

In this method, depending on the raw materials used, the water-insoluble silver compound may be formed together with a tetravalent metal phosphate or a divalent metal hydroxide.

In addition to the above-mentioned phosphates, tetravalent metals are
Some of them may form a water-insoluble hydroxide,
The divalent metal may form a water-insoluble phosphate in addition to the hydroxide.

(Iii) A water-insoluble phosphate of a tetravalent metal is first formed in an aqueous solution in which silver ions and tetravalent metal ions are present, and then a divalent metal ion is added thereto to form a silver insoluble compound or a divalent metal. A method for producing a metal hydroxide.

A) An aqueous solution containing silver ions and ions of a tetravalent metal is prepared. B) if the pH of the aqueous solution is 4 or higher, add acid to the aqueous solution while stirring to lower the pH to 4 or lower; C) adding phosphoric acid or phosphate to form a gel precipitate of insoluble phosphate of the tetravalent metal. D) aging the formed precipitate sufficiently. E) adding divalent metal ions to the aqueous solution; F) adjusting the pH of the aqueous solution to 4 or more with an alkali,
The desired mixed precipitate is obtained.

In this method, the same steps may be performed under the same conditions as in the above-mentioned production methods (i) and (ii).

The ripening of the phosphate of the tetravalent metal in d) may be performed in a relatively short time.

After step f), if necessary, the mixed precipitate may be aged by the same method as in step d).

In this method, the water-insoluble compound of silver may be formed together with a water-insoluble phosphate of a tetravalent metal or together with a water-insoluble hydroxide of a divalent metal. This is determined by the raw materials used.

In addition to the above-mentioned phosphates, tetravalent metals are
Some of them may form a water-insoluble hydroxide,
The divalent metal may form a water-insoluble phosphate in addition to the hydroxide.

(Iv) A water-insoluble phosphate of a tetravalent metal is first formed in an aqueous solution containing a tetravalent metal ion and a divalent metal ion, and then a silver ion is added thereto to form a silver insoluble compound or a divalent metal ion. A method for producing a metal hydroxide.

A) An aqueous solution containing tetravalent metal ions and divalent metal ions is prepared. B) if the pH of the aqueous solution is 4 or higher, add acid to the aqueous solution while stirring to lower the pH to 4 or lower; C) adding phosphoric acid or phosphate to form a gel precipitate of insoluble phosphate of the tetravalent metal. D) aging the formed precipitate sufficiently. E) adding silver ions to the aqueous solution; F) adjusting the pH of the aqueous solution to 4 or more with an alkali,
The desired mixed precipitate is obtained.

In this method, the same steps may be performed under the same conditions as in the above-mentioned production methods (i) to (iii).

The ripening of the phosphate of the tetravalent metal in d) may be performed in a relatively short time.

After step f), if necessary, the mixed precipitate may be aged by the same method as in step d).

In this method, the water-insoluble silver compound may be formed together with a water-insoluble hydroxide of a divalent metal.

In addition to the above-mentioned phosphates, tetravalent metals are
Some of them may form a water-insoluble hydroxide,
The divalent metal may form a water-insoluble phosphate in addition to the hydroxide.

The pH adjustment with an alkali in each of the above-mentioned production methods (i) to (iv) can be performed by the following method.

For example, a method in which an aqueous alkali solution is dropped into the reaction solution, and a method in which the reaction solution and the aqueous alkali solution are simultaneously dropped into a reaction vessel are exemplified. Among them, in the case of the simultaneous dropping method, the rate of dropping the reaction solution (usually acidic) and the aqueous alkali solution is adjusted so that the pH in the reaction vessel is always 4 or more, preferably 4 to 12, more preferably 5.5. ~ 1
Keep a certain range of 1.

In each of the above-mentioned production methods, the amount of each metal compound used is in the range of the amount of reagent corresponding to the above-mentioned amount of each metal.

The mixed precipitate obtained by the production methods (i) to (iv) and the like can be obtained as the composition of the present invention by a method known per se such as filtration, washing and drying. For example, the mixed precipitate-containing solution is filtered, and anion-exchange water is used to wash and remove anionic species mixed in the metal salt. Thereafter, the obtained residue is dried to obtain the target product.

The filtration operation may be performed by using a filter paper at normal temperature and normal pressure, a method using a filter cloth, a centrifugal separation method, a pressure filtration method, or a vacuum filtration method. In addition, the cleaning method may use an inclined cleaning method or the like.

The drying operation is performed by air drying or 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 in which a hydroxide of a divalent metal and a water-insoluble compound of silver are produced can be obtained by simply preparing each component individually. It has different physical properties from the composition obtained by mixing, and forms an amorphous complex. The composition of the present invention is one of preferred embodiments.

The composition containing silicon dioxide described above can be prepared according to the above-mentioned production method. For example, by forming a hydroxide of a divalent metal in the presence of a phosphate of a tetravalent metal, silver ions and / or a water-insoluble compound of silver and silicon dioxide and / or silicate ions, the desired silicon dioxide can be obtained. Can be obtained. In such a production method, the silicate ion becomes hydrated silicon dioxide simultaneously with the generation of the hydroxide of the divalent metal. A specific manufacturing method will be described.

(I) A method using an alkaline silicate solution as a neutralizing agent.

In each of the above-mentioned production methods (i) to (iv), an alkaline silicate solution is used as an alkali for adjusting the pH when generating a hydroxide of a divalent metal. Here, examples of the alkaline silicate solution include a sodium silicate aqueous solution and a potassium silicate aqueous solution.

(Ii) A method using a silicon dioxide sol or gel.

In each of the above-mentioned production methods (i) to (iv), a sol or gel of silicon dioxide prepared in advance is mixed before forming a hydroxide of a divalent metal. Here, the sol or gel may be commercially available silica gel, colloidal silica (silica hydrogel), or the like, or may be one prepared with an alkaline silicate and an acid.

An alkaline silicate may be added to an acidic solution containing a phosphate of a tetravalent metal as long as the pH does not become 4 or more. At this pH, the silicate ions become a sol or gel of silicon dioxide.

In this case, the water-soluble silicate compound as a silicon dioxide supply source includes alkali metal salts of silicate such as sodium silicate and potassium silicate, alkaline earth metal salts of silicate such as calcium silicate and barium silicate, and ammonium silicate. Can be used. In addition, silicon dioxide xerogel (silica gel), hydrosol or hydrogel of silicon dioxide can be used as a raw material even if it is not water-soluble. Usually, an alkaline silicate is used. In particular, sodium silicate is preferable in terms of cost and ease of handling.

The composition of the present invention can be used as it is. The composition may be pulverized and atomized before use. It is also possible to granulate these fine particles and form them into spheres, pellets, granules and the like. It can be used after being formed into a shape such as a honeycomb shape, a thin plate shape, and a film shape. This pulverized material can be supported on another substrate. It can also be kneaded into a polymer film or the like, or compounded with a synthetic fiber for use. In order to knead the synthetic fibers, the powder of the composition of the present invention is mixed with the resin at a high temperature. For example, in the case of a polyester resin, it is necessary to carry out at a high temperature of about 300 ° C. The composition of the present invention retains its antibacterial and deodorizing effects even under such high temperature conditions and is stable.

The composition of the present invention can be combed or coated on paper or the like, for example, in the form of a powder.
Such products are useful for toilet rugs, crate rugs, closet rugs, disposable diapers and the like.

In particular, since the composition of the present invention has an antibacterial and deodorant function, it can suppress the growth of microorganisms, prevent the generation of offensive odors, and adsorb and remove existing odors. For example, if the fiber containing the composition of the present invention is used, excellent daily necessities (curtains, carpets, blankets, synthetic cotton, shoe insoles, air conditioner filters, towels, sports equipment (clothing, armor, etc.), pantyhose, etc. Underwear, diapers, socks, gloves, sanitary products, etc.). It can also be applied to wallpaper, synthetic resin bathtubs, and even kitchenware. Clothing using fibers containing the composition of the present invention has a light-scattering effect (especially ultraviolet rays) and is effective in blocking heat and light from the outside. Also,
The composition of the present invention is also effective for the purpose of preventing spoilage of circulated water such as cooling water for a cooling tower or water-soluble cutting oil. In particular, 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 bacteriostatic and odor control of the circulating water can be efficiently achieved. . Further, such a honeycomb structure can be used by being mounted on an air purifier or an air conditioner.

The composition of the present invention can be used for ordinary antibacterial applications due to its antibacterial effect. Examples of microorganisms to be subjected to antibacterial and antifungal are as follows.

[0101] --- bacteria --- (1) gram-negative bacteria, Escherichia coli (Escherichi a coli, etc.), Pseudomonas aeruginosa (Pseudomona s aeruginosa, etc.), Salmonella (Sallmonel la typhimurium, etc.) - Kurebujera bacteria (Klebsiella neumoniae, etc. )Such.

(2) Gram-positive bacteria ・Staphylococcus aureus (such as Staphylococcus aureus) ・ Micrococcus (such as Micrococcus luteus) ・Corynebacterium xerosis
Etc.) Bacillus subtilis ( Bacillus subtilis etc.).

-Molds-(3) Molds-Black mold ( Aspergillus nigar, Aspergillus restric)
tus, Aspe rgillus graucus, etc.), and blue mold (Penicilliu m citrinum, etc.), clad port sports potassium (Cladospo rium cladosporioides
Etc. etc.), Chaetomium (Chaetomium globosum, etc.) · Wallemia sebi.

[0104] --- algae --- (4) green algae Chlorella (Chlorela pyrenoides, etc.), Scenedesmus (Scenedesm us quadricauda, etc.) - Selenastrum (Selenastrum capricornutum, or the like).

(5) Diatoms Skeletonema ( Skeletone ma costatum, etc.) and the like.

(6) Cyanobacteria- Oscillatoria ria rosea and the like.

The composition of the present invention has an antibacterial effect against microorganisms as described above, as well as a repellent effect against mites and pests.

For example, Actno myces is used for cotton, wool, and synthetic fibers.
sp. and Acremonium sp. propagate and contaminate and degrade the product. Blemmoria sp. For nylon and C for vinylon
l. herbarum, Pe.frequentans for hair and polyester
Breed. In the case of clothes, sweat and urine are a source of nutrition,
Easy Staphylococcus spp. And Bac illus genus breeding, to produce even the stench.

As described above, various odors and product deterioration caused by bacteria, molds, and the like are also reduced in socks, underwear, clothes, carpets, curtains, and the like made of fibers using the composition of the present invention. Can be prevented.

Further, by utilizing the antibacterial property and using the fiber kneaded with the composition of the present invention in white coats, curtains, sheets, mattresses, pillows, blankets, etc. used in hospitals, etc. It is also effective in preventing infection. It is also effective to knead the composition of the present invention into plastic and use it for equipment (catheter, filter) in hospitals to prevent hospital infection. The infection bacterial species in the hospital, Pseudomonas aeruginosa (Pseudomonas aeruginosa), Staphylococcus aureus (Staphy
lococus aureus ), especially MRSA (Methicillin
Resistant Staphylococcus aureus ) is typical.
It is possible to suppress infection of such bacterial species.

[0111]

The composition of the present invention has the following advantages.

(1) High adsorption performance to both acidic malodorous gas such as hydrogen sulfide and alkaline malodorous gas such as ammonia.

(2) The adsorption speed is high, and the deodorizing effect is quickly exhibited.

(3) The deodorizing effect lasts for a long time.

(4) It also has a broad antibacterial spectrum.

(5) Resistant to heat.

(6) Hardly discolored by sunlight or heat.

(7) It is harmless to the human body.

(8) It is effective for the adsorption and removal of methyl sulfide, which has been difficult in the past.

Therefore, the composition of the present invention can be effectively used for the purpose of removing offensive odor which is a problem in daily living environment and odor 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.

[0121]

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 examples.

[Example 1]Ag (I) -Z n (II) -Ti (I
V )Composition 34.5 g of zinc sulfate crystals (ZnSO_Four・ 7H_TwoO, Wako
Pure Chemical Reagent) was dissolved in 1 liter of distilled water. Then this
6.8 g of silver nitrate crystals (AgNO_Three, Wako Pure Chemical
Was added and dissolved. Furthermore, in this aqueous solution,
192.0 g of titanium sulfate solution (about 30% by weight,
(Special grade made by Kojun Pharmaceutical). In this aqueous solution,
04 mol of Ag (I) ion, 0.12 mol of Zn (II) ion
ON, containing 0.24 mole of Ti (IV) ions.
The pH of this aqueous solution was about 1.

This aqueous solution is stirred for about 33 hours at room temperature.
When 0 g of phosphoric acid solution (15% by weight) was added dropwise, a white precipitate formed. This was stirred at room temperature for 24 hours.
Next, a sodium hydroxide solution (15% by weight) was added dropwise to the aqueous solution containing the white precipitate under stirring at room temperature until the pH of the solution reached 7.0, whereby a further white precipitate was formed. Subsequently, stirring was continued at room temperature while the pH was maintained.
When the pH decreased, sodium hydroxide solution (15% by weight) was added to maintain the pH at 7.

When the stirring was continued until no decrease in pH was observed, a white mixed precipitate containing Ag (I) -Zn (II) -Ti (IV) was formed. Next, the white precipitate was filtered off with suction, sufficiently washed with warm deionized water, and dried at 40 ° C. This is crushed in a mortar to 120 microns or less.
A white powder containing (I) -Zn (II) -Ti (IV) was obtained. This powder contained silver phosphate, zinc hydroxide, and titanium phosphate.

[Example 2]Ag (I) -Z n (II) -Ti (I
V )Composition Ag (I) ion, Zn (II) ion and Ti (IV) ion
Is 0.08 mol, 0.12 mol,
Except for changing to 0.20 mol, exactly the same as in Example-1
Powder of mixed precipitate of Ag (I) -Zn (II) -Ti (IV) by the method
I got This powder is composed of silver phosphate, zinc hydroxide, titanium phosphate
It contained tongue.

[Example 3]Ag (I) -C u (II) -Ti (I
V )Composition As a divalent metal ion, instead of Zn (II) ion, Cu
(II) Ag was used in exactly the same manner as in Example 1 using ions.
A powder of a mixed precipitate of (I) -Cu (II) -Ti (IV) was obtained. What
The salt containing Cu (II) used was copper (II) sulfate (CuSO_Four
・ 5H_TwoO, Wako Pure Chemical Industries reagent special grade). This powder
The powder contains silver phosphate, copper hydroxide, and titanium phosphate
there were.

[Example-4]Ag (I) -C u (II) -Ti (I
V )Composition As a divalent metal ion, instead of Zn (II) ion, Cu
(II) Ag was prepared in exactly the same manner as in Example 2 using ions.
A powder of a mixed precipitate of (I) -Cu (II) -Ti (IV) was obtained. What
The salt containing Cu (II) used was copper (II) sulfate (CuSO_Four
・ 5H_TwoO, Wako Pure Chemical Industries reagent special grade). This powder
The powder contains silver phosphate, copper hydroxide, and titanium phosphate
there were.

[Comparative Example-1] Zn (II) -Ti (IV) composition In the same manner as in Example-1, except that no Ag (I) ion was added, and Zn (II) -Ti ( IV) A powder of the mixed precipitate was obtained. This powder contained zinc hydroxide and titanium phosphate.

Comparative Example 2 Cu (II) -Ti (IV) Composition In the same manner as in Example 3, no Ag (I) ions were added, and Cu (II) -Ti (IV) was mixed. A precipitate powder was obtained. This powder contained copper hydroxide and titanium phosphate.

[Example 5]Ag (I) -C u (II) -Ti (I
V ) Honeycomb structure of the composition Ag (I) -Cu (II) -Ti (IV) mixture obtained in Example-3
50 g of molding aid (Biopo
Lee^TM: Takeda Pharmaceutical) and an appropriate amount of water. this
The mixture is kneaded for 1 hour using a kneader, and kneaded for extrusion molding.
A composition was obtained. Next, the composition was extruded using an extruder (Honda
Honeycomb with a diameter of 30 mm using DE-35)
(300 cells / inch)^Two). This molding
Was dried at 40 ° C. all day and night to obtain a honeycomb body.

[Example-6] Ag (I) -Cu (II) -Ti (I
V) was dissolved -SiO ₂ composition 18.8g of crystals of copper sulfate (CuSO ₄ · 5H ₂ O, manufactured by Wako Pure Chemical Industries reagent special grade) in distilled water 1l. Next, 4.26 g of silver nitrate crystals (AgNO ₃ ; special grade of reagent manufactured by Wako Pure Chemical Industries) were added to and dissolved in this aqueous solution. Further, 120 g of a titanium sulfate solution (about 30% by weight, special grade of reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to the aqueous solution. In this aqueous solution,
0.025 mole Ag (I) ions, 0.075 mole Cu
(II) ions and 0.150 mol of Ti (IV) ions. The pH of this aqueous solution was about 1.

An aqueous solution of sodium silicate (Wako Pure Chemical Reagent diluted to 30% by weight with distilled water) was added dropwise to this aqueous solution, and the pH of the aqueous solution was adjusted to 1.5. The amount of the dropped sodium silicate aqueous solution was 420 g.

This aqueous solution was stirred at room temperature for about 22 minutes.
When 8 g of phosphoric acid solution (15% by weight) was added dropwise, a white precipitate formed. This was stirred at room temperature for 24 hours.
Next, 51 g of the above-mentioned aqueous solution of sodium silicate was added dropwise to the aqueous solution containing the white precipitate while stirring at room temperature, whereby a further blue-white precipitate was formed. Further, an aqueous solution of sodium hydroxide (15% by weight) was added dropwise until the pH of the solution became 7.0 (about 270 ml), and stirring was continued at room temperature.
% By weight) and the pH was maintained at 7.

When stirring was continued until no decrease in pH was observed, a pale white mixed precipitate containing Ag (I) -Cu (II) -Ti (IV) -SiO ₂ was formed.

Next, the blue-white precipitate was filtered off with suction, sufficiently washed with warm deionized water, and dried at 40 ° C. This is ground in a mortar to 120 microns or less, and Ag (I) -Cu (I
To give a pale powder containing _{I) -Ti (IV) -SiO 2} . The BET specific surface area of this powder was 498 m ² / g. This powder contained silver phosphate, copper hydroxide, and titanium phosphate.

[Example-7] Ag (I) -Cu (II) -Ti (I
V) was dissolved -SiO ₂ composition 18.8g of crystals of copper sulfate (CuSO ₄ · 5H ₂ O, manufactured by Wako Pure Chemical Industries reagent special grade) in distilled water 1l. Next, 8.5 g of silver nitrate crystals (AgNO ₃ ; special grade of reagent manufactured by Wako Pure Chemical Industries) were added to and dissolved in this aqueous solution. Further, 100 g of a titanium sulfate solution (approximately 30% by weight, special grade of reagent manufactured by Wako Pure Chemical Industries) was added to the aqueous solution. In this aqueous solution,
0.05 mole of Ag (I) ion, 0.075 mole of Cu (I
I) ions and 0.125 mol of Ti (IV) ions. The pH of this aqueous solution was about 1.

An aqueous solution of sodium silicate (Wako Pure Chemical Reagent diluted to 30% by weight with distilled water) was added dropwise to this aqueous solution, and the pH of the aqueous solution was adjusted to 1.5. The amount of the dropped sodium silicate aqueous solution was 240 g.

The aqueous solution was stirred at room temperature for about 19
A 2 g phosphoric acid solution (15% by weight) was added dropwise resulting in a white precipitate. This was stirred at room temperature for 24 hours.
Next, 231 g of the above-mentioned aqueous solution of sodium silicate was added dropwise to the aqueous solution containing the white precipitate while stirring at room temperature, whereby a further pale-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 80 ml), and stirring was continued at room temperature.
% By weight) and the pH was maintained at 7.

When stirring was continued until no decrease in pH was observed, a bluish white mixed precipitate containing Ag (I) -Cu (II) -Ti (IV) -SiO ₂ was formed.

Next, the blue-white precipitate was filtered off with suction, sufficiently washed with warm deionized water, and dried at 40 ° C. This is ground in a mortar to 120 microns or less, and Ag (I) -Cu (I
To give a pale powder containing _{I) -Ti (IV) -SiO 2} . The BET specific surface area of this powder was 510 m ² / g. This powder contained silver phosphate, copper hydroxide, and titanium phosphate.

[Example-8] Ag (I) -Cu (II) -Ti (I
V) -SiO ₂ composition 31.2 g of copper sulfate crystals (CuSO ₄ .5H ₂ O, special grade of Wako Pure Chemical Reagent) and 8.5 g of silver nitrate crystals (AgNO ₃ ,
Was dissolved in 1 liter of distilled water. Further, a 60 g titanium sulfate solution (about 30% by weight,
Wako Pure Chemical Reagent).

This aqueous solution contains 0.05 mol of Ag (I) ions, 0.125 mol of Cu (II) ions, and 0.075 mol of Ti (IV) ions. When about 123 g of a phosphoric acid solution (15% by weight) was added dropwise to this aqueous solution at room temperature with stirring, a white precipitate was formed. This was stirred overnight at room temperature (Solution A).

On the other hand, 471 g of sodium silicate solution (Wako Pure Chemical Reagent diluted to 30% by weight with distilled water: S
aqueous sodium hydroxide solution (15 wt%) was added 20ml 0.86 mol) as iO ₂ (B solution).

Into a container containing 500 ml of distilled water, p
When the solution A and the solution B were simultaneously dropped so that H was always 7.0, a blue-white precipitate was formed. Then on the water bath 6
Stirring was continued for another 2 hours while warming to 0 ° C.

Next, the blue-white precipitate was filtered off with suction, sufficiently washed with warm deionized water, and dried at 400 ° C. This is ground in a mortar to 120 microns or less, and Ag (I) -Cu
To give a pale powder containing (II) -Ti (IV) -SiO 2. The BET specific surface area of this powder was 403 m ² / g. This powder contained silver phosphate, copper hydroxide, titanium phosphate, and silicon dioxide.

Example 9 Ag (I) -Zn (II) -Ti (I
In V) -SiO ₂ composition of Example -8, zinc sulfate instead of copper sulfate (0.
125 mole: ZnSO ₄ · 7H ₂ O, Wako Pure Chemical reagent grade)
Ag (I) -Zn (II)-
A white powder containing Ti (IV) -SiO ₂ was obtained. B of this powder
The ET specific surface area was 403 m ² / g. This powder contained silver phosphate, zinc hydroxide, titanium phosphate, and silicon dioxide.

[Analysis-1] With respect to the powders obtained in Examples 1 and 3, X was determined in order to examine the crystallinity and chemical structure.
Line diffraction was performed. The test powder is packed in an aluminum holder,
The diffraction pattern was measured under the following conditions using an X-ray diffractometer (RINT
-1100 ^™ : Rigaku Corporation).

Measurement conditions: Tube: Cu Tube voltage: 40 kv Tube current: 20 mA Scanning speed: 2 ° / min Diverging slit: 1 ° Scattering slit: 1 ° Receiving slit: 0.3 mm Monochromator used.

As a result of the analysis, no diffraction intensity peak was detected. It was confirmed that the powder obtained in the example was not crystallized and was amorphous.

[Analysis-2] For each of the samples of Examples 1, 3 and 4, an SEM (Scanning Electron Microscope:
X-ray microanalyzer (Energry Dispersive X-ray Micro Analy) attached to JEOL JSM-6100
zer: The content ratio (atomic ratio) of Ag, Zn, Cu, Ti and P was analyzed by JED-2001 manufactured by JEOL. The results are shown in the following table.

[0151]

[Table 1]

[Test Example-1] Adsorption characteristics test The powder obtained in Examples-1 to 4 and 6-9 and Comparative examples -1 and 2 were evaluated for hydrogen sulfide, methyl mercaptan, methyl sulfide and ammonia. Was measured by the following methods.

[0153] 40 mg of the dried powder was weighed to 3.0
The mixture was placed in a 00 ml glass desiccator (with a stirrer) and sealed with a rubber stopper. Then, a malodorous component gas was injected into the desiccator using a syringe such that the initial concentration (Co) became 100 ppm. Thirty minutes after the gas was injected, the air in the desiccator was taken out with a micro syringe, and the gas chromatograph (manufactured by Shimadzu Corporation, Shimadzu GC-1)
4A), and the gas concentration (C ₃₀ ) was measured, and the removal rate was determined by [Equation 1]. The results are shown in [Table 2].

[0154]

(Equation 1)

[0155]

[Table 2]

Test Example 2 Antibacterial Test The antibacterial activity of each adsorbent powder obtained in Examples 1 to 4 was measured by the following method. As test strains, 15 kinds of [Table 3] were used. As a medium for enrichment, PYG is used for bacteria and yeast.
Medium (10 g Polypepton (Nippon Pharmaceutical), 5 g Yeast extra
ct (manufactured by Difco) and 20 g of Glucose (manufactured by Wako Pure Chemical Industries)
dissolved in distilled water and adjusted to pH 7.0 with NaOHaq.), and a PDA medium (Potato Dextrose Aga
r: Difco) to which yeast extract was added at a concentration of 5 g / l. As a culture medium for sensitivity measurement, bacteria and yeast were prepared by adding yeast extract to PDA medium at a concentration of 5 g / l, and mold was expressed by SD.
A medium; a (Sabouraud Dextrose Agar made Difco), Clad
osporium cladosporioides (CC), Tyromyces palustris
(TP) and Coriolus versicolor (CV) in PDA medium
What added east extract so that it might become 5 g / l was used.

100 mg of the adsorbent powder was added to 10 ml of methanol (special grade: manufactured by Wako Pure Chemical Industries), and ultrasonic dispersion was performed for 5 minutes to prepare a suspension (concentration of the adsorbent in this suspension: 10,000 ppm), and a dilution step suspension of the sample was prepared with sterile water.

In a Petri dish, a predetermined amount of the suspension at a dilution stage was added to a culture medium for sensitivity measurement at 50 ° C., and the mixture was shaken so that the powder became uniform and then solidified.

The inoculum was prepared by pre-culturing the test strain at 28 ° C. for 1 day in an enrichment medium for bacteria and yeast.
It was prepared with sterile water so that the number of bacteria was 10 ⁷ to 10 ⁸ cells / ml. For mold, one slant was suspended in 10 ml of sterilized water using a homogenizer. The bacterial suspension was used as a bacterial solution for inoculation. Approximately 10 ⁶ to 10 ⁷
/ ml bacteria.

The bacterial solution for inoculation thus obtained was inoculated into the solidified medium for measuring sensitivity using an inoculation device for MIC (Micro Planter ^™ : MIT-P type manufactured by Sakuma Seisakusho). Bacteria and yeast at 28 ° C for 1 day, mold at 2
The cells were cultured at 8 ° C for 2 days (CC, TP and CV at 23 ° C for 4 days).

After culturing for a predetermined period, the presence of colonies on the medium was observed, and the minimum growth inhibitory concentration (MIC) was determined. The results are shown in [Table 3].

[0162]

[Table 3]

[0163] As Test Example -3] Antimicrobial Test (liquid culture method) test bacteria, Bacillus s ubtilis IFO-13719 and Escheri
Two types of chia coli IFO-3301 were used. These strains were pre-cultured in PY medium at 37 ° C. and 24 hours.
One platinum loop of this fresh culture was suspended uniformly in 5 ml of sterile water. 0.25 ml of this bacterial solution is added to 10 ml of 0.1% (W / V).
TSB medium (BBL) containing sample was dispensed 100
inoculate an Erlenmeyer flask with a volume of
(00 rpm) at 28 ° C. for 24 hours.

After diluting the culture solution 10 times with water,
Turbidity (C ₁ ) at 0 nm was measured with a spectrophotometer (U-1080 Auto Sipper Photometer manufactured by Hitachi, Ltd.). In addition, the turbidity (C ₂ ) of the culture solution before culturing was also determined, and the antibacterial activity (%) was determined using [Equation 2].

As controls, the turbidity (C ₃ ) when the bacteria were cultured in a TSB medium containing no sample and the turbidity (C ₄ ) before the start of the culture were measured. Table 4 shows the obtained results.
Shown in

The PY medium was 10 g / L of polypeptone (manufactured by Nippon Pharmaceutical), 2 g / L of yeast extract (manufactured by Difco), and 1 g / L of magnesium sulfate (MgSO ₄ .7).
H ₂ O) and 20 g / L agar were dissolved in water to that concentration, and the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and this was used as a slant medium.

[0167]

(Equation 2)

[0168]

[Table 4]

Test Example 4 Heat Resistance Test (Discoloration) The powders obtained in Examples 1, 2 and 9 were dried in air at 115 ° C., 200 ° C. and 300 ° C. for 2 hours by an electric dryer. In addition, heating was performed in an electric furnace at 500 ° C. in air for 2 hours. As a control, a zeolite having silver supported thereon by the following method was subjected to the same test.

The discolored state of the powder at each temperature was observed. The results are shown in [Table 5].

(Production 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. To this solution was added 20 g of Na-4A type zeolite (Silton ^™ : manufactured by Mizusawa Chemical Industry, containing about 13% by weight of water), and at room temperature,
Stir for 2 hours. Thereafter, filtration, washing, drying and pulverization were performed in the same manner as in Example 1 to obtain a silver-zeolite powder. When this powder was measured by an atomic absorption spectrometer,
It contained silver by weight.

[0172]

[Table 5]

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-83906 (JP, A) JP-A-3-43457 (JP, A) JP-A-2-169027 (JP, A) JP-A-63-63 258644 (JP, A) Special Table Hei 5-504091 (JP, A) (58) Fields surveyed (Int. Cl. ⁷ , DB name) B01J 20/06 A61L 9/01 A61L 9/16

Claims (11)

(57) [Claims] An adsorptive composition comprising silver, a water-insoluble phosphate of a tetravalent metal and a hydroxide of a divalent metal. 2. The composition according to claim 1, wherein the tetravalent metal is a Group 4 element. 3. The composition according to claim 1, wherein the tetravalent metal is a Group 4A element. 4. The composition according to claim 1, wherein the tetravalent metal is titanium or zirconium. 5. The divalent metal is a divalent transition metal.
A composition according to any one of claims 1 to 4. 6. The method according to claim 1, wherein the divalent metal is copper or zinc.
5. The composition according to any one of the above items 4. 7. The method according to claim 1, wherein the silver is a water-insoluble compound of silver.
7. The composition according to any one of claims 6 to 6. 8. The composition according to claim 1, wherein the silver is silver phosphate. 9. The composition according to claim 1, which is amorphous. 10. The content ratio of a tetravalent metal to a divalent metal is 0.1 to 10 in a metal atom ratio (divalent metal / tetravalent metal),
The content ratio of the water-insoluble silver compound is 0.01 to 1 in terms of the metal atomic ratio [(silver) / (divalent metal + tetravalent metal)] with respect to the total amount of the tetravalent metal and the divalent metal. 1.0.
10. The composition according to any one of the above items 9. 11. The composition according to claim 1, wherein a water-insoluble compound of silver and a hydroxide of a divalent metal are formed in the presence of a water-insoluble phosphate of a tetravalent metal. Law.