JPH05277167A - Deodorant body and its production - Google Patents

Abstract

PURPOSE:To exhibit an excellent deodorant effect over a long period of time at a low cost without using special techniques and devices by holding a metal complex which decomposes or adsorbs malodorous materials on a granular or lumpy adsorber. CONSTITUTION:This deodorant body used as an ornament, etc., in a toilet or room or by being put into a refrigerator, clog cabinet, etc., has the granular adsorber which consists of an inorg. material, org. material or a mixture composed of these materials and has 0.5 to 50mm sizes or the lumpy adsorber molded to a required shape. The deodorant body is formed by holding the metal complex which decomposes or adsorbs the malodorous materials onto such adsorber. Porous beads of active carbon, acidic clay, diatomaceous earth, etc., and porous ceramics, etc., are used for the inorg. material. Pulp chips and sawdust are used as the org. material. Further, metal porphyrin, such as metal phthalocyanine deriv., are used as the metal complex.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as a toilet or indoor ornament, etc., put in a toilet bowl, or used as a foul odor source or a bad odor retention site such as a refrigerator, a shoe box or a trash box, and has an excellent deodorizing property. The present invention relates to a deodorant that develops and a method for producing the deodorant.

[0002]

2. Description of the Related Art Various malodorous substances such as ammonia, indole, skatole, sulfide, aldehyde, mercaptan, amines or hydrogen sulfide are generated from a malodorous source such as a toilet, a refrigerator, a shoe box or a trash can, and the user is injured. Various studies have been made in order not only to cause discomfort, but also to give discomfort to surrounding people.

Specifically, an aromatic agent is provided at the source of bad odor in a toilet or the like to mask the bad odor substance with an aromatic substance,
It is common to adsorb malodorous substances to activated carbon.

However, in the case of masking a malodorous substance with an aromatic substance, the aromatic substance is scattered inside the room and the malodor is erased by this scent. However, the smell is too strong at the beginning of the use of the aromatic agent. , Giving offense to the user,
On the other hand, when the fragrance is exhausted and almost no aromatic substance is scattered, masking of the malodorous substance becomes insufficient, resulting in malodor.

Further, although chemically synthesized fragrances are used, there is a question about the safety when such substances are absorbed over a long period of time.

On the other hand, when the malodorous substance is adsorbed on the activated carbon, since the adsorption capacity is limited, the adsorption effect of the malodorous substance is remarkably reduced from around the saturated adsorption amount (breakthrough point), and the deodorizing effect cannot be recognized.

Therefore, recently, the following deodorant fiber sheet or deodorant for refrigerators has been proposed.

That is, as the deodorant fiber sheet, a fiber obtained by mixing short fibers in which at least a part of constituent fibers carries a metal complex having a redox ability in an amount of 1% by weight or more and short fibers carrying metal ions. It is proposed to use a deodorizing curtain having a heat-adhesive substance interposed between the fibers and having a sheet shape retained by fusing of the heat-adhesive substance (Japanese Patent Application Laid-Open No. 2004-242242). 62-6954).

In this case, the short fibers were cut into several tens of millimeters and formed by mixing short fibers carrying 1% by weight or more of a metal complex and short fibers carrying metal ions and mixing them. It is a thing.

It is also proposed to use a deodorizing agent for a refrigerator, which mainly comprises a sheet containing an immobilization product having a metal complex of phthalocyanine and / or polyacrylic acid fixed on the surface as a deodorizing component. (Japanese Utility Model Publication No. 1-73334).

In this case, the refrigerator deodorant is a mixture of an immobilization product having a metal complex of phthalocyanine and / or polyacrylic acid fixed on the surface as a deodorizing component, and a fiber material, which is then molded into a sheet. is there.

[0012]

However, the above deodorant fiber sheet has the following problems.

That is, this deodorant fiber sheet is made by mixing short fibers carrying 1% by weight or more of a metal complex having redox ability with short fibers carrying metal ions, that is, mixing these short fibers. The deodorant function mainly depends on the metal complex.

That is, the short fibers carrying metal ions are
If various conditions such as the presence of water and hydrogen ion concentration are not adjusted, the deodorizing function will not be exhibited, and even if these conditions are set, this deodorizing function is mainly due to the fact that a metal complex is supported. Since the metal complex is nonuniformly present in the fiber sheet depending on the fiber, a sufficient deodorizing function is not exhibited.

By the way, according to the experimental results of the present inventor,
The decomposition or adsorption of the malodorous substance by the metal complex occurs on the surface of the metal complex. Therefore, in order to remove the malodorous substance efficiently, the metal complex should be present in the fiber sheet uniformly or almost uniformly. However, if the metal complex is unevenly present in the fiber sheet, the deodorizing effect is significantly reduced.

Therefore, this kind of deodorant fiber sheet has a fatal problem that not only the required deodorizing effect is not obtained but also the deodorizing effect is lost in a short period of time.

As described above, the deodorant fiber sheet is obtained by mixing the short fibers supporting the metal complex with the short fibers supporting the metal ions. The short fibers supporting the metal complex are likely to be biased,
From this point as well, it becomes extremely difficult to obtain a deodorant fiber sheet exhibiting a required deodorizing function and having stable quality.

This unevenness becomes more remarkable when the strength, length, thickness, density, etc. of the short fibers are different. Therefore, it is necessary to strictly control the short fibers, which makes quality control and production control extremely troublesome. Naturally, the range of combinations and selections of short fibers is narrowed, and the variety is poor.

Further, this deodorant fiber sheet is obtained by separately producing short fibers supporting a metal complex and short fibers supporting metal ions, and mixing them. As a result of increased man-hours and reduced productivity,
There are issues such as high production costs.

On the other hand, the above-mentioned refrigerator deodorant has a phthalocyanine and / or
Alternatively, the immobilization product to which the metal complex of polyacrylic acid is fixed and the fiber material are mixed, and this is molded into a sheet, and thus the immobilization product and the fiber material are made by a wet papermaking method and dried. Therefore, it has the same problem as the above-mentioned deodorant fiber sheet.

In particular, in this case, the complex-immobilized pulp (immobilized product) and untreated cut rayon are obtained by paper-making by a wet papermaking method and drying. In this case, the complex-immobilized pulp ( (Immobilized product) and untreated cut rayon differ in strength, length, thickness, density, etc. As a result, imbalance of the complex-immobilized pulp (immobilized product) is likely to occur, and from this point as well, the required deodorant function can be obtained. In addition to not being able to develop, it becomes extremely difficult to obtain a deodorant for refrigerators with stable quality, which not only makes quality control and production management extremely difficult, but also deodorizes refrigerators that exhibit the required deodorizing function. There is a fatal problem such that it becomes extremely difficult to obtain the agent, and there is also a problem that the fiber such as rayon cannot be used for a long period of time.

The present invention has been completed in view of the above technical problems, and a granular or massive adsorbent is allowed to retain a metal complex for decomposing or adsorbing a malodorous substance, whereby any special technique or apparatus can be provided. It is an object of the present invention to provide a deodorant and a method for producing the deodorant, which are excellent in deodorizing effect over a long period of time at low cost without using them, and have stable quality.

[0023]

In order to achieve the above object, the present invention provides a technical means in which a granular or lumpy adsorbent holds a metal complex that decomposes or adsorbs a malodorous substance. It was taken. Hereinafter, the present invention will be described in detail.

In the present invention, the adsorbent is not particularly limited as long as it is granular or lumpy and can hold a metal complex which decomposes or adsorbs a malodorous substance described later.

The adsorbent may be used as a figurine as it is, or may be put in a porous bag or container to be used as a toilet or indoor figurine, or put in a toilet bowl, and a foul odor may be generated in a refrigerator, a shoe box or a trash can. There is no particular limitation as long as it is used as a source.

As described above, the particulate adsorbent is used as it is because the metal complex to be described later can be easily retained in a large amount, the surface area is large, and the deodorizing effect is high. Moreover, the manufacturing cost is low, and a larger one can be used as it is, or instead, it can be put into a porous bag or container having a desired shape and used for various purposes, which is extremely useful.

The size of the granular adsorbent is not particularly limited and can be arbitrarily selected according to the application.
Generally 0.5 mm to 5 cm, especially 2 mm to 3
cm is preferable, and if it is less than 0.5 mm, it is not preferable because dust may scatter during manufacturing or handling, while if it is more than 5 cm, applications are limited, which is not preferable.

The absorbent body is not particularly limited to a lump, but is mainly placed in a toilet, a room, a hallway, etc., such as an ornament or an ornament.

That is, as the massive adsorbent,
Although not particularly limited, spherical, disc-shaped, spindle-shaped, cylindrical, conical, triangular prism, rectangular parallelepiped, cubic, and the like, particularly preferably used as a figurine, exhibit, or appreciable item.

This lump-shaped absorber can be used not only as a deodorant having an excellent deodorizing property, but also as a figurine or a decorative article such as a toilet, room or entrance, so that no uncomfortable feeling is produced. , Extremely beneficial.

In the present invention, the adsorbent may be an inorganic material, an organic material, or a mixture thereof.

In this case, the inorganic substance is not particularly limited as long as it can hold the metal complex described later, but in particular, charcoal such as activated carbon, acid clay, activated clay, diatomaceous earth, silica. , Zeolites or porous beads such as silicon oxide-based porous beads are desirable because they have good metal complex adsorbing properties and exhibit an excellent deodorizing effect for an extremely long period of time.

The organic substance is not particularly limited as long as it can hold the metal complex described below, but pulp chips, wood chips, sawdust, etc. are particularly good in adsorbing the metal complex. It is desirable because it exerts an excellent deodorizing effect for an extremely long period of time and can form an arbitrary shape by pressurizing or the like.

In the present invention, when forming a granular or lumpy adsorbent, an inorganic binder or an organic binder may be used to form the adsorbent into a predetermined shape.

In this case, the organic binder is not particularly limited as long as it is an organic substance and can harden the material of the adsorbent. Specifically, for example, various hot melt type thermoplastic adhesives are used. Agents and thermoplastic resins as well as thermosetting resin adhesives and various prepregs, and the inorganic binder is an inorganic substance,
Moreover, it is not particularly limited as long as it can harden the material of the adsorbent, and specific examples thereof include a sodium silicate adhesive, gypsum and various cements.

The deodorant body of the present invention is most characterized in that the deodorant body holds a metal complex which decomposes or adsorbs a malodorous substance.

As described above, by allowing the adsorbent to hold a metal complex that decomposes or adsorbs a malodorous substance, an excellent deodorizing effect is exhibited over a long period of time, and a stable quality product is obtained. Be done.

The metal complex used in the present invention is not particularly limited as long as it decomposes or adsorbs a malodorous substance such as ammonia, mercaptan, indole, skatole, sulfide, aldehyde, amines or hydrogen sulfide and deodorizes it. Not something.

The decomposition of the malodorous substance is not limited to the case where the metal complex directly decomposes the malodorous substance, and the metal complex serves as a catalyst to change the malodorous substance into a substance which does not emit a malodorous substance by the action of oxygen and moisture in the air The case etc. are mentioned.

The malodorous substance is adsorbed not only when the malodorous substance is physically adsorbed to the metal complex, for example, when it is adsorbed by dissolution, but also when the malodorous substance forms a salt with the metal complex. Be done.

Therefore, in the present invention, the metal complex which decomposes or adsorbs the malodorous substance is a general term for deodorizing the metal complex by chemically and / or physically acting on the malodorous substance.

As this metal complex, in particular, it has a large function of decomposing or adsorbing malodorous substances, and so on.
Examples thereof include metal porphyrins, metal polyphyrazine and derivatives thereof, and among these, the metal porphyrin derivative is most preferably a metal phthalocyanine derivative.

The metal porphyrin and its derivative are represented by the general formula 1, and the metal porphyrazine is represented by the general formula 2.

[0044]

[Chemical 1]

[0045]

[Chemical 2]

In the general formulas 1 and 2, M is an alkaline earth metal or a transition metal. Specific examples include ions of metals such as magnesium, calcium, barium, copper, iron, nickel, cobalt, manganese, titanium, vanadium, molybdenum, tungsten, silver or zinc.

In the general formulas 1 and 2, X and Y represent hydrogen or a substituent. Examples of the substituent include a hydroxyl group, an alkyl group, a chloromethyl group, a halogen group, a carboxyl group, a carbonyl chloride group, a carboxylamide group, a sulfone group, a sulfonyl chloride group, a sulfonamide group, a nitro group, an amino group, an azo group, Examples thereof include a thiocyanate group, a nitrile group, an alkoxyl group, a phenoxyl group, a thiol group, an alkylsilicon group, a vinyl group, and the like, and an alkali metal salt of a carboxyl group or a sulfonic acid group.

These may be used alone or in combination of two or more. Particularly, carboxyl group, hydroxyl group, amide group,
Those having at least one selected from a sulfone group, a halogen group and an amino group have a large deodorizing effect.

In the present invention, it is also advantageous that the metalloporphyrin derivative has an anion group, and the same or different metal is bound to this anion group to form a salt.

The anionic group is a carboxyl group,
Examples thereof include sulfone groups and phosphoric acid groups.

Examples of the metal ion bonded to the anion group include alkali metal ions such as sodium and potassium, and alkaline earth metal ions such as magnesium, calcium and barium.

Specific examples of this metal complex include iron phthalocyanine octacarboxylic acid, cobalt phthalocyanine octacarboxylic acid and cobalt phthalocyanine tetracarboxylic acid.

In the present invention, the above-mentioned metal complex is retained by the deodorant, and these metal complexes may be used alone or in combination of two or more kinds.

The ratio of the metal complex (A) held by the adsorbent (B) is not particularly limited as long as it is at a concentration at which the deodorant function is exhibited. Specifically, it generally depends on the type and application of the metal complex, but the range of 0.1 to 20% by weight, particularly preferably 0.2 to 15% by weight of the total of (A) and (B) is preferable. desirable.

When the amount of the metal complex retained is too large, a remarkable deodorizing effect can be obtained over a long period of time, but it is uneconomical. On the other hand, when the amount is too small, the required deodorizing effect cannot be obtained. Therefore, in order to maintain the required deodorizing effect for a relatively long period of time without losing the various properties required for the deodorant, the ratio of the metal complex retained is 0.5 to 0.5% as a whole.
The most preferable range is 10% by weight.

When the adsorbent is allowed to hold the above-mentioned metal complex, the adsorbent may be allowed to physically hold the metal complex, or the adsorbent is chemically reacted with a functional group such as a hydroxyl group, a carboxyl group or an amine group. May be combined with each other.

In the present invention, the adsorbent retains the metal complex that decomposes or adsorbs the malodorous substance. Thus, in order to obtain the deodorant by allowing the adsorbent to retain the metal complex, There is a method.

That is, in order to achieve the above object, the deodorant composition of the present invention is a solution or dispersion of a metal complex that decomposes or adsorbs a malodorous substance on an adsorbent composed of an inorganic substance, an organic substance or a mixture thereof. The metal complex obtained in the step (A) of applying a liquid, the step (B) of forming the adsorbent obtained in the step (A) into a granular or lump shape having a predetermined size, and the metal complex obtained in the step (B). It is characterized by comprising a step (C) of drying the contained adsorbent at a temperature not higher than the decomposition temperature of the metal complex.

As the adsorbent and the malodorous substance and the metal complex which are used in the present invention and which are made of the inorganic substance or the organic substance or the mixture thereof, the same ones as mentioned above can be mentioned, and therefore, the duplicated explanation will be avoided. Omitted for

Further, in the method for producing a deodorant of the present invention,
Forming the adsorbent into a specific size of granules or lumps,
Forming an adsorbent in the above shape.

In the method for producing a deodorant of the present invention, a solution or dispersion of a metal complex for decomposing or adsorbing a malodorous substance is previously adsorbed on an adsorbent composed of an inorganic substance, an organic substance or a mixture thereof. The point (A) is the step of applying, the step (A) of forming the particle into a granular or lump having a predetermined size (step B), and the step (C) of drying the metal complex at or below the decomposition temperature.

In the present invention, the method of applying the solution or dispersion of the metal complex to the adsorbent is not particularly limited, but specifically, for example, the adsorbent is dipped in the solution or dispersion of the metal complex. Or spray the solution or dispersion of the metal complex onto the adsorbent, spray the solution or dispersion of the metal complex onto the adsorbent, or apply the solution or dispersion of the metal complex onto the layer of the adsorbent. It is possible to apply a solution or dispersion of the metal complex to the adsorbent, and then dry the adsorbent at a temperature not higher than the decomposition temperature of the metal complex.

In this case, the concentration of the solution or dispersion of the metal complex varies depending on the type of adsorbent used and the metal complex and is not particularly limited, but in general,
It is desirable to set it in the range of 0.1 to 30% by weight, particularly 0.5 to 15% by weight. If this concentration is less than 0.1% by weight, the amount of one application is small and it is necessary to apply it several times or more. Therefore, productivity becomes poor, and when it exceeds 30% by weight, it is difficult to obtain a uniform dispersion liquid, and the adsorption amount of the metal complex may vary, which is not desirable.

The solvent or dispersion medium is not particularly limited as long as it is an inorganic or organic liquid and can be removed by drying. Specifically, for example, water or carbon number is used. 1 to 3 lower alcohols, ketones such as methyl ethyl ketone and acetone, and aliphatic hydrocarbons such as n-hexane are preferable because they are safe and easy to remove.

Furthermore, as a solvent, acetonitrile, tetrahydrofuran or an aromatic hydrocarbon such as benzene or toluene may be used, if desired.

Further, in order to improve the solubility of the metal complex in water, an alkali metal salt such as sodium or potassium is used, or in order to improve the dispersibility of the metal complex, an anionic surfactant or a cation is used. A surfactant such as a surfactant, a nonionic surfactant or an amphoteric surfactant, or another dispersant may be used.

Examples of the anionic surfactant include sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium 2-alkyl sulfate, sodium alkyl naphthalene sulfonate, sodium α-olefin sulfonate, sodium N-acyl amino acid, N-. (2-Sulfo) ethyl-N-methylalkanamide sodium, dialkyl sodium 2-sulfosuccinate and the like can be mentioned.

Examples of the above cationic surfactants include benzalkonium chloride, benzethonium chloride, alkylpyridinium sulfate, N-ethylalkanamide ammonium halide, alkyltrimethylammonium halide and the like.

Examples of the nonionic surfactants include fatty acid polyhydric alcohol esters, alkyl polyoxyethylene ethers, alkylcarbonyl polyoxyethylenes, p-alkylphenyl polyoxyethylene ethers, fatty acid polyhydric alcohol polyoxyethylenes and fatty acid esters. Examples thereof include sugar esters.

Examples of the amphoteric surfactant include alkyl betaine and alkyldiethylene triaminoacetic acid.

These surfactants can be used alone or, if desired, in combination of two or more kinds, and the mixing ratio thereof is 0.1 with respect to the solvent or the dispersion medium.
It may be in the range of 10% by weight.

In the present invention, when producing a deodorant, various properties such as absorption properties and usability required for the adsorbent are not lost, and the solvent and the solvent are used from various viewpoints such as easiness of drying. It is necessary to select and use a dispersion medium. Therefore, two or more kinds of solvents and dispersion media may be mixed and used.

In the present invention, the solution or dispersion of the metal complex may be applied to the adsorbent and then dried at atmospheric pressure or under reduced pressure.

In this case, the drying temperature must be below the temperature at which the metal complex decomposes and the deodorizing function is lost.

Further, in the present invention, the inorganic substances and organic substances, and the inorganic binders and organic binders include those mentioned above.

In the production method of the present invention, it is desirable that the granular adsorbent obtained in the step (B) has a size of 0.5 mm to 5 cm for the same reason as described above.
It is desirable that the block-shaped adsorbent obtained in this step (B) is a figurine, an exhibit, or an appreciation item.

Further, in the method for producing a deodorant of the present invention, a solution or dispersion of a metal complex for decomposing or adsorbing a malodorous substance is applied to an adsorbent made of an inorganic substance, an organic substance or a mixture thereof. Step (A), Step (B) of drying the adsorbent containing a metal complex obtained in (A) below the decomposition temperature of the metal complex, Step (B) above
The step (C) of obtaining a granular or lumpy adsorbent of a predetermined size by using the adsorbent containing a metal complex obtained in the above step.

That is, in the method for producing a deodorant described above, a solution or dispersion of a metal complex for decomposing or adsorbing a malodorous substance is applied to an adsorbent composed of an inorganic substance, an organic substance or a mixture thereof, and then, This is molded into a predetermined size and then dried at the end, whereas the invention of the method for producing a deodorant product is the solution of a metal complex in an adsorbent composed of an inorganic substance or an organic substance or a mixture thereof. Alternatively, it is characterized in that after the dispersion is applied, it is dried in advance and then formed into a predetermined shape.

Therefore, in this manufacturing method, the materials such as the adsorbent and the metal complex are the same as those in the above-mentioned case, and therefore will be omitted.

In the production method of the present invention, the method for applying the solution or dispersion of the metal complex to the adsorbent is not particularly limited, and specific examples thereof include the above-mentioned methods.

Further, in this case, since the solvent and the dispersion medium used are the above-mentioned ones, the description thereof will be omitted to avoid the duplicated description.

Further, in this method for producing a deodorant, in order to improve the solubility of the metal complex in water, an alkali metal salt such as sodium or potassium is used, or in order to improve the dispersibility of the metal complex. It is also possible to use a surface active agent such as an anionic surface active agent, a cationic surface active agent, a nonionic surface active agent or an amphoteric surface active agent, or another dispersant.

Examples of the surface active agent such as the anionic surface active agent, the cationic surface active agent, the nonionic surface active agent or the amphoteric surface active agent include those mentioned above.

Further, in the method for producing a deodorant of the present invention, in order to achieve the above object, an inorganic substance, an organic substance, or a mixture thereof is used to adsorb a granular or lump of a predetermined size. Step (A) of obtaining a body, above step (A)
The step (B) of applying a solution or dispersion of a metal complex that decomposes or adsorbs a malodorous substance to the adsorbent obtained in step (B), and the adsorbent containing the metal complex obtained in the above (B) is used as the metal complex. The step (C) of drying below the decomposition temperature of

As the adsorbent, the malodorous substance and the metal complex used in the present invention, the same ones as mentioned above can be mentioned, and therefore the explanation thereof will be omitted to avoid the duplicated explanation.

In addition, in the method for producing a deodorant of the present invention, after the production of a granular or lumpy adsorbent of a predetermined size,
This is because the adsorbent is provided with a solution or dispersion of a metal complex that decomposes or adsorbs a malodorous substance, and then dried at a temperature not higher than the decomposition temperature of the metal complex.

In the present invention, the method of applying the solution or dispersion of the metal complex to the adsorbent is not particularly limited, and specific examples thereof include the above-mentioned methods.

Further, in this case, since the solvent and the dispersion medium used are the above-mentioned ones, the description thereof will be omitted to avoid the duplicated description.

Further, in this method for producing a deodorant, in order to improve the solubility of the metal complex in water, an alkali metal salt such as sodium or potassium is used, or in order to improve the dispersibility of the metal complex. It is also possible to use a surface active agent such as an anionic surface active agent, a cationic surface active agent, a nonionic surface active agent or an amphoteric surface active agent, or another dispersant.

Examples of the surface active agent such as anionic surface active agent, cationic surface active agent, nonionic surface active agent or amphoteric surface active agent include those mentioned above.

[0091]

The deodorant body of the present invention has the above-mentioned constitution, and the adsorbent has a metal complex which decomposes or adsorbs a malodorous substance on the whole thereof, and the metal complex has the following reasons. It exhibits a remarkably excellent deodorizing effect.

That is, this deodorant body is installed as a figurine in a toilet, a room, a front door, etc., placed in a toilet bowl of a toilet, placed in a foul-smelling source such as a refrigerator, a shoe box or a trash box, or a stink-holding place. Then, the malodorous substance generated from this malodorous source comes into contact with the deodorant body.

Then, the malodorous substance and the metal complex held by the deodorant come into direct and efficient contact, and the metal complex acts on the malodorous substance in relation to oxygen in the air, The malodorous substance is oxidatively decomposed, or the malodorous substance is physically adsorbed on the metal complex, so that the unpleasant odor is eliminated.

In addition, since the malodorous substance and the metal complex are in direct contact with each other and the metal complex has a sterilizing / sterilizing action and an antibacterial action as described above, when the odorous substance and the metal complex are put in a toilet bowl, a trash can or the like in the toilet, The generation of offensive odors and offensive odors caused by the propagation of bacteria in S. cerevisiae can be suppressed, and from this point as well, it has a deodorizing action.

Therefore, the deodorant body of the present invention exerts an excellent deodorant effect over a long period of time, and thus has an effect that it can be used comfortably.

This bulk absorber can be used not only as a deodorant having an excellent deodorizing property, but also as a figurine or a decorative article such as a toilet, room, or entrance, so that no uncomfortable feeling is produced. , Extremely beneficial.

In the method for producing a deodorant of the present invention, a solution or dispersion of a metal complex for decomposing or adsorbing a malodorous substance is applied to an adsorbent composed of an inorganic substance or an organic substance or a mixture thereof, and then After molding it into a predetermined size, it is finally dried, or alternatively, a solution or dispersion of a metal complex is applied to an adsorbent composed of an inorganic substance, an organic substance or a mixture thereof. After that, it is dried in advance and then molded into a predetermined shape, which can be mass-produced at low cost and with excellent quality without using special technology or equipment. Have.

That is, in this method, a metal that decomposes or adsorbs a malodorous substance is previously adsorbed on an inorganic substance or an organic substance or a mixture thereof before producing a granular or lumpy adsorbent of a predetermined size. A solution or dispersion of the complex is applied and then dried at a temperature not higher than the decomposition temperature of the metal complex.

Furthermore, in the method for producing a deodorant of the present invention, an inorganic substance, an organic substance, or a mixture thereof is used in advance to obtain a granular or lumpy adsorbent having a predetermined size. A solution or dispersion of a metal complex for decomposing or adsorbing a malodorous substance is applied to this adsorbent, and the adsorbent containing the metal complex is dried at a temperature below the decomposition temperature of the metal complex. It has the effect of being able to mass-produce products of excellent quality at low cost without using any device.

That is, in this method, after producing a granular or lumpy adsorbent of a predetermined size, a solution or dispersion of a metal complex that decomposes or adsorbs a malodorous substance is applied to the adsorbent, and It is dried below the decomposition temperature of the metal complex.

[0101]

EXAMPLES The present invention will now be described in detail based on examples, but the present invention is not limited thereto.

Example 1 Zeolite powder (commercially available) having a diameter of 2 to 5 mm was used as an adsorbent, and the adsorbent was used as a dispersion of iron phthalocyanine / polycarboxylic acid (concentration 1% by weight, mixed solution of water and ethyl alcohol ( (1: 1 by volume), 0.5% by weight of a higher alcohol surfactant) and left for 1 hour, then drained and dried at 100 ° C. until there is no change in weight. A granular deodorant was obtained.

The content of iron phthalocyanine polycarboxylic acid in this granular deodorant product was 3.5% by weight.

Example 2 A tiger figurine made of commercially available Japanese paper was used, and a dispersion of iron phthalocyanine / polycarboxylic acid was added to the tiger figurine.
(Concentration 1% by weight, mixed liquid of water and ethyl alcohol (volume ratio 1: 1), higher alcohol surfactant 0.5% by weight
(Compounding) was sprayed and then dried at 85 ° C. under reduced pressure while sucking with an aspirator to obtain a block deodorant material of the present invention.

By the way, the content of iron phthalocyanine polycarboxylic acid in the above adsorbent was 2.8% by weight.

Comparative Example A commercially available rayon staple was cut into a length of 10 mm to obtain a rayon staple staple fiber.

Next, this rayon staple staple fiber was
It was immersed in a dispersion liquid of iron phthalocyanine / polycarboxylic acid similar to that used in Example 1, left for 1 hour and then dried to obtain deodorant rayon staple staple fibers.

The content of iron phthalocyanine polycarboxylic acid in the deodorant rayon staple staple fiber was 3.7% by weight.

This deodorant rayon staple staple fiber 10
0 parts by weight and untreated rayon staple staple 10
0 parts by weight and 5 parts by weight of a polyvinyl alcohol-based binder were dispersed, and paper was made by hand from a papermaking solution to obtain a deodorant nonwoven fabric having a basis weight of 25 g / m ² .

Experimental Example 1 25 g of the granular deodorant obtained in Example 1 was wrapped in a non-woven fabric and 25 g of the deodorant non-woven fabric obtained in the Comparative Example were left in a refrigerator to carry out a deodorant experiment.

In this case, raw fish (sardine 1 kg) was placed in a refrigerator (temperature: 7.5 ° C.) to carry out a deodorizing experiment.

As a result, in Example 1, no offensive odor was observed even after 10 days from being left, but in Comparative Example, an offensive odor drifted from the second day and a strong odor was emitted after 10 days. Was there.

Experimental Example 2 The block deodorant obtained in Example 2 and the comparative example product were allowed to stand in the toilet and a deodorant test was carried out. The odor disappeared, but the odor of the comparative example could not be eliminated.

Experimental Example 3 The granular deodorant used in Experimental Example 1 was placed outdoors and placed in a waste container (a plastic bucket with a lid having a capacity of 100 l) which smells like an onion. After 3 hours, the lid was opened to remove the odor. When I sniffed,
Almost no onion odor was observed.

Further, when the same deodorization experiment was conducted using the comparative example, it was confirmed that the onion odor did not disappear.

[0116]

EFFECT OF THE INVENTION The deodorant of the present invention has the above-mentioned constitution, and the adsorbent has a metal complex for decomposing or adsorbing a malodorous substance. It is installed as a figurine in a toilet, put in a toilet bowl, or placed in a foul-odor source such as a refrigerator, a shoe box, or a trash can.

The malodorous substance and the metal complex held by the deodorant come into direct and efficient contact, and the metal complex acts on the malodorous substance in association with oxygen in the air, The malodorous substance is decomposed, or the malodorous substance is physically adsorbed by the metal complex, and thus has an excellent deodorizing effect over a long period of time.

In addition, since the malodorous substance and the metal complex are in direct contact with each other and the metal complex has a sterilizing / sterilizing action and a bactericidal action as described above, when the odorous substance and the metal complex are put in a toilet bowl, a trash can or the like in the toilet, It is possible to suppress the generation of offensive odors and offensive odors caused by the reproduction of bacteria, and from this point as well, it is possible to exert an excellent deodorizing effect over a long period of time, which is extremely beneficial.

Furthermore, this lumped deodorant body is not only used as a deodorant body having an excellent deodorant property, but also as a figurine or a decorative article such as a toilet, room, or entrance, so that there is no sense of discomfort. As a result, it is extremely beneficial.

In the method for producing a deodorant of the present invention, a solution or dispersion of a metal complex for decomposing or adsorbing a malodorous substance is applied to an adsorbent composed of an inorganic substance, an organic substance or a mixture thereof, and then After molding it into a predetermined size, it is finally dried, or alternatively, a solution or dispersion of a metal complex is applied to an adsorbent composed of an inorganic substance, an organic substance or a mixture thereof. After that, this is used after being dried in advance and then molded into a predetermined shape, and it is possible to mass-produce products of excellent quality at low cost without using special technology or equipment. , Extremely beneficial.

Furthermore, in the method for producing a deodorant of the present invention, an inorganic substance, an organic substance, or a mixture thereof is used in advance to obtain a granular or lumpy adsorbent having a predetermined size, A solution or dispersion of a metal complex for decomposing or adsorbing a malodorous substance is applied to this adsorbent, and the adsorbent containing the metal complex is dried at a temperature below the decomposition temperature of the metal complex. It is extremely beneficial because it can be mass-produced at low cost and with excellent quality without using a device.

Claims (53)

[Claims] 1. A deodorant body in which a granular or lump-shaped adsorbent holds a metal complex that decomposes or adsorbs a malodorous substance. 2. The deodorant body according to claim 1, wherein the adsorbent comprises an inorganic substance, an organic substance, or a mixture thereof. 3. The inorganic substance is charcoal such as activated charcoal, acid clay,
The deodorant according to claim 2, which is activated clay, diatomaceous earth, silica, zeolite, porous beads such as silicon oxide porous beads, porous ceramics or porous glass. 4. The deodorant body according to claim 2, wherein the organic substance is pulp chips, wood chips or sawdust. 5. The granular adsorbent has a size of 0.5 mm to 5 c.
The deodorant body according to any one of claims 1 to 4, which is of m. 6. The deodorant body according to claim 1, wherein the block-shaped adsorbent is formed into a required shape. 7. The deodorant body according to claim 6, wherein the lump-shaped adsorbent body is a figurine, an exhibit or an appreciation item. 8. The deodorant body according to claim 1, wherein the granular or lumpy adsorbent is formed into a predetermined shape by using an inorganic binder or an organic binder. 9. The deodorant according to claim 1, wherein the metal complex comprises a metalloporphyrin derivative. 10. The deodorant according to claim 9, wherein the metalloporphyrin derivative is a metal phthalocyanine derivative. 11. The deodorant according to claim 9, wherein the metalloporphyrin derivative has at least one selected from a carboxyl group, a hydroxyl group, an amide group, a sulfone group, a halogen group and an amino group. 12. The deodorant according to claim 9, wherein the metalloporphyrin derivative has an anion group, and the same or different metal is bound to the anion group to form a salt. . 13. The deodorant according to claim 12, wherein the anionic group is a carboxyl group, a sulfone group or a phosphoric acid group. 14. The metal is an alkali metal, calcium,
The deodorant according to any one of claims 1 to 13, which is at least one selected from barium, magnesium, copper, iron, nickel, cobalt, manganese, titanium, vanadium, molybdenum, tungsten, silver or zinc. 15. A step (A) of applying a solution or dispersion of a metal complex capable of decomposing or adsorbing a malodorous substance to an adsorbent comprising an inorganic substance or an organic substance or a mixture thereof, which is obtained in the step (A). Step (B) of forming the obtained adsorbent into a granular or lump of a predetermined size, and drying the adsorbent containing the metal complex obtained in the above step (B) at a decomposition temperature of the metal complex or lower. The manufacturing method of the deodorant body which consists of process (C). 16. The inorganic substance is charcoal such as activated carbon, acid clay, activated clay, diatomaceous earth, silica, zeolite, porous beads such as silicon oxide porous beads, porous ceramics or porous glass. 15. The method for producing a deodorant body according to 15. 17. The method for producing a deodorant according to claim 15, wherein the organic substance is pulp chips, wood chips or sawdust. 18. The method for producing a deodorant according to claim 15, wherein the granular adsorbent obtained in step (B) has a size of 0.5 mm to 5 cm. 19. The method for producing a deodorant according to claim 15, wherein the lump-shaped adsorbent obtained in step (B) is formed into a desired shape. 20. The method for producing a deodorant according to claim 19, wherein the lump-shaped adsorbent obtained in the step (B) is a figurine, an exhibit or an appreciation item. 21. The granular or lumpy adsorbent obtained in step (B) is formed into a predetermined shape by using an inorganic binder or an organic binder, and the adsorbent is formed into a predetermined shape. Method for producing deodorant body. 22. The method for producing a deodorant according to claim 15, wherein the metal complex comprises a metalloporphyrin derivative. 23. The method for producing a deodorant according to claim 22, wherein the metalloporphyrin derivative is a metal phthalocyanine derivative. 24. The method for producing a deodorant according to claim 22, wherein the metalloporphyrin derivative has at least one selected from a carboxyl group, a hydroxyl group, an amide group, a sulfone group, a halogen group and an amino group. 25. The deodorant according to any one of claims 22 to 24, wherein the metalloporphyrin derivative has an anion group, and the same or different metal is bonded to the anion group to form a salt. Manufacturing method. 26. The method for producing a deodorant according to claim 25, wherein the anion group is a carboxyl group, a sulfone group or a phosphoric acid group. 27. The metal is an alkali metal, calcium,
27. The method for producing a deodorant according to any one of claims 15 to 26, which is at least one selected from barium, magnesium, copper, iron, nickel, cobalt, manganese, titanium, vanadium, molybdenum, tungsten, silver or zinc. . 28. A step (A) of applying a solution or dispersion of a metal complex for decomposing or adsorbing a malodorous substance to an adsorbent comprising an inorganic substance or an organic substance or a mixture thereof, which is obtained in the above (A). In addition, an adsorbent containing a metal complex,
Step (B) of drying below the decomposition temperature of the metal complex, Step of obtaining a granular or lumpy adsorbent of a predetermined size using the adsorbent containing the metal complex obtained in the above step (B) A method for producing a deodorant comprising (C). 29. The inorganic substance is charcoal such as activated carbon, acid clay, activated clay, diatomaceous earth, silica, zeolite, porous beads such as silicon oxide porous beads, porous ceramics or porous glass. 28. The method for producing a deodorant body according to item 28. 30. The method for producing a deodorant according to claim 28, wherein the organic substance is pulp chips, wood chips or sawdust. 31. The method for producing a deodorant according to claim 28, wherein the granular adsorbent obtained in step (C) has a size of 0.5 mm to 5 cm. 32. The method for producing a deodorant according to claim 28, wherein the lump-shaped adsorbent obtained in step (C) is formed into a required shape. 33. The method for producing a deodorant according to claim 32, wherein the massive adsorbent obtained in the step (C) is a figurine, an exhibit, or an appreciation item. 34. The granular or lumpy adsorbent obtained in step (C) is formed into a predetermined shape by using an inorganic binder or an organic binder, and the adsorbent is formed into a predetermined shape. Method for producing deodorant body. 35. The method for producing a deodorant according to claim 28, wherein the metal complex comprises a metalloporphyrin derivative. 36. The method for producing a deodorant according to claim 35, wherein the metalloporphyrin derivative is a metal phthalocyanine derivative. 37. The method for producing a deodorant according to claim 35 or 36, wherein the metalloporphyrin derivative has at least one selected from a carboxyl group, a hydroxyl group, an amide group, a sulfone group, a halogen group and an amino group. 38. The deodorant according to claim 35, wherein the metalloporphyrin derivative has an anion group, and the same or different metal is bonded to the anion group to form a salt. Manufacturing method. 39. The method for producing a deodorant according to claim 38, wherein the anion group is a carboxyl group, a sulfone group or a phosphoric acid group. 40. The metal is an alkali metal, calcium,
The method for producing an odor eliminating substance according to any one of claims 28 to 39, which is at least one selected from barium, magnesium, copper, iron, nickel, cobalt, manganese, titanium, vanadium, molybdenum, tungsten, silver or zinc. . 41. A step (A) of obtaining a granular or lumpy adsorbent of a predetermined size by using an inorganic substance or an organic substance or a mixture thereof, the adsorbent obtained in the step (A) Step (B) of applying a solution or dispersion of a metal complex that decomposes or adsorbs a malodorous substance, and the adsorbent containing the metal complex obtained in (B) above,
The manufacturing method of the deodorant body which consists of a process (C) which dries below the decomposition temperature of the said metal complex. 42. The inorganic material is charcoal such as activated carbon, acid clay, activated clay, diatomaceous earth, silica, zeolite, porous beads such as silicon oxide porous beads, porous ceramics or porous glass. 41. The method for producing a deodorant body according to item 41. 43. The method for producing a deodorant according to claim 41, wherein the organic substance is pulp chips, wood chips or sawdust. 44. The method for producing a deodorant according to claim 41, wherein the granular adsorbent obtained in step (A) has a size of 0.5 mm to 5 cm. 45. The method for producing a deodorant body according to any one of claims 41 to 44, wherein the massive adsorbent obtained in step (A) is formed into a required shape. 46. The method for producing a deodorant according to claim 45, wherein the massive adsorbent obtained in step (A) is a figurine, exhibit or appreciation item. 47. The granular or lumpy adsorbent obtained in step (A) is formed into a predetermined shape by using an inorganic binder or an organic binder, and the adsorbent is formed into a predetermined shape. Method for producing deodorant body. 48. The method for producing a deodorant according to claim 41, wherein the metal complex comprises a metalloporphyrin derivative. 49. The method for producing a deodorant according to claim 48, wherein the metalloporphyrin derivative is a metal phthalocyanine derivative. 50. The method for producing a deodorant according to claim 48 or 49, wherein the metalloporphyrin derivative has at least one selected from a carboxyl group, a hydroxyl group, an amide group, a sulfone group, a halogen group and an amino group. 51. The deodorant according to claim 48, wherein the metalloporphyrin derivative has an anion group, and the same or different metal is bonded to the anion group to form a salt. Manufacturing method. 52. The method for producing a deodorant according to claim 51, wherein the anion group is a carboxyl group, a sulfone group or a phosphoric acid group. 53. The metal is an alkali metal, calcium,
The method for producing a deodorant according to any one of claims 41 to 52, which is at least one selected from barium, magnesium, copper, iron, nickel, cobalt, manganese, titanium, vanadium, molybdenum, tungsten, silver or zinc. .